WO2004022531A1 - Procede de sulfatation doux - Google Patents

Procede de sulfatation doux Download PDF

Info

Publication number
WO2004022531A1
WO2004022531A1 PCT/EP2003/008747 EP0308747W WO2004022531A1 WO 2004022531 A1 WO2004022531 A1 WO 2004022531A1 EP 0308747 W EP0308747 W EP 0308747W WO 2004022531 A1 WO2004022531 A1 WO 2004022531A1
Authority
WO
WIPO (PCT)
Prior art keywords
alcohol
acid
alkyl
alcohols
sulfated
Prior art date
Application number
PCT/EP2003/008747
Other languages
German (de)
English (en)
Inventor
Hans-Christian Raths
Gerhard Hermanns
Rainer Rüben
Original Assignee
Cognis Deutschland Gmbh & Co. Kg
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cognis Deutschland Gmbh & Co. Kg filed Critical Cognis Deutschland Gmbh & Co. Kg
Publication of WO2004022531A1 publication Critical patent/WO2004022531A1/fr

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • A61K8/463—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfuric acid derivatives, e.g. sodium lauryl sulfate
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H11/00—Compounds containing saccharide radicals esterified by inorganic acids; Metal salts thereof
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/16—Sulfonic acids or sulfuric acid esters; Salts thereof derived from divalent or polyvalent alcohols

Definitions

  • the present invention relates to a process for producing sulfated alcohols, in which an alcohol to be sulfated or a mixture of two or more alcohols to be sulfated is reacted with an acidic product of sulfation of an alcohol or a mixture of two or more alcohols, at least one sulfate group is transferred to at least one alcohol to be sulfated.
  • the present invention further relates to a composition which can be obtained by the process according to the invention and sulfated cyclic alcohols.
  • the present invention further relates to a composition which contains at least one product produced by a process according to the invention.
  • the sulfation of alcohols is a tried and tested method that has been known for a long time and is mainly used industrially to produce anionic surfactants.
  • the neutralized sulfate salts of alcohols or ethoxylated alcohols are excellent surface-active compounds and are often used in detergents and cleaning agents, mild detergents and cleaning agents, shampoos and other mild cleaning agents as well as in cosmetics.
  • Alcohol sulfates are particularly preferred for detergents and cleaning agents because of their foam properties and their washing power.
  • the alkyl ether sulfates in addition to the alkyl sulfates, the alkyl ether sulfates in particular have become indispensable for many of the above-mentioned areas.
  • a disadvantage of these anionic surfactants is the fact that alkyl sulfates, especially dodecyl sulfate, do not have the desired mild properties on the skin and hair. For this reason, these products are generally combined with other "mild" co-surfactants.
  • mild anionic surfactants or non-ionic surfactants can also be used here.
  • the known nonionic surfactants have the disadvantage that they often have only limited water solubility and a comparatively low foaming power. Despite their otherwise excellent properties, the range of use of such nonionic surfactants is therefore limited.
  • WO 91/13057 describes a process for the co-sulfation of ethoxylated alkyl alcohols together with unsaturated fatty alcohols.
  • unsaturated alcohols are treated together with ethoxylated alkyl alcohols with a sulfating agent, a mixed product containing an unsaturated fatty alcohol sulfate being obtained.
  • a sulfating agent a mixed product containing an unsaturated fatty alcohol sulfate being obtained.
  • particularly sensitive alcohols for example alkyl oligo- or polyglycosides, cannot be sulfated satisfactorily with the aid of the described method.
  • the sulfonation of alkyl glycosides in dimethylformamide can also be carried out with a complex of sulfur trioxide and an amine.
  • the high-boiling organic solvent component must be separated off after sulfonation and neutralization. This step is with a high apparatus and time involved; in many cases traces of the solvent remain in the product, which is undesirable for some applications.
  • DE 38 34 911 AI relates to a process for the sulfation of alkyl oligoglycosides with alkyl radicals having 8 to 22 carbon atoms and an average degree of oligomerization of 1 to 5 with the aid of conventional sulfating agents.
  • the sulfation is carried out using customary sulfating agents in inert organic solvents with a boiling point (under normal conditions from 30 to 100 ° C.)
  • the problem with the described process is not only the fact that organic solvents are used, which are expensive to produce Because of their high volatility, these solvents cannot normally be used on typical sulfonation plants which work with SO 3 / air mixtures as sulfonation agents.
  • alcohols such as alkyl polyglycosides or sterols are popular components of detergent and cleaning compositions as well as cosmetics.
  • the use of such alcohols has hitherto been restricted almost exclusively to their use as nonionic surfactants, since known processes for endowing such alcohols with anionic groups, in particular sulfation, have failed because of the sensitivity of these compounds.
  • nonionic surfactants since known processes for endowing such alcohols with anionic groups, in particular sulfation, have failed because of the sensitivity of these compounds.
  • sulfation of alkyl polyglycosides by conventional sulfation processes, for example using chlorosulfonic acid, sulfuric acid or sulfur trioxide, only a carbonized product is obtained. Sulfated alkyl polyglycoside is hardly detectable in such compositions.
  • anionic surfactants which have the mild surfactant properties of the above-mentioned nonionic surfactants, but which have better water solubility, better sensory properties and improved foaming power.
  • the object of the present invention was therefore to provide a process for the preparation of anionic surfactants which does not have the disadvantages of the processes known from the prior art. Furthermore, the present invention was based on the object of providing anionic surfactants which have mild surfactant properties and excellent foaming power. Furthermore, it was an object of the present invention to provide compositions which contain particularly mild anionic surfactants with good foaming power and which can be used, for example, as detergent and cleaning compositions or in cosmetic products. The present invention was also based on the object of providing a process with which a sulfate group or its precursor can also be introduced into sensitive alcohols via reaction with sulfur trioxide on plants which are available on an industrial scale, in particular sulfation plants.
  • the present invention therefore relates to a process for the preparation of sulfated alcohols, in which an alcohol to be sulfated or a mixture of two or more alcohols to be sulfated is reacted with an acidic sulfation product of an alcohol or a mixture of two or more acidic sulfation products of alcohols, where at least one acidic sulfation product of an alcohol transfers at least some of its sulfate groups to at least one alcohol to be sulfated under the conversion conditions.
  • an “alcohol to be sulfated” is understood to mean a compound having at least one OH group, at least one OH group of this compound being sulfated in the course of the reaction according to the invention. It is provided in the context of the present invention that an alcohol to be sulfated has only one OH group. However, it is also possible for an alcohol to be sulfated the alcohol has two or more OH groups, for example 3, 4, 5 or 6 OH groups.
  • alcohols which can be equipped with a sulfate group in the context of a reaction according to the invention can be used as alcohols to be sulfated in the context of the present invention.
  • Particularly suitable alcohols are those which are completely or partially decomposed under the conditions of sulfation reactions known from the prior art or, for example, can only be prepared with low yields and poor or changing product quality due to side reactions.
  • the alcohols to be sulfated are therefore alcohols which contain, for example, unsaturated cyclic or saturated or unsaturated heterocyclic structural elements, for example alkyl polyglycosides, alcohols which contain secondary OH groups, esters which contain an OH group, for example the esters of ⁇ -hydroxy acids, fatty acid (poly) alkylene glycol esters, glycerol esters, in particular partial glycerides, or sterols.
  • the alcohols to be sulfated are compounds which have at least one unsaturated cyclic or one saturated or unsaturated heterocyclic structural element.
  • Suitable alcohols to be sulfated are, for example, the compounds from the group of the alkyl polyglycosides.
  • alkyl or alkenyl oligoglycosides or alkyl or alkenyl polyglycosides which follow the formula (I) are suitable,
  • the alkyl and alkenyl oligo- or polyglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose.
  • the preferred alkyl and alkenyl oligo- or polyglycosides are thus alkyl and alkenyl oligo- or polyglycosides.
  • the alkyl or alkenyl radical R can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capronic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.
  • the alkyl or alkenyl radical R can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms.
  • Alkyl oligoglycosides are preferably based on hydrogenated C 1/14 - coconut alcohol with a DP of 1 to 3
  • alkyl oligo- and alkyl polyglycosides can each be sulfated individually in the process according to the invention. However, within the scope of the process according to the invention it is also provided that mixtures of two or more different alkyl oligo- and alkyl polyglycosides are present together in the reaction mixture subjected to the sulfation.
  • alkyl oligo- and alkyl polyglycosides are generally referred to as “alkyl polyglycosides”, or abbreviated with the letters “APG”, unless something else is expressly described.
  • Alcohols from the group of sterols for example phytosterols such as generol, ergosterol, stigmasterol, sitosterol, fucosterol, brassicasterol, fungisterol, campesterol or zymosterol, are also suitable for use as alcohol to be sulfated.
  • phytosterols such as generol, ergosterol, stigmasterol, sitosterol, fucosterol, brassicasterol, fungisterol, campesterol or zymosterol
  • alcohols from the group of the polysaccharides such as the homoglycans starch, glycogen, cellulose, dextran, inulin, chitin, chitosan or alginic acids, or also from heteroglycans such as pectins, mannans, galactans, xylans, hyaluronic acids and the like ,
  • a reaction mixture used in the context of a method according to the invention can contain one or more compounds of a certain type of compound, for example a certain alkyl polyglycoside or a mixture of two or more certain alkyl polyglycosides.
  • a mixture of different types of compounds for example a mixture of alkylpolyglycosides and sterols or a mixture of alkylpolyglycosides, sterols and chitin, are sulfated together in one reaction mixture in the context of a method according to the invention.
  • an alcohol to be sulfated or a mixture of two or more alcohols to be sulfated is mixed with at least one acid sulfation product of an alcohol or a mixture of two or more acid sulfates.
  • acid sulfation products of alcohols either alone or in a mixture of two or more thereof, are also referred to as “carriers” in the context of the present text.
  • alcohols are suitable as precursors for the carriers in the context of the present invention which, under the reaction conditions, bring about sulfation of the alcohol to be sulfated or the mixture of two or more alcohols to be sulfated.
  • alcohols are used which have a lower molecular weight than the alcohol to be sulfated, or, in a mixture of two or more alcohols to be sulfated, than the alcohol with the lowest molecular weight to be sulfated.
  • methanol or ethanol and the isomers of the higher alkyl alcohols having 3 to about 22 carbon atoms such as propanol, butanol, pentanol, hexanol, heptanol, octanol and the like are suitable for producing a carrier.
  • the mono- or polyunsaturated, linear or branched alkenyl alcohols with 3 to about 22 carbon atoms are suitable.
  • dihydric alcohols such as ethylene glycol, propylene glycol, the isomeric butanediols, pentanediols or hexanediols, the mixtures of two or more thereof, the reaction products of the compounds mentioned with 1 to 10 mol of alkylene oxide, in particular ethylene oxide, or mixtures of two or more of the mentioned connections.
  • Highly functional alcohols such as glycerol, trimethylolpropane, pentaerythritol and oligomeric ethers of the substances mentioned with themselves or in a mixture of two or more of the compounds mentioned, for example polyglycerol with a degree of polymerization of about 2 to about 4, are also suitable Reaction products of polyfunctional alcohols such as glycerol, trimethylolethane or trimethylolpropane, pentaerythritol or the reaction products of mixtures of two or more thereof with 1 to 10 moles of ethylene oxide are suitable as precursors for the preparation of a carrier in the context of the present invention. According to the invention, it is not necessary for the carriers to be sulfated on each OH group. It is also possible to use an acidic sulfation product of an alcohol or a mixture of two or more acidic sulfation products of alcohols which have one or more OH groups as carriers.
  • acidic sulfation products of alcohols those with only one acidic sulfate group.
  • acid sulfation products of alcohols which have two or more acid sulfate groups. It is basically irrelevant whether a sulfated alcohol may have one or more OH groups in addition to an acidic sulfate group.
  • the acid sulfation products of methanol, ethanol, propanol, isopropanol, isobutanol, t-butanol, pentanol, neopentyl alcohols, hexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, ethylene propylene glycol, glycerol, for example, are used as carriers.
  • Trimethylolpropane, triethylolpropane or pentaerythritol or mixtures of two or more thereof are used.
  • acid sulfation products of alcohols are used as carriers which essentially no longer have any free OH groups.
  • the ratio of carrier to the alcohols to be sulfated can essentially be chosen arbitrarily in the process according to the invention. Basically, it can be assumed that with a molar excess of OH groups to be sulfated relative to acidic sulfate groups in the carrier, the alcohol to be sulfated cannot be completely sulfated. However, if the carrier, based on the acidic sulfate groups in the carrier and the alcohol to be sulfated, is used in an excessively high molar excess, the number of side reactions may increase undesirably, if appropriate.
  • the molar ratio of alcohol groups in the alcohol to be sulfated to acidic sulfate groups in the carrier in the reaction mixture is about 1: 0.5 to about 1: 2, for example about 1: 0.7 to about 1: 1.8 or about 1: 0.8 to about 1: 1.3 or up to about 1: 1.2 ,
  • the reaction of the carrier with the alcohol to be sulfated which takes place in the context of the process according to the invention, is carried out, for example, without solvents, but preferably in the presence of a solvent.
  • solvents which dissolve or at least disperse the reaction products in such a way that the desired reaction takes place are suitable as solvents.
  • Solvents which do not react with SO 3 are preferably used.
  • hydrocarbons in particular saturated hydrocarbons, ketones, ethers, halogenated hydrocarbons, each in cyclic or acyclic form, are suitable.
  • Acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, or halogenated hydrocarbons such as dichloroethane, dichloromethane, for example, are particularly suitable.
  • solvents in the process according to the invention which react with SO 3 to form sulfate. This is particularly advantageous when different organic sulfates are to be produced in a single sulfation step. If, for example, mixtures of different organic sulfates are to be produced, a solid alcohol component to be sulfated can be dissolved in a liquid alcohol component to be sulfated, with both compounds (solvent and dissolved alcohol) being sulfated during the subsequent sulfation.
  • Suitable sulfatable solvents are, for example, linear or branched, saturated or unsaturated alkyl alcohols having 8 to about 24 carbon atoms and fatty alcohol polyethylene glycol ether.
  • the amount of solvent is preferably selected so that the reaction mixture can be readily stirred at the temperatures prevailing during the reaction.
  • the reaction mixture preferably has an appropriate solvent in such an amount that the viscosity at the reaction temperature is about 50 to about 1000 mPas, for example about 100 to about 500 mPas (measured according to Brookfield).
  • reaction of the alcohol to be sulfated or the mixture of two or more alcohols to be sulfated with the alcohol sulfate or the mixture of two or more aluminum alcohol sulfates are preferably carried out at a temperature of about 15 to about 70 ° C, for example at about 20 to about 60 ° C, in particular at about 25 to about 40 ° C. Reaction temperatures of approximately 20 to approximately 40 ° C., for example approximately 22 to approximately 35 or approximately 25 to approximately 30 ° C., are particularly suitable.
  • reaction can take place in any reactor.
  • implementation in a batch process or implementation in the context of continuous processes is possible.
  • stirred vessels, flow reactors, reaction tubes, mixers, circulation reactors and the like are suitable for this.
  • Suitable carriers can be obtained, for example, by customary sulfation processes according to the prior art known to the person skilled in the art.
  • the alcohols mentioned above are reacted with SO 3 at a temperature of about 15 to about 60 ° C., for example at a temperature of about 25 to about 40 ° C.
  • the molar ratio of OH groups to SO 3 is preferably about 1: 0.7 to about 1: 2, in particular about 1: 0.8 to about 1: 1.2.
  • the alcohol sulfates can in principle be produced in all reactors known to those skilled in the art for the production of sulfated products. Batch, cascade or falling film reactors are suitable, for example.
  • the carriers produced in this way can be used immediately in the process according to the invention for the sulfation according to the invention.
  • the alcohol sulfates can be stored for a period of up to about a year, for example up to about six months or up to about four months after their production.
  • the entry of water should preferably be avoided.
  • carriers are used which have been stored at room temperature for a period of approximately one week to approximately two months, in particular for a period of approximately three to approximately six weeks.
  • the acidic sulfation product of ethylene glycol is particularly preferred as a carrier.
  • the components involved in the reaction mixture can be added to the reaction mixture essentially in any order.
  • the alcohol to be sulfated or the mixture of two or more alcohols to be sulfated is dissolved or dispersed in the solvent and the carrier is then added to the reaction mixture.
  • the carrier can essentially be added over any period of time.
  • the carrier is preferably fed to the reaction mixture within a period of about five minutes to about ten hours, for example within a period of about 30 minutes to about two hours.
  • the circulation time of the reaction mixture must be dimensioned accordingly with regard to the addition of the carrier.
  • the product mixtures resulting from the reaction according to the invention can in principle be stored in the present form or processed further.
  • the reaction step described above is preferably followed by a neutralization step.
  • the reaction products are reacted with a neutralizing agent, so that the acid group formed in the course of the reaction is neutralized.
  • a neutralizing agent which react with the acid group formed in the course of the reaction to form a salt are suitable for this purpose.
  • the neutralizing agents can be used in solid or liquid, but preferably in liquid form.
  • inorganic or organic neutralizing agents are suitable as neutralizing agents.
  • Suitable inorganic neutralizing agents are, for example, the hydroxides of lithium, sodium, potassium, calcium or magnesium.
  • the oxides, carbonates or hydrogen carbonates of the compounds mentioned are also suitable.
  • Ammonia or organic amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethanolamine, diethanolamine or triethanolamine and the like are also suitable for neutralization.
  • the neutralization is preferably carried out by adding the reaction product to a solution of the neutralizing agent.
  • the reaction product is introduced continuously or in portions into a solution of the neutralizing agent.
  • the neutralization can be carried out batchwise or continuously.
  • an inorganic neutralizing agent preferably lithium hydroxide, sodium hydroxide or potassium hydroxide
  • Aqueous solutions of the neutralizing agents mentioned above are particularly suitable.
  • the neutralization step is carried out in such a way that at least some, but preferably all, of the acid groups in the reaction product are neutralized. It has been found to be suitable if the neutralization is carried out up to a pH of the resulting solution of about 5 to about 11, in particular from about 6 to about 8.5, for example about 7 to about 8
  • the amount of neutralizing agent is selected in relation to the amount of reaction product such that surfactant solutions with solids contents of about 10 to about 70, for example about 25 to about 45% by weight are obtained after the neutralization has been completed.
  • the removal of the solvent used leads, depending on the amount of solvent used in the neutralization and on the type of solvent used for the neutralization and its amount, to a liquid to dry end product.
  • An aqueous solution of the neutralizing agent is preferably used in the neutralization, the water not being withdrawn from the reaction mixture or only in an insignificant amount being removed from the reaction mixture in the course of removing the solvent.
  • the reaction product is present in liquid to pasty form after removal of the solvent from the reaction mixture.
  • the components involved in the reaction are used in such amounts that the reaction product, after removal of the solvent, has a solids content of about 10 to about 70% by weight, in particular a solids content of about 20 to 60 or about 25 to about 45 weight percent.
  • the reaction product can be subjected to further treatment steps.
  • Another suitable treatment step is, for example, the bleaching of the reaction mixture obtained.
  • the coloring compounds contained in the reaction mixture can be bleached in a manner known to those skilled in the art by adding bleaching agents, for example by adding hydrogen peroxide or sodium hypochlorite.
  • the bleaching agents based on the solids content of the reaction product, are used in an amount of about 0.2 to about 2% by weight.
  • reaction mixture can be stabilized with suitable buffering agents, for example with sodium phosphate or citric acid, in order to stabilize the pH.
  • suitable buffering agents for example with sodium phosphate or citric acid
  • reaction mixture can be preserved by adding suitable preservatives, for example by adding formaldehyde, p-hydroxybenzoate, sorbic acid or other known preservatives.
  • reaction mixture is in the form of a liquid or a paste, it can be dried in the process according to the invention by processes known from the prior art and known to the person skilled in the art. Suitable drying processes are, for example, spray drying, fluidized bed drying or granulation. Particularly suitable processes for drying anionic surfactants can be found, for example, in DE 198 53 893, DE 42 09 339 or DE 4446 444.
  • compositions produced by the process according to the invention contain a comparatively high proportion of sulfated, mild surfactants, as has been the case up to now processes known from the prior art were not obtainable or were not obtainable in sufficient purity.
  • the present invention therefore also relates to compositions such as are obtainable by a process according to the invention.
  • reaction products In the context of the present invention, it is provided, for example, to bleach the reaction products.
  • all processes are suitable for this which cause the reaction products to be decolorized.
  • the reaction products are bleached by treatment with activated carbon or by treatment with peroxo compounds, for example hydrogen peroxide or performic acid or a mixture of two or more of the processes mentioned.
  • compositions produced by a process according to the invention are particularly suitable for use in detergents and cleaning agents and in cosmetics.
  • the compositions produced by a process according to the invention are mixed with further ingredients, as described below.
  • Non-ionic surfactants or additional anionic surfactants are suitable as additives for the use of the compounds or compositions produced by a process according to the invention as detergents and cleaning agents and as cosmetics.
  • Suitable nonionic surfactants for the purposes of the present invention are, for example, alkyl and alkenyl oligoglycosides, fatty acid N-alkylpolyhydroxyalkylamides, alcohol alkoxylates, alkoxylated carboxylic esters, preferably alkyl and alkenyl oligoglycosides.
  • Alkyl and / or alkenyl oligoglycosides are known nonionic surfactants which have the general formula
  • RO (G) p (I) in which R stands for an alkyl and / or alkenyl residue with 4 to 22 carbon atoms, G stands for a sugar residue with 5 or 6 carbon atoms and p stands for numbers from 1 to 10.
  • the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose.
  • the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
  • Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 4.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.6.
  • the alkyl or alkenyl radical R can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms.
  • Typical examples are butanol, capronic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.
  • the technical oxo alcohols from Shell which are marketed under the names Dobanol® or Neodol®, are particularly preferred.
  • the alkyl or alkenyl radical R can also be derived from primary alcohols having 12 to 22, preferably 12 to 18, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and the technical mixtures obtained as described above, which are obtained as described above, and their technical mixtures that can.
  • nonionic surfactants which are used in the context of the present invention either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain , in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • nonionic surfactants are polyhydroxy fatty acid amides of the formula (II),
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (III)
  • R "for a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms R 2 for a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R 3 for a linear, branched or cyclic alkyl radical or a Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C 1 -alkyl or phenyl radicals being preferred and [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this residue.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • a reducing sugar with an alkylamine or an alkanolamine
  • acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • US Pat. Nos. 1,985,424, 2,016,962 and 2,703,798 and international patent application WO 92/06984.
  • Alcohol ethoxylates can also be used as nonionic surfactants. For production reasons, these are referred to as fatty alcohol or oxo alcohol ethoxylates and preferably follow the formula (IV), R '"- O (CH 2 CH 2 O) n H (IV),
  • R '" stands for a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms and n for numbers from 1 to 50.
  • Typical examples are the adducts of 1 to 50 on average, preferably 5 to 40 and in particular 10 to 25 mol of caprone alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, brassyl alcohol, aryl alcohol alcohol, aryl alcohol alcohol, aryl alcohol alcohol Technical mixtures which are obtained, for example, in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as a monomer fraction in the dimerization of unsaturated
  • Alkoxylated carboxylic acid esters can also be used as nonionic surfactants. Such connections are known from the prior art. For example, such alkoxylated carboxylic acid esters are accessible by esterification of alkoxylated carboxylic acids with alcohols.
  • the compounds are preferably prepared by reacting carboxylic acid esters with alkylene oxides using catalysts, in particular using calcined hydrotalcite according to German Offenlegungsschrift DE 3914131 A, which provide compounds with a restricted homolog distribution. Both carboxylic acid esters of monohydric alcohols and polyhydric alcohols can be alkoxylated by this process. According to the present invention, preference is given to alkoxylated carboxylic acid esters of monohydric alcohols which follow the general formula (V)
  • Alkylene oxide and R 5 is an aliphatic alkyl radical derived from a monohydric aliphatic alcohol.
  • Alkoxylated carboxylic acid esters are particularly suitable Formula (V) in which R 4 CO for an aliphatic acyl radical having 6 to 30, preferably 6 to 22 and in particular 10 to 18 carbon atoms, OAlk for a CH 2 CH 2 O-, CHCH 2 CH 2 O- and / or CH n -CHCH 2 O radical, n on average represents numbers from 1 to 30, preferably 5 to 20 and in particular 10 to 15 and R 5 represents an aliphatic alkyl radical having 1 to 4 and preferably 1 and / or 2 carbon atoms.
  • Formula (V) in which R 4 CO for an aliphatic acyl radical having 6 to 30, preferably 6 to 22 and in particular 10 to 18 carbon atoms, OAlk for a CH 2 CH 2 O-, CHCH 2 CH 2 O- and / or CH n -CHCH 2 O radical, n on
  • Preferred acyl radicals are derived from carboxylic acids having 6 to 22 carbon atoms of natural or synthetic origin, in particular from linear, saturated and / or unsaturated fatty acids, including technical mixtures thereof, as are obtainable by fat cleavage from animal and / or vegetable fats and oils, for example from coconut oil, palm kernel oil, palm oil, soybean oil, sunflower oil, turnip oil, cotton seed oil, fish oil, beef tallow and lard.
  • carboxylic acids examples include caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arenachic acid, gadachene acid, gadoleic acid, gadoleic acid, gadoleic acid, gadoleic acid, gadic acid, gadic acid, or erucic acid.
  • Preferred alkyl radicals are derived from primary, aliphatic monofunctional alcohols having 1 to 4 carbon atoms, which can be saturated and / or unsaturated.
  • suitable monoalcohols are methanol, ethanol, propanol and butanol, in particular methanol.
  • OAlk stands for the alkylene oxides which are reacted with the carboxylic acid esters and include ethylene oxide, propylene oxide and / or butylene oxide, preferably ethylene oxide and / or propylene oxide, in particular ethylene oxide alone.
  • Alkoxylated carboxylic acid esters of the formula (V) are particularly suitable, in which OAlk represents a CH 2 CH 2 O radical, n on average represents numbers from 10 to 15 and R 5 represents a methyl radical. Examples of such compounds are methyl, lauric acid, methyl coconut fatty acid and methyl tallow fatty acid alkoxylated on average with 5, 7, 9 or 11 mol ethylene oxide.
  • the nonionic surfactants can be used in amounts of 20 to 95, preferably 50 to 80 and in particular 60 to 70, based on the final concentration. hydroxy mixed
  • the hydroxy mixed ethers which are also suitable as nonionic surfactants, are known nonionic surfactants with an asymmetrical emer structure and polyalkylene glycol components, which can be obtained, for example, by subjecting olefin epoxides to a ring opening reaction with fatty alcohol polyglycol ethers.
  • HME hydroxy mixed ethers
  • Corresponding products and their use in the field of cleaning hard surfaces are the subject of, for example, the European patent EP 0693049 B1 and the international patent application WO 94/22800 and the documents mentioned therein.
  • the hydroxy mixed ethers typically follow the general formula (VI)
  • R 6 represents hydrogen or a linear or branched alkyl radical having 2 to 18, preferably 10 to 16 carbon atoms
  • R 7 represents hydrogen or a linear or branched alkyl radical having 2 to 18 carbon atoms
  • R 8 represents hydrogen or methyl
  • R 9 represents one linear or branched, alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and n being numbers from 1 to 50, preferably 2 to 25 and in particular 5 to 15, with the proviso that the sum of the carbon atoms in the radicals R 6 and R 7 is at least 4 and preferably 12 to 18.
  • the HME ring opening products can be either internal olefin epoxides (R 7 not equal to hydrogen) or terminal olefin epoxides (R 7 equal to hydrogen), the latter being preferred in view of the easier preparation and the more advantageous application properties.
  • the polar part of the molecule can be a polyethylene glycol or a polypropylene glycol chain; Mixed chains of PE and PP units are also suitable, be it in statistical or block distribution.
  • Typical examples are ring opening products of 1,2-hexenepoxide, 2,3-hexenepoxide, 1,2-octene epoxide, 2,3-octene epoxide, 3,4-octene epoxide, 1,2-decene epoxide, 2,3-decene epoxide and 3,4-decene epoxide , 4,5-decenepoxide, 1,2-dodecenepoxide, 2,3-dodecenepoxide, 3,4-dodecenepoxide, 4,5-dodecenepoxide, 5,6-dodecenepoxide, 1,2-tetradecenepoxide, 2,3-tetradecenepoxide, 3 , 4-Tetradecenepoxid, 4,5-Tetradecenepoxid, 5,6-Tetradecenepoxid, 6,7- Tetradecenepoxid
  • capronic alcohol caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolenyl alcohol, linolenyl alcohol, linolenyl alcohol Erucyl alcohol and brassidyl alcohol and their technical mixtures.
  • the HJME are usually contained in the moldings in amounts of 0.1 to 20, preferably 0.5 to 8 and in particular 3 to 5% by weight.
  • anionic surfactants suitable as additives are soaps, alkylbenzene sulfonates, secondary alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, ⁇ -methyl ester sulfonates, sulfo fatty acids, alkyl and / or alkenyl sulfates, alkyl ether sulfates, glyceryl ether ether sulfates, fatty alcohol ether sulfates, ether ether sulfates, hydroxyl ether sulfates, phosphates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide
  • Preferred additives are selected from the group consisting of alkyl and / or alkenyl sulfates, alkyl ether sulfates, alkyl benzene sulfonates, soaps, monoglyceride (ether) sulfates and alkane sulfonates, especially fatty alcohol sulfates, fatty alcohol ether sulfates, secondary alkane sulfonates and linear alkyl benzene sulfonates.
  • Alkyl and / or alkenyl sulfates which are also often referred to as fatty alcohol sulfates, are to be understood as meaning the sulfation products of primary alcohols which follow the formula (VII)
  • R 10 represents a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • alkyl sulfates which can be used in the context of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, aryl selyl alcohol, elaidyl alcohol alcohol, gadoleyl alcohol, behenyl alcohol and erucyl alcohol and their technical mixtures, which are obtained by high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis.
  • the sulfation products can preferably be used in the form of their alkali metal salts and in particular their sodium salts.
  • Alkyl sulfates based on C 16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts are particularly preferred.
  • ether sulfates are known anionic surfactants which are produced on an industrial scale by SO 3 - or chlorosulfonic acid (CSA) sulfation of fatty alcohol or oxo alcohol polyglycol ethers and subsequent neutralization.
  • CSA chlorosulfonic acid
  • ether sulfates are suitable which follow the formula (VIII)
  • R n O- (CH 2 CH 2 O) a SO 3 X (VIII) in which R 11 represents a linear or branched alkyl and / or alkenyl radical with 6 to 22 carbon atoms, a for numbers from 1 to 10 and X for an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • Typical examples are the sulfates of addition products with an average of 1 to 10 and in particular 2 to 5 mol ethylene oxide onto capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoley alcohol, stearyl alcohol, oleyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, Petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brasidyl alcohol as well as their technical mixtures in the form of their sodium and / or magnesium salts.
  • the ether sulfates can have both a conventional and a narrow homolog distribution. It is particularly preferred to use ether sulfates based on adducts of an average of 2 to 3 mol ethylene oxide with technical C 12/1 or C 12/18 coconut fatty alcohol fractions in the form of their sodium and / or magnesium salts.
  • Alkylbenzenesulfonates preferably follow the formula (IX),
  • R 12 represents a branched, but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph a phenyl radical and X an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • Dodecylbenzenesulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in the form of the sodium salts are preferably used. Soap
  • soaps are to be understood as meaning fatty acid salts of the formula (JX)
  • R 13 CO represents a linear or branched, saturated or unsaturated acyl radical having 6 to 22 and preferably 12 to 18 carbon atoms and again X represents alkali and / or alkaline earth metal, ammonium, alkylammonium or alkanolammonium.
  • Typical examples are the sodium, potassium, magnesium, ammonium and triethanolammonium salts of caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, Elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures.
  • coconut or palm kernel fatty acid is preferably used in the form of its sodium or potassium salts.
  • Monoglyceride sulfates and monoglyceride ether sulfates are known anionic surfactants which can be obtained by the relevant methods of preparative organic chemistry.
  • the usual starting point for their production is triglycerides, which, if appropriate, are transesterified to the monoglycerides after ethoxylation and subsequently sulfated and neutralized.
  • suitable sulfating agents preferably gaseous sulfur trioxide or chlorosulfonic acid [cf. EP 0561825 B1, EP 0561999 B1 (Henkel)].
  • the neutralized substances can be subjected to ultrafiltration in order to reduce the electrolyte content to a desired level [DE 4204700 AI (Henkel)].
  • Overviews of the chemistry of the monoglyceride sulfates are, for example, by AK Biswas et al. in J.Am.Oil.Chem.Soc. 37, 171 (1960) and FU Ahmed J.Am.Oil.Chem.Soc. 67, 8 (1990).
  • the monoglyceride (ether) sulfates to be used in accordance with the invention follow the formula (JXI),
  • R 14 CO for a linear or branched acyl radical having 6 to 22 carbon atoms, c, d and e in total for 0 or for numbers from 1 to 30, preferably 2 to 10, and X for alkali and / or alkaline earth metal, ammonium , Alkyl ammonium or alkanol ammonium.
  • Typical examples of monoglyceride (ether) sulfates which are suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride as well as their ethylene oxide adduct formulas with their sulphonate adduct formulas with their sulfur sulfonate adducts sodium sulfates with their sulfuric oxide adducts or their sulfuric acid adducts with their sulfuric oxide adducts and their sulfuric acid adduct with their sulfuric oxide adducts.
  • Monoglyceride sulfates of the formula (XI) are preferably used in which R 14 CO stands for a linear acyl radical having 8 to 18 carbon atoms.
  • Alkane sulfonates can be divided into primary and secondary alkane sulfonates. This means compounds of the formula (XII)
  • R 15 is hydrogen and R 16 is an alkyl radical having 1 to about 50 carbons.
  • the secondary alkanesulfonates are preferred.
  • the proportion of anionic surfactants in the preparations according to the invention is about 1 to about 60% by weight, in particular about 5 to about 50 or about 10 to about 40% by weight.
  • the preparations according to the invention can be used as detergents or cleaning agents. They are suitable as powder detergents, as granular detergents or as chunky detergents, for example as detergent tablets.
  • preparations according to the invention can also contain further typical ingredients and auxiliaries and additives, as are listed below.
  • the detergents and cleaning agents can also contain other typical ingredients, such as, for example, builders, bleaches, bleach activators, detergency boosters, enzymes, enzyme stabilizers, graying inhibitors, optical brighteners, soil repellants, foam inhibitors, inorganic salts and fragrances and colorants.
  • finely crystalline, synthetic and bound water-containing zeolite such as zeolite NaA in detergent quality is used as a solid builder.
  • zeolite NaX and mixtures of NaA and NaX are also suitable.
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its production.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C12-Cis fatty alcohols with 2 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22, in particular 20 to 22% by weight of bound water.
  • Suitable substitutes or partial substitutes for zeolites are crystalline, layered sodium silicates of the general formula NaMSi-xO2x + 1-yH2O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and is preferred Values for x are 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP 0164514 A.
  • Preferred crystalline phyllosilicates are those in which M in the general formula represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na2Si2O5-yH2O are preferred, with ⁇ -sodium disilicate being able to be obtained, for example, by the process described in the international patent application. avoidance WO 91/08171 is described.
  • the powder detergents according to the invention preferably contain 10 to 60% by weight of zeolite and / or crystalline layered silicates as solid builders, mixtures of zeolite and crystalline layered silicates in any ratio being particularly advantageous.
  • the agents contain 20 to 50% by weight of zeolite and / or crystalline layered silicates.
  • Particularly preferred agents contain up to 40% by weight of zeolite and in particular up to 35% by weight of zeolite, in each case based on the anhydrous active substance.
  • Other suitable ingredients of the agents are water-soluble amorphous silicates; they are preferably used in combination with zeolite and / or crystalline layered silicates.
  • the content of amorphous sodium silicates in the agents is preferably up to 15% by weight and preferably between 2 and 8% by weight.
  • Phosphates such as tripolyphosphates, pyrophosphates and orthophosphates can also be present in small amounts in the compositions.
  • the content of the phosphates in the compositions is preferably up to 15% by weight, but in particular 0 to 10% by weight.
  • the compositions can additionally contain layered silicates of natural and synthetic origin.
  • Layered silicates of this type are known, for example, from patent applications DE 2334899 B, EP 0026529 A and DE 3526405 A. Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here. Suitable layered silicates, which belong to the group of water-swellable smectites, are, for example, montmorrilonite, hectorite or saponite. In addition, small amounts of iron can be incorporated into the crystal lattice of the layered silicates of the above compounds.
  • the layered silicates can contain hydrogen, alkali, alkaline earth ions, in particular Na "and Ca2 '.
  • the amount of water of hydration is usually in the range from 8 to 20% by weight and is dependent on the swelling state or the type of processing Suitable layer silicates are known, for example, from US 3,966,629, US 4,062,647, EP 0026529 A and EP 0028432 A.
  • Layer silicates which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment are preferably used.
  • Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these , Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • NTA nitrilotriacetic acid
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. The use of polymeric polycarboxylates is not absolutely necessary.
  • agents are preferred which are biodegradable polymers, for example terpolymers, the monomers acrylic acid and maleic acid or salts thereof, and vinyl alcohol or vinyl alcohol derivatives, or the monomers acrylic acid and 2-alkylallylsulfonic acid or salts thereof as well as sugar derivatives.
  • terpolymers which are obtained according to the teaching of German patent applications DE 4221381 A and DE 4300772 A are particularly suitable.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP 0280223 A.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other bleaching agents are, for example, peroxy carbonate, citrate perhydrates and salts of peracids, such as perbenzoates, peroxyphthalates or diperoxydodecanedioic acid. They are usually used in amounts of 8 to 25% by weight.
  • the use of sodium perborate monohydrate in amounts of 10 to 20% by weight and in particular 10 to 15% by weight is preferred. Due to its ability to bind free water with the formation of the tetrahydrate, it contributes to increasing the stability of the agent.
  • bleach activators can be incorporated into the preparations.
  • these are N-acyl or O-acyl compounds which form organic peracids with hydrogen peroxide, preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate.
  • the bleach activators contain bleach activators in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.
  • Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylenediamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Their proportion can be about 0.2 to about 2% by weight. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. In addition to the mono- and polyfunctional alcohols and the phosphonates, the agents can contain further enzyme stabilizers.
  • 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • boron compounds for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid, metaboric acid and pyrobic acid, is particularly advantageous. Graying inhibitors have the task of keeping the dirt detached from the fibers suspended in the liquor and thus preventing graying.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose.
  • Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc.
  • Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition, are preferred.
  • the agents can contain derivatives of diaminostilbenesulfonic acid or its alkali metal salts.
  • Suitable are, for example, salts of 4,4'-bis (2-aniino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2 , -disulfonic acid or compounds of the same structure which instead of the morpholino- Group carry a diethanolamine group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenyl styrene type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfo-styryl-diphenyl, or 4 - (4-chlorostyryl) -4 '- (2-sulfostyryl) - diphenyls.Mixtures of the above-mentioned brighteners can also be used.Uniform white granules are obtained if, apart from the usual brighteners, the agents are used in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, also contain small amounts of a blue dye A particularly preferred dye is Tinolux® (commercial product from Ciba-Geigy).
  • Suitable soil repellants are substances which preferably contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, the molar ratio of ethylene terephthalate to polyethylene glycol terephthalate being in the range from 50:50 to 90:10.
  • the molecular weight of the linking polyethylene glycol units is in particular in the range from 750 to 5,000, ie the degree of ethoxylation of the polymers containing polyethylene glycol groups can be approximately 15 to 100.
  • the polymers have an average molecular weight of about 5,000 to 200,000 and can have a block, but preferably a random structure.
  • Preferred polymers are those with molar ratios of ethylene terephthalate / polyethylene glycol terephthalate from about 65:35 to about 90:10, preferably from about 70:30 to 80:20. Also preferred are those polymers which have linking polyethylene glycol units with a molecular weight of about 750 to about 5,000, preferably from about 1000 to about 3000 and a molecular weight of the polymer from about 10,000 to about 50,000. Examples of commercially available polymers are the products Milease® T (ICI) or Repelotex® SRP 3 (Rhone-Poulenc).
  • Wax-like compounds can be used as defoamers.
  • Compounds which have a melting point at atmospheric pressure above 25 ° C. (room temperature), preferably above 50 ° C. and in particular above 70 ° C., are understood to be “waxy”.
  • the waxy defoamer substances are practically insoluble in water, ie at 20 ° C. they have a solubility of less than 0.1% by weight in 100 g of water.
  • all wax-like defoamer substances known from the prior art can be contained.
  • Suitable wax-like compounds are, for example, bisamides, fatty alcohols, fatty acids, carboxylic acid esters of mono- and polyhydric alcohols, and paraffin waxes or mixtures thereof.
  • the silicone compounds known for this purpose can of course also be used.
  • Suitable paraffin waxes generally represent a complex mixture of substances without a sharp melting point. For characterization, one usually determines its melting range by differential thermal analysis (DTA), as described in "The Analyst” 87 (1962), 420, and / or its solidification point , This is the temperature at which the paraffin changes from the liquid to the solid state by slow cooling. Paraffins which are completely liquid at room temperature, that is to say those having a solidification point below 25 ° C., cannot be used according to the invention.
  • the soft waxes which have a melting point in the range from 35 to 50 ° C., preferably include the group of petrolates and their hydrogenation products.
  • the solid hydrocarbons separated from highly viscous, paraffin-containing lubricating oil distillates during dewaxing are also suitable Melting points between 63 and 79 ° C.
  • These petrolates are mixtures of microcrystalline waxes and high-melting n-paraffms.
  • the paraffin wax mixtures known from EP 0309931 A1 for example from 26% by weight to 49% by weight of microcrystalline paraffin wax with a solidification point from 62 ° C. to 90 ° C., 20% by weight to 49% by weight hard paraffin, can be used with a solidification point from 42 ° C to 56 ° C and 2% by weight 60% to 25% by weight soft paraffin with a solidification point from 35 ° C to 40 ° C.
  • Paraffins or paraffin mixtures which solidify in the range from 30 ° C. to 90 ° C. are preferably used. It should be noted that even paraffin wax mixtures that appear solid at room temperature can contain different proportions of liquid paraffin. In the paraffin waxes which can be used according to the invention, this liquid fraction is as low as possible and is preferably absent entirely.
  • Particularly preferred paraffin wax mixtures at 30 ° C have a liquid fraction of less than 10% by weight, in particular from 2% by weight to 5% by weight, at 40 ° C a liquid fraction of less than 30% by weight, preferably of 5 % By weight to 25% by weight and in particular from 5% by weight to 15% by weight, at 60 ° C.
  • the temperature at which a liquid content of 100% by weight of the paraffin wax is reached is still below 85 ° C., in particular at 75 ° C. to 82 ° C., in particularly preferred paraffin wax mixtures.
  • the paraffin waxes can be petrolatum, microcrystalline waxes or hydrogenated or partially hydrogenated paraffin waxes.
  • Suitable bisamides as defoamers are those derived from saturated fatty acids with 12 to 22, preferably 14 to 18, carbon atoms and from alkylenediamines with 2 to 7 carbon atoms.
  • Suitable fatty acids are lauric acid, myristic acid, stearic acid, arachic acid and behenic acid and mixtures thereof, as can be obtained from natural fats or hydrogenated oils, such as tallow or hydrogenated palm oil.
  • Suitable diamines are, for example, ethyl lendiamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine.
  • Preferred diamines are ethylenediamine and hexamethylenediamine.
  • Particularly preferred bisamides are bismyristoylethylenediamine, bispalmitoylethylenediamine, bisstearoylethylenediamine and their mixtures and the corresponding derivatives of hexamethylenediamine.
  • Suitable carboxylic acid esters as defoamers are derived from carboxylic acids with 12 to 28 carbon atoms.
  • these are esters of behenic acid, stearic acid, hydroxystearic acid, oleic acid, palmitic acid, myristic acid and / or lauric acid.
  • the alcohol part of the carboxylic acid ester contains a mono- or polyhydric alcohol with 1 to 28 carbon atoms in the hydrocarbon chain.
  • suitable alcohols are behenyl alcohol, arachidyl alcohol, coconut alcohol, 12-hydroxystearyl alcohol, oleyl alcohol and lauryl alcohol as well as ethylene glycol, glycerin, polyvinyl alcohol, sucrose, er thritol, pentaerythritol, sorbitan and / or sorbitol.
  • Preferred esters are those of ethylene glycol, glycerol and sorbitan, the acid part of the ester being selected in particular from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid.
  • Suitable esters of polyvalent alcohols include xylitol monopalmitate, Pentarythritmonostearat, glycerol, ethylene glycol and sorbitan, sorbitan, sorbitan Sorbitandilaurat, sorbitan, sorbitan dioleate, and also mixed tallowalkyl and diesters.
  • Glycerol esters which can be used are the mono-, di- or triesters of glycerol and the carboxylic acids mentioned, the mono- or diesters being preferred.
  • Glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate and glycerol distearate are examples of this.
  • suitable natural esters as defoamers are beeswax and carnauba wax, which is a mixture of carnauba acid alkyl esters, often in combination with small proportions of free carnauba acid, other long-chain acids, high-molecular alcohols and hydrocarbons.
  • Suitable carboxylic acids as a further defoamer compound are, in particular, behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid and lauric acid, and mixtures thereof, as are obtainable from natural fats or optionally hardened oils, such as tallow or hydrogenated palm oil. Saturated fatty acids with 12 to 22, in particular 18 to 22, carbon atoms are preferred. Suitable fatty alcohols as a further defoamer compound are the hydrogenated products of the fatty acids described.
  • Dialkyl ethers may also be present as defoamers.
  • the ethers can be constructed asymmetrically or symmetrically, i. H. contain two identical or different alkyl chains, preferably with 8 to 18 carbon atoms.
  • Typical examples are di-n-octyl ether, di-i-octyl ether and di-n-stearyl ether; dialkyl ethers which have a melting point above 25 ° C., in particular above 40 ° C., are particularly suitable.
  • Suitable defoamer compounds are fatty ketones, which can be obtained by the relevant methods of preparative organic chemistry. For their preparation, one starts from, for example, carboxylic acid magnesium salts which are pyrolyzed at temperatures above 300 ° C. with the elimination of carbon dioxide and water, for example according to German published patent application DE 25 53 900 OS.
  • Suitable fat ketones are those which are prepared by pyrolysis of the magnesium salts of lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, petroselinic acid, arachic acid, gadoleic acid, behenic acid or erucic acid.
  • Suitable defoamers are fatty acid polyethylene glycol esters, which are preferably obtained by base-homogeneously catalyzed addition of ethylene oxide to fatty acids.
  • the addition of ethylene oxide to the fatty acids takes place in the presence of alkanolamines as catalysts.
  • alkanolamines especially triethanolamine, leads to an extremely selective ethoxylation of the fatty acids, especially when it comes to producing low-ethoxylated compounds.
  • the paraffin waxes described are particularly preferably used alone as wax-like defoamers or in a mixture with one of the other wax-like defoamers, the proportion of paraffin waxes in the mixture preferably making up more than 50% by weight, based on the wax-like defoamer mixture.
  • the paraffin waxes can be applied to carriers if necessary. All known inorganic and / or organic carrier materials are suitable as carrier materials. Examples of typical inorganic carrier materials are alkali carbonates, aluminosilicates, water-soluble layer silicates, alkali silicates, alkali sulfates, for example sodium sulfate, and alkali phosphates.
  • the alkali silicates are preferably a compound with a molar ratio of alkali oxide to SiO of 1: 1.5 to 1: 3.5.
  • the use of such silicates results in particularly good grain properties, in particular high abrasion stability and nevertheless high dissolution rate in water.
  • the aluminosilicates referred to as carrier material include, in particular, the zeolites, for example zeolite NaA and NaX.
  • the compounds referred to as water-soluble layered silicates include, for example, amorphous or crystalline water glass.
  • Silicates which are commercially available under the name Aerosil® or Sipernat® can also be used.
  • suitable organic carrier materials are film-forming polymers, for example polyvinyl alcohols, polyvinyl pyrrolidones, poly (meth) acrylates, polycarboxylates, cellulose derivatives and starch.
  • Usable cellulose ethers are, in particular, alkali carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and so-called cellulose mixed ethers, such as, for example, methyl hydroxyethyl cellulose and methyl hydroxypropyl cellulose, and mixtures thereof.
  • Particularly suitable mixtures are composed of sodium carboxymethyl cellulose and methyl cellulose, the carboxymethyl cellulose usually having a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methyl cellulose having a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit.
  • the mixtures preferably contain alkali carboxymethyl cellulose and nonionic cellulose ethers in weight ratios from 80:20 to 40:60, in particular from 75:25 to 50:50.
  • native starch which is composed of amylose and amylopectin. Starch is referred to as native starch, as it is available as an extract from natural sources, for example from rice, potatoes, corn and wheat.
  • Carrier materials which can be used individually or more than one of the abovementioned compounds, in particular selected from the group of alkali metal carbonates, alkali metal sulfates, alkali metal phosphates, zeolites, water-soluble sheet silicates, alkali metal silicates, polycarboxylates, cellulose ethers, polyacrylate / polymethacrylate and strength.
  • alkali carbonates in particular sodium carbonate, alkali silicates, in particular sodium silicate, alkali sulfates, in particular sodium sulfate and zeolites are particularly suitable.
  • Suitable silicones are conventional organopolysiloxanes, which can have a content of finely divided silica, which in turn can also be silanized. Such organopolysiloxanes are described, for example, in European patent application EP 0496510 AI. Polydiorganosiloxanes and in particular polydimethylsiloxanes, which are known from the prior art, are particularly preferred. Suitable polydiorganosiloxanes have an almost linear chain and have a degree of oligomerization of 40 to 1500. Examples of suitable substituents are methyl, ethyl, propyl, isobutyl, tert. Butyl and phenyl.
  • silicones in general and the polydiorganosiloxanes in particular contain finely divided J silicic acid, which can also be silanated.
  • Silica-containing dimethylpolysiloxanes are particularly suitable for the purposes of the present invention.
  • the polydiorganosiloxanes advantageously have a Brookfield viscosity at 25 ° C.
  • silicones in the range from 5000 mPas to 30,000 mPas, in particular from 15,000 to 25,000 mPas.
  • the silicones are preferably used in the form of their aqueous emulsions.
  • the preparations according to the invention can contain minor amounts, for example up to about 2% by weight, of cationic surfactants.
  • cationic surfactants are, in particular, tetraalkylammonium compounds, for example dimethyldistearylammonium chloride or hydroxyethylhydroxycetyldimmonium chlorides (Dehyquart E) or esterquats. These are, for example, quaternized fatty acid triethanolamine ester salts of the formula (XIII), R 19 rR 17 CO- (OCH 2 CH 2 ) ml OCH 2 CH2-N + -CH 2 CH 2 O- (CH 2 CH 2 O) m2 R 18 ] Y (XEO)
  • R 17 CO for an acyl radical with 6 to 22 carbon atoms
  • R 18 and R 19 independently of one another for hydrogen or R 17 CO
  • ml, m2 and m3 in total for 0 or numbers from 1 to 12, m4 for numbers from 1 to 12 and Y for halide, alkyl sulfate or alkyl phosphate.
  • ester quats which can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and their technical mixtures , as they occur, for example, in the pressure splitting of natural fats and oils.
  • Technical C 12/14 coconut fatty acids and in particular partially hardened palm fatty acids and high-elaidic acid C t e / is fatty acid cuts are preferably used.
  • the fatty acids and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1.
  • an application ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1 has proven to be particularly advantageous
  • Quaternized fatty acid triethanolamine ester salts of the formula (VIII) have been found to be particularly advantageous in which R 17 CO is an acyl radical having 16 to 18 carbon atoms, R 18 is R "CO, R 19 f stands for hydrogen, R 20 for a methyl group, ml, m2 and m3 for 0 and Y for methyl sulfate.
  • quaternized ester salts of fatty acids with diethanolalkylamines of the formula (XIV) are also suitable as ester quats.
  • R 21 CO for an acyl radical with 6 to 22 carbon atoms
  • R 22 for hydrogen or R 21 CO
  • R 23 and R 24 independently of one another for alkyl radicals with 1 to 4 carbon atoms
  • m5 and m6 in total for 0 or numbers from 1 to 12
  • Y again represents halide, alkyl sulfate or alkyl phosphate.
  • suitable ester quats are the quaternized ester salts of fatty acids with 1,2-dihydroxypropyl dialkylamines of the formula (XV)
  • R 25 CO for an acyl radical with 6 to 22 carbon atoms
  • R 2 for hydrogen or R 25 CO
  • R 27 , R 28 and R 29 independently of one another for alkyl radicals with 1 to 4 carbon atoms, m7 and m.8 in total for 0 or numbers from 1 to 12
  • Y again represents halide, alkyl sulfate or alkyl phosphate.
  • ester quats are substances in which the ester bond is replaced by an amide bond and which preferably follow the formula (XVI) based on diethylenetriamine,
  • R 30 CO for an acyl radical having 6 to 22 carbon atoms
  • R 31 for hydrogen or R 30 CO
  • R 32 and R 33 independently of one another for alkyl radicals with 1 to 4 carbon atoms
  • Y again represents halide, alkyl sulfate or alkyl phosphate.
  • amide ester quats are available on the market, for example, under the Incroquat® (Croda) brand.
  • suitable amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines.
  • alkyl betaines are the carboxyalkylation products of secondary and in particular tertiary amines, which follow the formula (JXVII),
  • R 34 represents alkyl and / or alkenyl radicals with 6 to 22 carbon atoms
  • R 35 for hydrogen or alkyl radicals with 1 to 4 carbon atoms
  • R 36 for alkyl radicals with 1 to 4 carbon atoms
  • ql stands for numbers from 1 to 6 and X represents already has the meaning given above.
  • Typical examples are the carboxymethylation products of Hexylmethyla- min, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, Dodecylethylmethylamin, C12 / 14-cocodimethylamine, My- ristyldimethylamin, cetyldimethylamine, stearyldimethylamine, stearyl, O- leyldimethylamin, C t e / is tallow alkyl dimethyl amine, and their technical mixtures.
  • R 37 CO for an aliphatic acyl radical with 6 to 22 carbon atoms and 0 or 1 to 3 double bonds
  • R 38 for hydrogen or alkyl radicals with 1 to 4 carbon atoms
  • R 39 for alkyl radicals with 1 to 4 carbon atoms
  • q2 for numbers from 1 to 6
  • q3 for numbers is from 1 to 3 and X again has the meaning given above.
  • Typical examples are reaction products of fatty acids with 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, aradacholeic acid, elaeoleic acid , Behenic acid and erucic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine, which are condensed with sodium chloroacetate. It is preferred to use a condensation product of C 8/18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate.
  • Imidazolinium betaines are also suitable. These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines, such as, for example, aminoethylethanolamine (AEEA) or diethylene triamine.
  • polyhydric amines such as, for example, aminoethylethanolamine (AEEA) or diethylene triamine.
  • AEEA aminoethylethanolamine
  • the corresponding carboxyalkylation products are mixtures of different open-chain betaines.
  • Typical examples are condensation products of the above-mentioned fatty acids with AEEA, preferably hnidazolines based on lauric acid or again C12 / 14 coconut fatty acid, which are subsequently betainized with sodium chloroacetate.
  • the total proportion of auxiliaries and additives can be 1 to 70% by weight, preferably 5 to 60% by weight, based on the overall preparation.
  • fragrance compounds e.g. B. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type can be used. Fragrance compounds of the ester type are e.g. B.
  • the ethers include, for example, benzyl ethyl ether; the aldehydes include, for. B.
  • the linear alkanals with 8-18 C atoms citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones z.
  • the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • Such perfume may also contain natural fragrance mixtures as are obtainable from plant sources, e.g. B. pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • the fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles through a slower fragrance release.
  • Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perf m complexes can additionally be coated with further auxiliaries.
  • the final preparations can also contain inorganic salts as fillers or fillers, for example sodium sulfate, which is preferably present in amounts of 0 to 10, in particular 1 to 5% by weight, based on the composition.
  • inorganic salts for example sodium sulfate, which is preferably present in amounts of 0 to 10, in particular 1 to 5% by weight, based on the composition.
  • the product thus produced was added to a solution of 64 g of 50% sodium hydroxide solution (0.8 mol) in 400 g of water while checking the pH (pH> 7.5).
  • the aqueous solution was freed of THF on a rotary evaporator and before analysis
  • Example 2 is reproduced with a carrier which has been stored at room temperature for more than 1 month and is produced according to Example 1. After neutralization on a rotary evaporator, the aqueous solution is freed of THF and freeze-dried before analysis. The following composition is obtained:
  • the APG sulfate compound prepared according to Example 3 was compared to APG (a commercially available alkyl polyglycoside from Henkel KGaA with the composition C 12 -i 6 H 25. 33 O (C6H 1 oO 5 )) and Texapon N ( a commercially available sodium lauryl ether sulfate from Henkel KGaA) was examined in a foam foam test according to Götte. The product shows a generally improved foaming power compared to APG. At 0 ° dH comparable foam values are obtained at 40 ° C with Texapon N, lower temperatures at 20 ° C. At 15 ° dH the values at 2g AS / 1 at 20 and 40 ° C are comparable to Texapon N.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Veterinary Medicine (AREA)
  • Wood Science & Technology (AREA)
  • Public Health (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Epidemiology (AREA)
  • Birds (AREA)
  • Dermatology (AREA)
  • Biochemistry (AREA)
  • Biotechnology (AREA)
  • Genetics & Genomics (AREA)
  • Molecular Biology (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé pour produire des alcools sulfatés. Ce procédé consiste à mettre en réaction un alcool à sulfater ou un mélange de deux ou plusieurs alcools à sulfater avec un produit de sulfatation acide d'un alcool (support) ou un mélange de deux ou plusieurs produits de sulfatation acides d'alcools (support). Dans les conditions de réaction, au moins un produit de sulfatation acide d'un alcool transfère au moins une partie de ses groupes sulfate acides sur au moins un alcool à sulfater La présente invention concerne également une composition obtenue selon ledit procédé, ainsi qu'une composition contenant au moins un produit qui a été produit selon ledit procédé.
PCT/EP2003/008747 2002-08-16 2003-08-07 Procede de sulfatation doux WO2004022531A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10237412.0 2002-08-16
DE2002137412 DE10237412A1 (de) 2002-08-16 2002-08-16 Schonendes Sulfatierverfahren

Publications (1)

Publication Number Publication Date
WO2004022531A1 true WO2004022531A1 (fr) 2004-03-18

Family

ID=30469751

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2003/008747 WO2004022531A1 (fr) 2002-08-16 2003-08-07 Procede de sulfatation doux

Country Status (2)

Country Link
DE (1) DE10237412A1 (fr)
WO (1) WO2004022531A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105884914A (zh) * 2014-12-26 2016-08-24 厦门大学 一种淀粉硫酸酯及其盐合成新工艺

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102019000092A1 (de) * 2019-01-10 2020-07-16 Henkel Ag & Co. Kgaa Neue anionische Tenside und Wasch- und Reinigungsmittel, welche diese enthalten

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE208790C (fr) *
US2099214A (en) * 1937-11-16 Process fob forming the sulphuric
US4977253A (en) * 1988-10-13 1990-12-11 Huels Aktiengesellschaft Process for the sulfation of alkyloligoglycosides
WO1991013057A1 (fr) * 1990-03-01 1991-09-05 The Procter & Gamble Company Co-sulfatation d'alcools ethoxylates et d'alcools gras insatures

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE208790C (fr) *
US2099214A (en) * 1937-11-16 Process fob forming the sulphuric
US4977253A (en) * 1988-10-13 1990-12-11 Huels Aktiengesellschaft Process for the sulfation of alkyloligoglycosides
WO1991013057A1 (fr) * 1990-03-01 1991-09-05 The Procter & Gamble Company Co-sulfatation d'alcools ethoxylates et d'alcools gras insatures

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105884914A (zh) * 2014-12-26 2016-08-24 厦门大学 一种淀粉硫酸酯及其盐合成新工艺
CN105884914B (zh) * 2014-12-26 2021-02-19 厦门大学 一种淀粉硫酸酯及其盐合成工艺

Also Published As

Publication number Publication date
DE10237412A1 (de) 2004-02-19

Similar Documents

Publication Publication Date Title
EP1240290B1 (fr) Granulats de tensioactifs presentant une plus grande vitesse de dissolution
WO2001048133A1 (fr) Detergent solide
EP1240287A1 (fr) Pastilles de detergent
EP1250412B1 (fr) Procede de production de granules tensioactifs
WO2001057170A1 (fr) Melange tensioactif contenant des alcoxylats d'alcools gras a base de matieres vegetales
EP1274822A1 (fr) Detergents et nettoyants
DE10163281A1 (de) Wasch- und reinigungsaktive Zubereitungen, enthaltend feste granuläre nichtion ische Tenside
EP1188819A1 (fr) Tablettes détergentes
EP1188816B1 (fr) Produits de lavage et de nettoyage à base de mélanges d'oligoglycosides d'alkyle et/ou d'alcenyle et d'alcools gras
WO2001048134A1 (fr) Corps moules d"agents de lavage et de nettoyage presentant des proprietes de decomposition ameliorees
WO2001018164A1 (fr) Detergents
WO2001027238A1 (fr) Pastilles detergentes
WO2004022531A1 (fr) Procede de sulfatation doux
WO2001034746A1 (fr) Granules d'antimousse
EP1212401B1 (fr) Detergent en pastilles
EP1205536A2 (fr) Utilisation des mélanges tensioactifs
DE10002010A1 (de) Tablettensprengmittel
EP1090979A1 (fr) Granulés anti-mousse
DE10002008A1 (de) Verfahren zur Herstellung von Tablettensprengmitteln
EP1212400B1 (fr) Detergent en pastilles
EP1207193A1 (fr) Utilisation d'un mélange d'agents tensioactif pour la préparation de compositions détergentes et de lavage
EP1249489A1 (fr) Corps moules d'agents de lavage et de nettoyage présentant des proprietés de décomposition améliorées
EP1090982A1 (fr) Article moulé ayant une solubilité dans l'eau améliorée
EP1310550A1 (fr) Composition démoussante et son utilisation
WO2001034757A1 (fr) Corps façonnes presentant une solubilite dans l'eau amelioree

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): JP US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP