EP1204635A1 - Sulfates d'ethers d'alcools gras ramifies et largement insatures - Google Patents

Sulfates d'ethers d'alcools gras ramifies et largement insatures

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Publication number
EP1204635A1
EP1204635A1 EP00960443A EP00960443A EP1204635A1 EP 1204635 A1 EP1204635 A1 EP 1204635A1 EP 00960443 A EP00960443 A EP 00960443A EP 00960443 A EP00960443 A EP 00960443A EP 1204635 A1 EP1204635 A1 EP 1204635A1
Authority
EP
European Patent Office
Prior art keywords
branched
unsaturated fatty
acid
largely
largely unsaturated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00960443A
Other languages
German (de)
English (en)
Inventor
Alfred Westfechtel
Norbert Hübner
Ansgar Behler
Hans-Christian Raths
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Personal Care and Nutrition GmbH
Original Assignee
Cognis Deutschland GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cognis Deutschland GmbH and Co KG filed Critical Cognis Deutschland GmbH and Co KG
Publication of EP1204635A1 publication Critical patent/EP1204635A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
    • A61K47/20—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing sulfur, e.g. dimethyl sulfoxide [DMSO], docusate, sodium lauryl sulfate or aminosulfonic acids
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C305/00—Esters of sulfuric acids
    • C07C305/02—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton
    • C07C305/14—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton being acyclic and unsaturated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair

Definitions

  • the invention is in the field of anionic surfactants and relates largely to unsaturated fatty alcohol ether sulfates which, as a result of branching in the hydrocarbon chain, have significantly improved properties compared with linear homologues, a process for their preparation and their use for the preparation of surface-active agents.
  • Sulfates of unsaturated fatty alcohol ethoxylates which are essentially obtained by ethoxylation, sulfation and subsequent neutralization of the corresponding sebum-based alkenols, are important raw materials for the production of both cosmetic preparations and detergents, dishwashing detergents and cleaning agents.
  • the advantageous properties of these substances are: the presence of the double bond in the molecule is linked, but this also poses problems since the unsaturated fatty alcohol ether sulfates are easily susceptible to autoxidation, which is associated with discoloration and undesirable chemical changes (for example formation of peroxides and hydroperoxides).
  • the process described above is technically complex due to the two hydrogenation steps and, with the isostearyl alcohol ether sulfates, provides substitutes which can only partially replace the unsaturated fatty alcohol ether sulfates.
  • the task of the present task was to provide unsaturated fatty alcohol ether sulfates which are characterized by improved application properties, preferably higher oxidation stability.
  • the invention relates to branched, largely unsaturated fatty alcohol ether sulfates, obtainable in that
  • the branched, largely unsaturated fatty alcohol ether sulfates have a significantly higher autoxidation stability than the linear homologues of the same chain length and the same iodine number. Further advantages are improved wetting capacity, quicker solubility in cold water and easier biodegradability.
  • Another object of the invention relates to a process for the production of branched, largely unsaturated fatty alcohol ether sulfates, in which
  • the sequence of steps (a) to (d) provides on the basis of dimerized, preferably monounsaturated C ⁇ to C ⁇ fatty acids, ie oleic acid, elaidic acid, petro- selinsic gadoleic acid and erucic acid and their mixtures branched, largely unsaturated fatty alcohols in the iodine number range from 45 to 85 This is undoubtedly completely sufficient for a number of applications, but if fatty substances which have a higher content of unsaturated compounds are required, it is recommended that the The monomer fraction obtained in the dimerization is first subjected to a fractional crystallization and the resulting liquid phase is subjected, if appropriate after distillation, to the esterification.
  • the resulting fatty acid and its methyl ester are a fairly pure isoolic acid or methyl isoolate, which have an iodine number in the range 75 to 95 In in any case it is advisable to take the methylest to subject it and
  • the esterification of the fatty acids with methanol is carried out according to the methods of the prior art and is used to produce methyl esters which are relatively easy to hydrogenate instead of the methyl esters other low alkyl esters, such as ethyl, propyl or butyl esters, can of course also be produced and then hydrogenated, the choice of alcohol is not critical per se and is based solely on economic criteria and availability.
  • methyl or low alkyl esters it is in principle also possible to hydrogenate the fatty acids directly, but special catalysts are then required for this purpose, which do not form salts with the acids, and the reactor material must also be corrosion-resistant.
  • the previously obtained branched, largely unsaturated fatty alcohols are then alkoxylated in a manner known per se, ie added to the hydroxyl group ethylene oxide, propylene oxide or their mixtures in random or block distribution. On average 1 to 50, in particular 5 to 15, moles of ethylene oxide and / or 1 up to 5 moles of propylene oxide added
  • the alkoxylation is carried out by the processes of the prior art, i.e. usually in the presence of alkaline homogeneous or heterogeneous catalysts, such as, for example, sodium methylate, potassium tert-butoxide or calcined hydrotalcite or hydrophobicized with fatty acids. Accordingly, the alkoxylates can also be conventional have broad or narrow homolog distribution Sulfation and neutralization
  • the fatty alcohol alkoxylates previously prepared can also be converted into the sulfates in a manner known per se.
  • the attack of the sulfonating agent can take place both on the hydroxyl group and on the double bond.
  • the sulfation takes place about 10 times faster than the sulfonation, ie the addition of sulfur trioxide to the double bond, especially at low temperatures in the range of about 30 ° C., predominantly, ie to more than 90% by weight, (ether) sulfates are obtained .
  • the reaction of the branched, largely unsaturated fatty alcohols, for example with gaseous sulfur trioxide can be carried out in the manner known for fatty acid lower alkyl esters [J.Falbe (ed.), "Surfactants in consumer products"; Springer Verlag, Berlin-Heidelberg, 1987, p.61] take place, with reactors working according to the falling film principle being preferred.
  • the sulfur trioxide is diluted with an inert gas, preferably air or nitrogen, and used in the form of a gas mixture which contains the sulfonating agent in a concentration of 1 to 8, in particular 2 to 5,% by volume.
  • the molar ratio of alkoxylate to sulfating agent is usually 1: 0.95 to 1: 1.8, but preferably 1: 1.0 to 1: 1.6. and in particular 1: 1, 3 to 1: 1, 5.
  • the sulfation is usually carried out at temperatures of 25 to 90, preferably 35 to 80 ° C.
  • chlorosulfonic acid or amidosulfonic acid can also be used as the sulfonating agent.
  • the acidic sulfates obtained in the reaction are stirred into aqueous bases, neutralized and adjusted to a pH of 6.5 to 8.5.
  • the neutralization is selected with bases from that of alkali metal hydroxides such as sodium, potassium and lithium hydroxide, alkaline earth metal oxides and hydroxides such as magnesium oxide, magnesium hydroxide, calcium oxide and calcium hydroxide, ammonia, mono-, di- and tri-C2-alkanolamines, for example mono -, Di- and triethanolamine and primary, secondary or tertiary C 4 alkylamines formed group.
  • the neutralization bases are preferably used in the form of 5 to 55% by weight aqueous solutions, with 25 to 50% by weight aqueous sodium hydroxide solution being preferred.
  • the sulfates obtainable by the process according to the invention are present as aqueous solutions with an active substance content of 20 to 80, preferably 30 to 50% by weight.
  • the sulfates can be bleached in a manner known per se by adding hydrogen peroxide or sodium hypochlorite solution in order to achieve a further color brightening which is desired for many applications.
  • Based on the solids content in the sulfate solution 0.2 to 2% by weight of hydrogen peroxide, calculated as 100% by weight substance, or corresponding amounts of sodium hypochlorite are used.
  • the pH of the solutions can be adjusted using suitable buffering agents, e.g. B. be kept constant with sodium phosphate or citric acid. To stabilize against bacterial attack, conservation is also recommended, e.g. B. with formaldehyde solution, p-hydroxybenzoate, sorbic acid or other known preservatives.
  • the new branched, largely unsaturated fatty alcohol ether sulfates are notable for particular oxidation stability and are therefore suitable for the production of surface-active agents, preferably washing, rinsing, cleaning and finishing agents, as well as cosmetic and / or pharmaceutical preparations in which they are present in amounts of 1 to 50, preferably 5 to 35 and in particular 10 to 25 wt .-% can be contained.
  • branched, largely unsaturated fatty alcohol sulfates according to the invention are used as raw materials for the production of washing, rinsing, cleaning or finishing agents (“softeners”), they are usually in liquid form, ie as aqueous solutions or pastes; for the production of powder detergents
  • the aqueous mixtures can subsequently be dried.
  • Liquid preparations can have a non-aqueous fraction in the range from 5 to 50 and preferably 15 to 35% by weight.
  • the agent in the context of this invention, they are aqueous solutions of the mixtures mentioned
  • "essentially anhydrous" means that the agent preferably does not contain free water which is not bound as water of crystallization or in comparable form Water tolerable, especially in quantities bi
  • the detergents used can contain other typical ingredients, such as builders, bleaching agents, bleach activators, solvents, detergent boosters, enzymes, enzyme stabilizers, viscosity regulators, graying inhibitors, optical brighteners, soil repellants, foam inhibitors, inorganic Contain salts and fragrances and dyes.
  • Suitable liquid builders are ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acid and inorganic phosphonic acids such as e.g. the neutral reacting sodium salts of 1-hydroxyethane-1,1-diphosphonate, which can be present in amounts of 0.5 to 5, preferably 1 to 2,% by weight.
  • finely crystalline, synthetic and bound water-containing zeolite such as zeolite NaA in detergent quality is used as the 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 manufacture.
  • the zeolite can contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated Ci2-Ci8 fatty alcohols with 2 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • SITUATE Nete 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 NaMSixO ⁇ x + ryH ⁇ O, 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 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 layered silicates are those in which M in the general formula stands for sodium and x assumes the values 2 or 3.
  • Powder detergents based on the branched, largely branched fatty alcohol ether sulfates 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 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.
  • Particularly preferred are agents which, above all, sodium silicate with a molar ratio (module) Na ⁇ O; SiO 2 from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, included.
  • 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 agents can also 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 sheet silicates, which belong to the group of water-swellable smectites, are, for example, those of the general formulas
  • the layered silicates can hydrogen, alkali, alkaline earth ions, in particular Contain Na + and Ca 2+ .
  • the amount of water of hydration is usually in the range of 8 to 20% by weight and depends on the swelling condition or the type of processing.
  • Useful sheet silicates are known, for example, from US 3,966,629, US 4,062,647, EP 0026529 A and EP 0028432 A.
  • Layer silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.
  • 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.
  • 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 containing their salts and sugar derivatives.
  • terpolymers which are obtained according to the teaching of German patent applications DE 4221381 A and DE 4300772 A are particularly preferred.
  • Further suitable builder substances are 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 mixtures thereof 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 organic solvents are mono- and / or polyfunctional alcohols having 1 to 6 carbon atoms, preferably having 1 to 4 carbon atoms.
  • Preferred alcohols are ethanol, 1, 2-propanediol, glycerol and mixtures thereof.
  • the compositions preferably contain 2 to 20% by weight and in particular 5 to 15% by weight of ethanol or any mixture of ethanol and 1, 2-propanediol or in particular of ethanol and glycerol.
  • the preparations either contain, in addition to the mono- and / or polyfunctional alcohols having 1 to 6 carbon atoms or solely polyethylene glycol with a relative molecular weight between 200 and 2000, preferably up to 600, in amounts of 2 to 17% by weight ,
  • toluenesulfonate, xylenesulfonate, cumene sulfonate or mixtures thereof can be used as hydrotropes.
  • 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.
  • sodium formate 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 (H3BO3), metaboric acid (HBO2) and pyrobic acid (tetraboric acid H2B4O7), is particularly advantageous.
  • Viscosity regulators which can be used are, for example, hardened castor oil, salts of long-chain fatty acids, preferably in amounts of 0 to 5% by weight and in particular in amounts of 0.5 to 2% by weight, for example sodium, potassium, aluminum, magnesium - and titanium stearates or the sodium and / or potassium salts of behenic acid, and further polymeric compounds are used the.
  • the latter preferably include polyvinylpyrrolidone, urethanes and the salts of polymeric polycarboxylates, for example homopolymeric or copolymeric polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those composed of 50% to 10% maleic acid.
  • the relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, preferably between 50,000 to 120,000, based on the free acid.
  • Water-soluble polyacrylates which are crosslinked, for example, with about 1% of a polyallyl ether of sucrose and which have a relative molecular weight above one million are also particularly suitable. Examples of this are the polymers with thickening action available under the name Carbopol® 940 and 941.
  • the crosslinked polyacrylates are preferably used in amounts not exceeding 1% by weight, preferably in amounts of 0.2 to 0.7% by weight.
  • the agents can additionally contain about 5 to 20% by weight of a partially esterified copolymer, as described in European patent application EP 0367049 A.
  • These partially esterified polymers are obtained by copolymerizing (a) at least one C 4 -C28 olefin or mixtures of at least one C 4 -C28 olefin with up to 20 mol% of Ci-C ⁇ -alkyl vinyl ethers and (b) ethylenically unsaturated Dicarboxylic acid anhydrides with 4 to 8 carbon atoms in a molar ratio of 1: 1 to copolymers with K values from 6 to 100 and subsequent partial esterification of the copolymers with reaction products such as C 1 -C 3 alcohols, C 3 -C 22 fatty acids, C 1 -C 2 alkyl phenols, secondary C2-C3o-amines or mixtures thereof with at least one C2-C-alkylene oxide or tetrahydrofuran and hydrolysis of the anhydride groups of the copolymers to give carboxyl groups, the partial esterification of the copolymers being carried out to such an extent that 5 to 50% of the carb
  • the partially esterified copolymers can be present either in the form of the free acid or preferably in partially or completely neutralized form.
  • the copolymers are advantageously used in the form of an aqueous solution, in particular in the form of a 40 to 50% strength by weight solution.
  • the copolymers not only contribute to the primary and secondary washing performance of the liquid washing and cleaning agent, but also bring about a desired reduction in the viscosity of the concentrated liquid washing agent.
  • the use of these partially esterified copolymers gives concentrated aqueous liquid detergents which are flowable under the sole influence of gravity and without the action of other shear forces.
  • the concentrated aqueous liquid detergents preferably contain partially esterified copolymers in amounts of 5 to 15% by weight and in particular in amounts of 8 to 12% by weight.
  • 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, 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, acidic Group-containing polyamides are suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, eg degraded starches, strong aldehydes etc. Polyvinylpyrrod is also useful.
  • cellulose ethers such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as Methylhydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof and polyvinyl pyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition
  • the agents can contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts.
  • examples include salts of 4,4'-B ⁇ s (2-an ⁇ l ⁇ no-4-morphol ⁇ no-1, 3,5-t ⁇ az ⁇ nyl-6-am ⁇ no) st ⁇ lben- 2,2'-disulfonic acid or compounds of the same structure which carry a diethanolamino group, a methylamino group, an anino group or a 2-methoxyethylamino group instead of the morpho-imo group.
  • Brighteners of the substituted diphenylstyryl type can also be present, for example those Alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2nd -suifostyryl) -d ⁇ phenyls Mixtures of the aforementioned brighteners can also be used.
  • Uniformly 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 in small amounts, for example 10 6 to 10 3 % By weight, preferably around 10 5 % by weight, of a blue dye.
  • a particularly preferred dye is Tinolux® (commercial product of 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 5000, ie the degree of ethoxylation of the polymers containing polyethylene glycol groups can be approximately 15 to 100.
  • the polymers are characterized by an average molecular weight of approximately 5000 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 750 to 500 0, preferably from 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 (Rh ⁇ ne-Poulenc)
  • foam inhibitors When used in machine washing processes, it may be advantageous to add conventional foam inhibitors to the detergents.
  • Soaps of natural or synthetic origin for example, which have a high proportion of Ci8-C24 fatty acids are suitable.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, if appropriate signed silica as well as paraffins, waxes, microcrystalline waxes and their mixtures with signed silica or bistearylethylenediamide.
  • Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
  • the foam inhibitors, in particular silicone or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
  • the pH of liquid, in particular also liquid-concentrated, agents is generally 7 to 10.5, preferably 7 to 9.5 and in particular 7 to 8.5. Higher pH values, for example above 9, can be set by using small amounts of sodium hydroxide solution or alkaline salts such as sodium carbonate or sodium silicate.
  • the liquid preparations generally have viscosities between 150 and 10,000 mPas (Brookfield viscometer, spindle 1, 20 revolutions per minute, 20 ° C.). Viscosities between 150 and 5000 mPas are preferred for the essentially water-free agents.
  • the viscosity of these aqueous agents is preferably below 2000 mPas and is in particular between 150 and 1000 mPas.
  • the bulk density of the solid preparations is generally 300 to 1200 g / l, in particular 500 to 1100 g / l.
  • They can be produced by any of the known processes such as mixing, spray drying, granulating and extruding. Processes in which several partial components, for example spray-dried components and granulated and / or extruded components, are mixed with one another are particularly suitable. It is also possible for spray-dried or granulated components to be subsequently treated, for example with nonionic surfactants, in particular ethoxylated fatty alcohols, by the customary processes.
  • the anionic surfactants in the form of a spray-dried, granulated or extruded compound, either as an additive component in the process or as an additive to other granules.
  • the preferred heavier granules with bulk densities above 600 g / l preferably contain components which improve the detergent behavior and / or improve the dissolving behavior of the granules.
  • alkoxylated fatty alcohols with 12 to 80 moles of ethylene oxide per mole of alcohol, for example tallow fatty alcohol with 14 EO, 30 EO or 40 EO, and polyethylene glycols with a relative molecular weight between 200 and 12000, preferably between 200 and 600, are advantageously used.
  • Suitable surface modifiers are known from the prior art.
  • suitable, finely divided zeolites, silicas, amorphous silicates, fatty acids or fatty acid salts for example calcium stearate, but in particular mixtures of zeolite and silicas or zeolite and calcium stearate are particularly preferred.
  • the branched, largely unsaturated fatty alcohol ether sulfates according to the invention can also be used to produce cosmetic and / or pharmaceutical preparations, such as, for example, hair shampoos, hair lotions, foam baths, shower baths, creams, gels, lotions, alcoholic and aqueous / alcoholic solutions, emulsions, wax / fat compositions, Stick preparations, powders or ointments are used.
  • cosmetic and / or pharmaceutical preparations such as, for example, hair shampoos, hair lotions, foam baths, shower baths, creams, gels, lotions, alcoholic and aqueous / alcoholic solutions, emulsions, wax / fat compositions, Stick preparations, powders or ointments are used.
  • agents can also be used as further auxiliaries and additives, mild surfactants, oil bodies, emulsifiers, superfatting agents, pearlescent waxes, consistency enhancers, thickeners, polymers, silicone compounds, fats, waxes, stabilizers, biogenic agents, deodorants, antiperspirants, antidandruff agents, film formers, swelling agents, Contain UV protection factors, antioxidants, hydrotropes, preservatives, insect repellents, self-tanners, solubilizers, perfume oils, dyes and the like.
  • Suitable mild, i.e. particularly skin-compatible surfactants are fatty alcohol sulfates, monoglyceride sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid isethionates, Fettklaresarco- Sinate, fatty acid taurides, fatty acid glutamates, ⁇ -olefin sulfonates, ethercarboxylic acids, alkyl oligoglucosides de, fatty acid glucamides, alkylamidobetaines and / or protein fatty acid condensates, the latter preferably based on wheat proteins.
  • esters of linear C6-C22 fatty acids with branched alcohols in particular 2-ethylhexanol
  • esters of hydroxycarboxylic acids with linear or branched C6-C22 fatty alcohols in particular dioctyl malates
  • esters of linear and / or branched fatty acids with polyhydric alcohols are suitable (such as propylene glycol, dimer diol or trimer triol) and / or Guerbet alcohols, triglycerides based on C ⁇ -Cio fatty acids, liquid mono- / di- / triglyceride mixtures based on C ⁇ -Cis fatty acids
  • esters of C6-C22 fatty alcohols get and / or Guerbet alcohols with aromatic carboxylic acids, especially benzoic acid, esters of C2-Ci2-dicarboxylic acids with linear or branched alcohols with 1 to 22 carbon atoms or polyols with 2 to 10 carbon atoms and 2 to
  • Finsolv® TN linear or branched, symmetrical or asymmetrical dialkyl ethers with 6 to 22 carbon atoms per alkyl group, ring opening products of epoxidized fatty acid esters with polyols, silicone oils and / or aliphatic or naphthenic hydrocarbons, such as squalane , Squalene or dialkylcyclohexanes.
  • Suitable emulsifiers are nonionic surfactants from at least one of the following groups:
  • Partial esters of polyglycerol (average degree of self-condensation 2 to 8), polyethylene glycol (molecular weight 400 to 5000), trimethylolpropane, pentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (e.g.
  • cellulose / or unsaturated, linear or branched fatty acids with 12 to 22 carbon atoms and / or hydroxycarboxylic acids with 3 to 18 carbon atoms and their adducts with 1 to 30 moles of ethylene oxide; > Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE 1165574 PS and / or mixed esters of fatty acids with 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol.
  • adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols or with castor oil are known, commercially available products. These are mixtures of homologs whose average degree of alkoxylation is the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate, with which the addition reaction is carried out.
  • Ci ⁇ / is fatty acid monoesters and diesters of adducts of ethylene oxide with glycerol are known from DE 2024051 PS as refatting agents for cosmetic preparations.
  • Alkyl and / or alkenyl oligoglycosides their preparation and their use are known from the prior art. They are produced in particular by reacting glucose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms.
  • the glycoside residue both monoglycosides in which a cyclic sugar residue is glycosidically bonded to the fatty alcohol and oligomeric glycosides with a degree of oligomerization of up to about 8 are suitable.
  • the degree of oligomerization is a statistical mean value which is based on a homolog distribution customary for such technical products.
  • Suitable partial glycerides are hydroxystearic acid monoglyceride, stearic acid diglyceride hydroxy, isostearic acid, Isostearinklarediglycerid, oleic acid monoglyceride, oleic acid diglyceride, Ricinolklaremoglycerid, Ricinolklarediglycerid, Linolklaremonoglycerid, linoleic acid diglyceride, LinolenTalkremonoglycerid, Linolenklastedigiycerid, Erucaklaremonoglycerid, erucic acid diglyceride, rid Weinchuremonoglycerid, Weinklarediglycerid, Citronenklamonoglycerid, Citronendiglyce-, Malic acid monoglyceride, malic acid diglyceride and their technical mixtures, which may still contain minor amounts of triglyceride from the manufacturing process. Addition products of 1 to 30, preferably 5 to
  • polyglycerol esters are polyglyceryl-2 dipolyhydroxystearates (Dehymuls® PGPH), polyglycerol-3-diisostearates (Lameform® TGI), polyglyceryl-4 isostearates (Isolan® Gl 34), polyglyceryl-3 oleates, diisostearoyl polyglyearylate-3 (Isolan® PDI), Polyglyceryl-3 Methylglucose Distearate (Tego Care® 450), Polyglyceryl-3 Beeswax (Cera Bellina®), Polyglyceryl-4 Caprate (Polyglycerol Caprate T2010 / 90), Polyglyceryl-3 Cetyl Ether (Chimexane® NL) , Polyglyceryl-3 Distearate (Cremophor® GS 32) and Polyglyceryl Polyricinoleate (Admul® WOL 1403) Polyglyceryl Dimerate Is
  • polystyrene resin examples include the mono-, di- and triesters of trimethylolpropane or pentaerythritol with lauric acid, coconut fatty acid, taig fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like which are optionally reacted with 1 to 30 mol of ethylene oxide.
  • Zwitterionic surfactants can also be used as emulsifiers.
  • Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule.
  • Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N, N-dimethylammonium glycinate, for example coconut alkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example coconut acylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxylm -hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate.
  • betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example coconut alkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for
  • Suitable emulsifiers are ampholytic surfactants.
  • Ampholytic surfactants are surface-active compounds which, in addition to a C ⁇ -alkyl or -acyl group, contain at least one free amino group and at least one -COOH or -S ⁇ 3H group in the molecule and are capable of forming internal salts.
  • ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 bisacid acids 18 carbon atoms in the alkyl group.
  • ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and Ci2 / i8-acylsarcosine.
  • cationic surfactants are also suitable as emulsifiers, those of the ester quat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred.
  • Substances such as, for example, lanolin and lecithin and polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides can be used as superfatting agents, the latter simultaneously serving as foam stabilizers.
  • Pearlescent waxes are: alkylene glycol diesters, especially ethylene glycol distearate; Fatty acid alkanolamides, especially coconut fatty acid diethanolamide; Partial glycerides, especially stearic acid monoglyceride; Esters of polyvalent, optionally hydroxy-substituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; Fatty substances, such as, for example, fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which have a total of at least 24 carbon atoms, especially lauron and distearyl ether; Fatty acids such as stearic acid, hydroxystearic acid or behenic acid, ring opening products of olefin epoxides with 12 to 22 carbon atoms with fatty alcohols with 12 to 22 carbon atoms and / or polyols with 2 to 15 carbon atom
  • Suitable consistency agents are primarily fatty alcohols or hydroxyfatty alcohols with 12 to 22 and preferably 16 to 18 carbon atoms and also partial glycerides, fatty acids or hydroxyfatty acids. A combination of these substances with alkyl oligoglucosides and / or fatty acid N-methylglucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates is preferred.
  • Suitable thickeners are, for example, Aerosil types (hydrophilic silicas), polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, and also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates , (eg Carbopole® from Goodrich or Synthalene® from Sigma), polyacrylamides, polyvinyl alcohol and polyvinylpyrrolidone, surfactants such as ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with a narrow homolog distribution or alkyl oligoglucosides as well as Cooking salt and ammonium chloride.
  • Aerosil types hydrophilic silicas
  • polysaccharides in
  • Suitable cationic polymers are, for example, cationic cellulose derivatives, such as, for example, a quaternized hydroxyethyl cellulose, which is available under the name Polymer JR 400® from Amerchol, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers, such as, for example, Luviquat® (BASF) Condensation products of polyglycols and amines, quaternized collagen polypeptides such as lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat®L / Grünau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers, such as amidomethicones, copolymers of adipic acid and dimethylaaminohydroxypropyldiethylenetriamine (Cartaretine® / Sandoz), copolymers of acrylic acid with dimethyl
  • Suitable anionic, zwitterionic, amphoteric and nonionic polymers are, for example, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and esters thereof, uncrosslinked and polyol-crosslinked polyacrylic acids, acrylamidopropyl / Acrylate copolymers, octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxyproyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, vinylpyrrolidone / dimethylaminoethyl methacrylate / vinylcaprolactam terpolymer and optionally der
  • Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside- and / or alkyl-modified silicone compounds, which can be both liquid and resinous at room temperature.
  • Simethicones which are mixtures of dimethicones with an average chain length of 200 to 300 dimethylsiloxane units and hydrogenated silicates, are also suitable.
  • a detailed overview of suitable volatile silicones can also be found by Todd et al. in Cosm.Toil. 91, 27 (1976).
  • fats are glycerides
  • waxes include natural waxes, e.g. Candelilla wax, camauba wax, japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, montan wax, beeswax, shellac wax, walnut, lanolin (wool wax), pretzel fat, ceresin, ozokerite (earth wax), petrolatum, paraffin wax, wax ; chemically modified waxes (hard waxes), e.g. Montanester waxes, Sasol waxes, hydrogenated jojoba waxes and synthetic waxes, such as Polyalkylene waxes and polyethylene glycol waxes in question.
  • natural waxes e.g. Candelilla wax, camauba wax, japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax
  • Biogenic active substances are, for example, tocopherol, tocopheroiacetate, tocopherol palmitate, ascorbic acid, deoxy ⁇ bonucleic acid, retinol, bisabolol, allantoin, phytant ⁇ ol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes
  • deodorants counteract body odors, mask or eliminate body odors caused by the action of skin bacteria on apocromatic sweat, whereby unpleasant smelling degradation products are formed. Accordingly, deodorants contain active ingredients which act as germ inhibitors, enzyme inhibitors, odor absorbers or odor suppressants
  • Suitable enzyme inhibitors are, for example, esterase inhibitors. These are preferably methyl alkyl citrates such as methyl methyl citrate, methyl propyl citrate, trisopropyl citrate, methyl butyl citrate and especially methyl citrate (Hydagen® CAT, Henkel KGaA, Dusseldorf / FRG).
  • methyl alkyl citrates such as methyl methyl citrate, methyl propyl citrate, trisopropyl citrate, methyl butyl citrate and especially methyl citrate (Hydagen® CAT, Henkel KGaA, Dusseldorf / FRG).
  • esterase inhibitors are sterolsulfates or phosphates, such as, for example, Lanoste ⁇ n-, Choleste ⁇ n-, Campesterm-, Stigmastenn- and Sitosten ⁇ nsulfate or -phosphate, dicarboxylic acids and their esters, such as, for example, glutaric acid, glutaric acid monoethyl ester, glutteroate ester acid, glutarsoate ester, Diethyl adipate, malonic acid and diethyl malonate, hydroxycarbonates and their esters such as citric acid, malic acid, tartaric acid or tartaric acid diethyl ester, and zinc glycinate
  • sterolsulfates or phosphates such as, for example, Lanoste ⁇ n-, Choleste ⁇ n-, Campesterm-, Stigmastenn- and Sitosten ⁇ nsulfate or -phosphate
  • dicarboxylic acids and their esters such as, for example
  • Suitable as odor absorbers are substances that absorb and largely retain odor-forming compounds.You can lower the partial pressure of the individual components and thus also reduce their rate of propagation.It is important that perfumes must remain unaffected.Odor absorbers have no activity against bacteria.For example, they contain a complex zinc salt as the main component the ricinoleic acid or special, largely odorless fragrances known to the person skilled in the art as "fixators", such as extracts of labdanum or styrax or certain abietic acid derivatives. Odorants or perfumes function as odor reflectors
  • Perfume oils are, for example, mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers, stems and leaves, fruits, fruit peels, roots, woods, herbs and grasses, needles and branches as well as resins and balms. Animal raw materials, such as civet and castoreum, are also suitable. Typical synthetic fragrance compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, p-tert-butylcyclohexyl acetate, linalyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate.
  • the ethers include, for example, benzyl ethyl ether
  • the aldehydes include, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal
  • the ketones include, for example, the jonones and methylcedryl ketone
  • the alcohols are anethole, citronellellone Eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol
  • the hydrocarbons mainly include the terpenes and balsams.
  • fragrance oils of lower volatility which are mostly used as aroma components, are also suitable as perfume oils, e.g. sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labdanum oil and lavandin oil.
  • Antiperspirants reduce the formation of sweat by influencing the activity of the eccrine sweat glands and thus counteract axillary ingress and body odor.
  • Aqueous or anhydrous formulations of antiperspirants typically contain the following ingredients:
  • non-aqueous solvents such as As ethanol, propylene glycol and / or glycerin.
  • Salts of aluminum, zirconium or zinc are particularly suitable as astringent antiperspirant active ingredients.
  • suitable antiperspirant active ingredients are, for example, aluminum chloride, aluminum chlorohydrate, aluminum dichlorohydrate, aluminum sesquichlorohydrate and their complex compounds, for. B. with propylene glycol-1, 2nd Aluminum hydroxyallantoinate, aluminum chloride tartrate, aluminum zirconium trichlorohydrate, aluminum zirconium tetrachlorohydrate, aluminum zirconium pentachlorohydrate and their complex compounds z.
  • B. with amino acids such as glycine.
  • conventional oil-soluble and water-soluble auxiliaries can be present in smaller amounts in antiperspirants. Examples of such oil-soluble auxiliaries are:
  • water-soluble additives are e.g. Preservatives, water-soluble fragrances, pH adjusters, e.g. Buffer mixtures, water soluble thickeners, e.g. water-soluble natural or synthetic polymers such as e.g. Xanthan gum, hydroxyethyl cellulose, polyvinyl pyrrolidone or high molecular weight polyethylene oxides.
  • Climbazole, octopirox and zinc pyrethione can be used as antidandruff agents.
  • Common film formers are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid or its salts and similar compounds.
  • Montmorillonites, clay minerals, pemules and alkyl-modified carbopol types can serve as swelling agents for aqueous phases. Further suitable polymers or swelling agents can be found in the overview by R. Lochhead in Cosm.Toil. 108, 95 (1993).
  • UV light protection factors are understood to mean, for example, organic substances (light protection filters) which are liquid or crystalline at room temperature and which are able to absorb ultraviolet rays and absorb the energy absorbed in the form of longer-wave radiation, e.g. To give off heat again.
  • UVB filters can be oil-soluble or water-soluble. As oil-soluble substances e.g. to call:
  • 3-benzylidene camphor or 3-benzylidene norcampher and its derivatives for example 3- (4-methylbenzylidene) camphor as described in EP 0693471 B1; > 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate; Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate (octocrylene);
  • esters of salicylic acid preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropylbenzyl ester, salicylic acid homomethyl ester;
  • benzophenone preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone;
  • Esters of benzalmalonic acid preferably di-2-ethylhexyl 4-methoxybenzmalonate; Triazine derivatives, e.g. 2,4,6-trianilino- (p-carbo-2'-ethyl-1 '-hexyloxy) -1, 3,5-triazine and octyl triazone as described in EP 0818450 A1 or dioctyl butamido triazone (Uvasorb ® HEB);
  • Triazine derivatives e.g. 2,4,6-trianilino- (p-carbo-2'-ethyl-1 '-hexyloxy) -1, 3,5-triazine and octyl triazone as described in EP 0818450 A1 or dioctyl butamido triazone (Uvasorb ® HEB);
  • UV-A filters -4'-methoxydibenzoyl-methane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione and enamine compounds, as described in DE 19712033 A1 (BASF).
  • the UV-A and UV-B filters can of course also be used in mixtures.
  • insoluble light protection pigments namely finely dispersed metal oxides or salts, are also suitable for this purpose.
  • suitable metal oxides are, in particular, zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof.
  • Silicates (talc), barium sulfate or zinc stearate can be used as salts.
  • the oxides and salts are used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics.
  • the particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They can have a spherical shape, but it is also possible to use particles which have an ellipsoidal shape or a shape which differs from the spherical shape in some other way.
  • the Pig elements can also be surface-treated, ie hydrophilized or hydrophobized.
  • Typical examples are coated titanium dioxides, such as titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Silicones, and in particular trialkoxyoctylsilanes or simethicones, are particularly suitable as hydrophobic coating agents. So-called micro- or nanopigments are preferably used in sunscreens. Micronized zinc oxide is preferably used. Further suitable UV light protection filters can be found in the overview by P.Finkel in S ⁇ FW-Journal 122, 543 (1996).
  • secondary light stabilizers of the antioxidant type can also be used, which interrupt the photochemical reaction chain which is triggered when UV radiation penetrates the skin.
  • Typical examples are amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (e.g. urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L-carnosine and their derivatives (e.g. anserine) , Carotenoids, carotenes (e.g.
  • ⁇ -carotene, ß-carotene, lycopene) and their derivatives chlorogenic acid and their derivatives, lipoic acid and their derivatives (e.g. dihydroliponic acid), aurothioglucose, propylthiouracil and other thiols (e.g.
  • thioredoxin glutathione, cysteine, Cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, ⁇ -linoleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thio propionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine compounds (eg buthioninsulfoximines, homocysteine sulfoximine, butioninsulfones, penta-, hexa-, himathion in) in very low tolerable doses (e.g.
  • ⁇ -hydroxy fatty acids e.g. citric acid, lactic acid, malic acid
  • humic acid e.g. galienic acid, bile extracts, biirubin, biliverdin, EDTA, EGTA and its derivatives
  • unsaturated fatty acids and their derivatives e.g. ⁇ -linolenic acid, linoleic acid, oleic acid
  • folic acid and their derivatives ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives (e.g.
  • vitamin E acetate vitamin E acetate
  • vitamin A palmitate vitamin A palmitate
  • ZnO, ZnS0 selenium and its derivatives (e.g. Selenium-methionine), stilbenes and their derivatives (e.g. stilbene oxide, trans-stilbene oxide) and the derivatives (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these active substances which are suitable according to the invention.
  • stilbenes and their derivatives e.g. stilbene oxide, trans-stilbene oxide
  • derivatives salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids
  • Hydrotropes such as ethanol, isopropyl alcohol, or polyols can also be used to improve the flow behavior.
  • Polyols that come into consideration here preferably have 2 to 15 carbon atoms and at least two hydroxyl groups.
  • the polyols can still contain further functional groups, in particular amino groups, or be modified with nitrogen. Typical examples are
  • Alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and polyethylene glycols with an average molecular weight of 100 to 1,000 daltons;
  • Methyl compounds such as in particular trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;
  • Dialcohol amines such as diethanolamine or 2-amino-1, 3-propanediol.
  • Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid and the further classes of substances listed in Appendix 6, Parts A and B of the Cosmetics Ordinance.
  • N, N-diethyl-m-toluamide, 1, 2-pentanediol or ethyl butylacetylaminopropionate are suitable as insect repellents, and dihydroxyacetone is suitable as a self-tanning agent.
  • Perfume oils include mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers (lily, lavender, roses, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, caraway, juniper), fruit peel (bergamot, lemon, Oranges), roots (mace, angelica, celery, cardamom, costus, iris, calmus), wood (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme), Needles and twigs (spruce, fir, pine, mountain pine), resins and balms (galbanum, elemi, benzoin, myrrh, olibanum, opoponax).
  • Typical synthetic fragrance compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl benzylatepylpropionate, and
  • the ethers include, for example, benzyl ethyl ether, the aldehydes, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde,
  • Essential oils of lower volatility which are mostly used as aroma components, are also suitable as perfume oils, for example sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labolanum oil and lavandin oil.
  • bergamot oil dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, ⁇ -hexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, Boisambrene Forte, Ambroxan, indole, hedione, Sandelice, lemon oil, mandarin oil, orange oil, allyl amyl glycolate, Cyclovertal, lavandin oil, muscatel Sage oil, ß-damascone, geranium oil bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilllate, irot
  • the dyes which can be used are those substances which are suitable and approved for cosmetic purposes, as compiled, for example, in the publication "Cosmetic Dyes” by the Dye Commission of the German Research Foundation, Verlag Chemie, Weinheim, 1984, pp. 81-106. These dyes are usually used in concentrations of 0.001 to 0.1% by weight, based on the mixture as a whole.
  • the total proportion of auxiliaries and additives can be 1 to 50, preferably 5 to 40,% by weight, based on the composition.
  • the agents can be produced by customary cold or hot processes; the phase inversion temperature method is preferably used.
  • Example 1 23 kg of monomeric fatty acid Edenor® 935 (Henkel KGaA) were esterified with 20 kg of methanol for 2 hours at 240 ° C. and 100 bar. After the water / methanol mixture had been separated off, the same amount of fresh methanol was added and the process was repeated twice. The ester thus obtained had an acid number of 0.8. The methyl ester was hydrogenated in a fixed bed mode over a Zn-Cr catalyst to obtain the double bond. Here, 0.5 volume units of methyl ester per hour - based on the total volume of the plant - were enforced. After the methanol had been driven off, the crude alcohol was distilled (3% lead, 90% main run, 6% residue).
  • the resulting alcohol showed a hydroxyl number of 192, a saponification number of 0.9 and an iodine number of 74; the fixed point was 25.8 ° C.
  • 293 g (1 mol) of the isooleyl alcohol thus obtained were placed in a stirred autoclave and dried at 100 ° C. for about 45 minutes.
  • the ethoxylation was carried out with 88 g (2 mol) of ethylene oxide at 120 to 160 ° C. and an autogenous pressure of 5 bar. After cooling the reaction mixture was evacuated to remove traces of unreacted ethylene oxide.
  • Example 2 Monomer fatty acid was largely freed from straight-chain, saturated fatty acids by crystallization from methanol / water (Emersol method). In this way, approximately 20% by weight of fatty acid, predominantly palmitic and stearic acid, were separated off.
  • the liquid fatty acid mixture obtained after distilling off the solvent had a titer of 5 ° C. and was first converted into the methyl ester analogously to Example 1 and then hydrogenated to the unsaturated fatty alcohol. This showed a hydroxyl number of 191, a saponification number of 1.7 and an iodine number of 87; the fixed point was 3.8 ° C.
  • Cosmetic preparations water, preservatives ad 100 wt.

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Abstract

L'invention concerne des sulfates d'éthers d'alcools gras ramifiés et largement insaturés que l'on obtient de la manière suivante : (a) on dimérise de manière connue en soi des acides gras insaturés ayant 16 à 22 atomes de carbone, (b) on sépare la fraction monomère produite lors de la dimérisation, (c) on transforme les acides gras ramifiés et largement insaturés contenus dans cette fraction en esters méthyliques d'acides gras, (d) on procède à l'hydrogénation de ces esters méthyliques d'acides gras ramifiés et largement insaturés en alcools gras ramifiés et largement insaturés avec obtention des liaisons doubles et (e) on alcoxyle, sulfate et neutralise ces alcools gras de manière connue en soi.
EP00960443A 1999-08-20 2000-08-11 Sulfates d'ethers d'alcools gras ramifies et largement insatures Withdrawn EP1204635A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19939537 1999-08-20
DE1999139537 DE19939537A1 (de) 1999-08-20 1999-08-20 Verzweigte, weitgehend ungesättigte Fettalkoholethersulfate
PCT/EP2000/007846 WO2001014326A1 (fr) 1999-08-20 2000-08-11 Sulfates d'ethers d'alcools gras ramifies et largement insatures

Publications (1)

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EP1204635A1 true EP1204635A1 (fr) 2002-05-15

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EP00960443A Withdrawn EP1204635A1 (fr) 1999-08-20 2000-08-11 Sulfates d'ethers d'alcools gras ramifies et largement insatures

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EP (1) EP1204635A1 (fr)
DE (1) DE19939537A1 (fr)
WO (1) WO2001014326A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108117936A (zh) * 2016-11-30 2018-06-05 黎凯华 一种低泡沫洁厕剂

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4300321A1 (de) * 1993-01-08 1994-07-14 Henkel Kgaa Oligoglycerinethersulfate
DE4422858C1 (de) * 1994-06-30 1995-07-27 Henkel Kgaa Ungesättigte Fettalkohole mit verbessertem Kälteverhalten
DE19542569A1 (de) * 1995-11-15 1997-05-22 Henkel Kgaa Fettalkohol(ether)sulfate mit verbessertem Kälteverhalten
AUPO846297A0 (en) * 1997-08-08 1997-09-04 Ici Australia Operations Proprietary Limited Anionic alkoxylate surfactant

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0114326A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108117936A (zh) * 2016-11-30 2018-06-05 黎凯华 一种低泡沫洁厕剂

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DE19939537A1 (de) 2001-02-22

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