WO1994018291A1 - Tensioactifs anioniques a solubilite amelioree - Google Patents

Tensioactifs anioniques a solubilite amelioree Download PDF

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Publication number
WO1994018291A1
WO1994018291A1 PCT/EP1994/000207 EP9400207W WO9418291A1 WO 1994018291 A1 WO1994018291 A1 WO 1994018291A1 EP 9400207 W EP9400207 W EP 9400207W WO 9418291 A1 WO9418291 A1 WO 9418291A1
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Prior art keywords
ether
sulfates
anionic surfactants
alkyl
hydrophobic structure
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PCT/EP1994/000207
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German (de)
English (en)
Inventor
Karl Schmid
Andreas Syldath
Michael Neuss
Ditmar Kischkel
Thomas Krohnen
Hubert Pawelczyk
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Henkel Kommanditgesellschaft Auf Aktien
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Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to EP94906150A priority Critical patent/EP0682690B1/fr
Priority to KR1019950703245A priority patent/KR960701181A/ko
Priority to JP6517587A priority patent/JPH08506366A/ja
Priority to DE59403312T priority patent/DE59403312D1/de
Publication of WO1994018291A1 publication Critical patent/WO1994018291A1/fr

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    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • 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
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether carboxylic acids
    • 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
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates 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
    • C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/126—Acylisethionates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/16—Sulfonic acids or sulfuric acid esters; Salts thereof derived from divalent or polyvalent alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/34—Derivatives of acids of phosphorus
    • C11D1/345—Phosphates or phosphites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/667—Neutral esters, e.g. sorbitan esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • the invention relates to anionic surfactants with improved solubility, a process for their preparation in which poorly soluble surfactants are processed together with hydrophobic structure breakers and selected polymeric solidifying agents to form solid, readily water-soluble products, solid surface-active agents which contain these anionic surfactants and the use of the anionic surfactants for the production of surface-active agents.
  • Anionic surfactants are important components of detergents, dishwashing detergents and cleaning agents. In contrast to nonionic surfactants, which have an inverse solubility behavior and, owing to hydrogen bonds, are more soluble in cold water than in warm ones, anionic surfactants behave conventionally , ie their solubility increases more or less linearly with temperature until the solubility product is reached. For technical applications - for example with regard to the induction capacity during the waking process - however, there is a need for anionic surfactants that have sufficient solubility, especially in cold water.
  • the best-known hydrotropes undoubtedly include the short-chain alkylarylsulfonates, such as, for example, toluene, xylene or cumene sulfonate. They are suitable, for example, as dissolving agents for anionic and nonionic surfactants in the production of liquid detergents.
  • the improved solubility is probably due to an advantageous mixed micelle formation.
  • solubility in cold water in particular of fatty alcohol sulfates
  • surfactants with high HLB values for example highly ethoxylated polyglycol ethers (tallow alcohol 40 EO adduct) or the like, as hydrotropes.
  • HLB values for example highly ethoxylated polyglycol ethers (tallow alcohol 40 EO adduct) or the like
  • German patent application DE-Al-40 30 688 (Henkel).
  • the droplets of surfactant are spontaneously heated to the boiling point of the water.
  • the high internal surface area resulting in this way leads to a substantially improved dissolution rate, for example in comparison to conventionally spray-dried products.
  • the method described is associated with a high level of technical complexity.
  • solid detergents with a high bulk density and improved solubility are obtained by mixing mixtures of anionic and nonionic surfactants with polyethylene glycol ether having a molecular weight in the range from 200 to 12,000, preferably 200 to 600 adds, and then dries and / or solidifies.
  • spray-dried detergent compositions are disclosed in general form which, in addition to anionic surfactants, contain nonionic surfactants, polyacrylates and polyethylene glycol ethers with an average molecular weight in the range from 1,000 to 20,000.
  • the teaching of this document is that the dispersibility of anionic surfactants can be improved by adding nonionic surfactants, polyethylene glycol ethers and polyacrylates to them.
  • the PEGs actually used are of low molecular weight and preferably have molecular weights in the range from 4,000 to 20,000 (see page 4, section 2).
  • the only exemplary embodiment describes a mixture comprising alkylbenzenesulfonate and fatty alcohol sulfate, to which a Ci2 / i3-oxoalcohol-6.5 EO adduct, sodium polyacrylate and polyethylene glycol with a molecular weight of approximately 8,000 are added.
  • the weight ratio between nonionic surfactant and PEG is 1: 1.
  • DE-OS 21 24 526 relates to detergent and cleaning agent mixtures with controlled foam behavior.
  • compositions which contain tallow alcohol sulfate, alkylbenzenesulfonate and polyethylene glycol with a molecular weight of approximately 20,000.
  • solid detergents are known from international patent application WO 92/09676 (Henkel), which are obtained by treating aqueous alkyl sulfate pastes with soda and zeolites and then extruding them. The document does not reveal anything about the dissolution rate of the solids.
  • the object of the invention was to provide anionic surfactants which are readily soluble even in cold water and whose production is free from the disadvantages described.
  • the invention relates to anionic surfactants with improved solubility, obtainable by selecting sparingly soluble anionic surfactants from the group consisting of alkylbenzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, oc-methyl ester sulfonates, sulfofatty acids, fatty alcohol sulfates - Holether sulfates, glycerol ether sulfates, hydroxymischether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) - sulfates, sulfosuccinates, sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids, isethionates, sarcosines, taurides, al
  • anionic surfactants according to the invention which have a content of hydrophobic structural breakers and selected polymeric strengthening agents, are distinguished from conventional products by a particularly advantageous dissolution rate.
  • the invention is based on the knowledge that conventional manufacturing processes are unable to produce anionic surfactants with a minimum grain size required for good solubility. Conversely, commercial surfactants are too coarse-grained to be sufficiently soluble. Another problem is that even finely divided powders during solidification, e.g. B. by extrusion, again to coarse-grained and therefore less water-soluble Ma ⁇ material.
  • the inventive concept now consists in subsequently structuring the anionic side grain by introducing a hydrophobic structure breaker and in this way within of the grain to produce anionic surfactant zones which are separated from one another by the hydrophobic additive.
  • the conventional coarse grain to a certain extent the "single crystal” results in a conglomerate of fine grains which are separated by the hydrophobic structure breaker and thus have a considerably improved solubility even after mechanical compaction.
  • This approach to solving the problem is fundamentally different from the known approaches. In particular, it represents a reversal of the principle of adding poorly soluble surfactants to hydrophilizing substances.
  • a further finding on which the invention is based is that there is a critical molecular weight limit of 12,000 when using polyethylene glycol ether as a polymeric strengthening agent.
  • the desired effect namely a significant improvement in the dissolution rate, is not achieved below this limit.
  • R 1 is an alkyl and / or alkenyl radical having 12 to 22, preferably 16 to 18 carbon atoms and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • the invention further relates to a process for the preparation of anionic surfactants with improved solubility, in which sparingly soluble anionic surfactants are selected from the group consisting of alkylbenzenesulfonates, alkanesulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, Methyl ester sulfonates, sulfofatty acids, fatty alcohol sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxymixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, sulfosuccinates, sulfosuccinamates, sulfotriglycerides, amide soaps, alkylethionate, urethane, sarucinate, suc
  • anionic surfactants are all known substances.
  • J.Falbe ed.
  • Sudfactants in consumer products Springer Verlag, Berlin, 1987, pp. 54-85
  • J.Falbe U. Hasserodt
  • Catalysts surfactants and mineral oil additives
  • Thieme Verlag, Stuttgart, 1978, pp. 126-139 surface-active substances of this type show a more or less poor cold water solubility. If they are used, for example, in detergent formulations, problems arise during the washing-in process in the washing machine.
  • alkylbenzenesulfonates dodecylbenzenesulfonates
  • o-methyl ester sulfonates o-methyl ester sulfonates
  • fatty alcohol sulfates fatty alcohol sulfates
  • Fatty alcohol sulfates are usually produced by sulfating alcohols with gaseous sulfur trioxide or chlorosulfonic acid and subsequent neutralization with bases. They follow formula (I)
  • R 1 is an alkyl and / or alkenyl radical having 12 to 22 carbon atoms and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or gluca - monium.
  • Typical examples are the sulfates of stylalkohol lauryl alcohol, myristic alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, Petroseli- nylalkohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol and erucyl alcohol and technical mixtures such as fractions for example, in the hydrogenation of Fettklaremethylester ⁇ or aldehydes from Roelen's oxosynthesis.
  • Fatty alcohol sulfates of the formula (I) are preferably used in which R 1 is an alkyl radical having 16 to 18 carbon atoms and X is sodium; the preferred fatty alcohol sulfate is therefore a tallow alcohol sulfate with a
  • Non-ionic surfactants which have an HLB value in the range from 0.5 to 10 are particularly suitable as hydrophobic structure breakers.
  • this includes, for example, fatty alcohols and / or fatty alcohol polyglycol ethers of the formula
  • n is 0 or numbers from 1 to 3 and m is 0 or numbers from 1 to 10.
  • fatty alcohol polyglycol ethers which can be used as hydrophobic structure breakers in the sense of the invention are addition products of an average of 1 to 3 mol of propylene oxide and / or 1 to 10 mol of ethylene oxide with capron alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol , Palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol and erucyl alcohol as well as their technical mixtures such as high-pressure hydrogenation, as described for example by high pressure hydrogenation ester fractions or aldehydes from Roele
  • the alkoxylation products can have both a conventional and, in particular, a narrowed homogeneous distribution.
  • Fatty alcohol polyglycol ethers of the type mentioned which have a conventionally broad homolog distribution and a low degree of alkoxylation, contain a significant proportion of free fatty alcohol, up to 35% by weight. can be.
  • this fact is in no way a disadvantage for the suitability of such surfactants.
  • it has rather proven that the free fatty alcohols alone are extremely effective as structure breakers.
  • A_Ucyioligoglycosides of the formula (III) are also suitable as structure breakers,
  • R3 is an alkyl radical having 12 to 22 carbon atoms
  • G is a sugar radical having 5 or 6 carbon atoms
  • p is a number from 1 to 10.
  • Alkyl oligoglycosides are known substances which can be obtained by the relevant processes in preparative organic chemistry.
  • EP-A1-0 301 298 and WO 90/3977 are known substances which can be obtained by the relevant processes in preparative organic chemistry.
  • the alkyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose.
  • the preferred alkyl oligoglycosides are thus alkyl oligoglucos de.
  • Alkyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, those alkyl oligoglycosides are preferred whose degree of oligomerization is less than 1.7 and is in particular between 1.2 and 1.4.
  • the alkyl oligoglycosides can also be used in a mixture with fatty alcohols. Suitable for this purpose raw products, for example, which still contain fatty alcohols which have not been converted due to production.
  • Fatty acid esters of the formula (IV) are also suitable as hydrotropic structure breakers
  • R ⁇ CO stands for an acyl radical with 16 to 22 carbon atoms and R5 for an alkyl radical with 1 to 4 carbon atoms, a glycerol or oligoglycerol radical.
  • glyeerin or oligoglycerol esters can be present as full esters, but in particular as partial esters.
  • Ci6 18 ⁇ Ta 19 ⁇ ettsauremetn yl ⁇ esters are preferably used.
  • dialkyl ethers of the formula (V) can also be used.
  • the dialkyl ethers which are particularly preferred for the purposes of the invention are thus di-n-octyl ether and di-2-ethylhexyl ether.
  • Fat ketones of the formula (VI) are also suitable as hydrophobic structure breakers
  • R ⁇ and R ⁇ are independently alkyl radicals having 7 to 17 carbon atoms.
  • Fat ketones are known substances that can be obtained by the relevant methods of preparative organic chemistry. Goes to their manufacture one, for example, from fatty acid magnesium salts which are pyrolyzed at temperatures above 300 ° C. with elimination of CO2 and water [DE-OS 25 53 900].
  • Typical fat ketones which can be considered as hydrophobic structure breakers are obtained by pyrolysis of the magnesium salts of palmitic acid, stearic acid, arachic acid, behenic acid and their technical mixtures, for example cig-C 1-6 tallow fatty acid.
  • the use of stearone (pentatriacontanone-18) is preferred.
  • the substance classes suitable as structure breakers also include Guerbet alcohols of the formula (VII),
  • x stands for numbers from 6 to 16.
  • These are primary, branched alcohols which are prepared in a known manner by base-catalyzed dimerization of fatty alcohols. Typical examples are 2-hexyldecanol, 2-0ctyldodecanol and 2-decyltetradecanol.
  • further structure breakers are saturated hydrocarbons, as are usually used as oil bodies in many products. These are preferably paraffins which have a density of 0.81 to 0.875.
  • the hydrophobic structure breakers can usually be added to the anionic surfactants in amounts of 1 to 50, preferably 2 to 15 and in particular 5 to 10% by weight, based on the mixture.
  • the structure breakers in question are liquid under normal conditions, the question arises as to how it can be ensured that the structure breaker remains in the anionic surfactant grain, structures it permanently and does not "bleed out".
  • a large number of investigations carried out by the applicant have surprisingly shown that the dry grain of anionic surfactants has an amazing absorption power compared to the liquid structure breakers mentioned. For example, 5 to 10, in some cases even up to 15% by weight of the liquid structure breakers can be processed with the anionic surfactants to form a solid, easily soluble product without the structure breaker gradually bleeding out and the dissolution rate decreasing over a long period of storage .
  • polymeric strengthening agents In particular when larger amounts (above 10% by weight) of the structure breakers are to be added to the anionic surfactants, it has been found that bleeding can be prevented reliably by the addition of so-called polymeric strengthening agents.
  • PEG Polyethylene glycol ethers
  • Typical examples are polyethylene glycols with an average molecular weight of 12,000 to 100,000. In this context, the use of PEG with an average molecular weight of 12,000 to 100,000 and in particular of 15,000 to 35,000 has proven to be particularly advantageous.
  • y represents 0 or numbers from 1 to 12, with polyethylene glycol ethers which have an average molecular weight of 400 to 20,000.
  • Typical examples are esters and polyesters of oxalic acid, succinic acid and adipic acid with PEG 400, PEG 5000 and PEG 12,000. Products of this type are distinguished by a particularly advantageous biodegradability.
  • transesterification products of dialkyl carbonate with polyethylene glycol ethers which have an average molecular weight of 400 to 20,000.
  • Typical examples are transesterification products of methyl ethyl carbonate with PEG 400, PEG 5000 and PEG 12,000.
  • the products are usually mono / di-ester mixtures, which - according to the statistics - can still contain portions of the alkyl radicals of the dialkyl carbonate used as starting material.
  • polymeric solidifying agents are olgosaccharides or polysaccharides with a degree of condensation of 5 to 1000. It is preferably polyglucose or polysorbitol.
  • the polymeric strengthening agents can be added to the hydrophobic structure breakers in amounts of 1 to 50, preferably 2 to 30% by weight, based on the structure breakers. Although it is fundamentally possible to process ternary mixtures of anionic surfactants, hydrophobic structure breakers and polymeric strengthening agents into easily soluble products, it is usually a. It is more advantageous to first add the polymeric solidifying agents to the structure breakers and to further process this preformed mixture after hardening with the anionic surfactants.
  • the selected solidifying agents can be added to the hydrophobic structure breakers, an intimate mixing with stirring or kneading having to be ensured if necessary with heating.
  • the structure breaker is a polyglycol ether and the polymeric solidifying agent is a PEG
  • the mixture can also be produced in situ by alkoxylating a mixture of fatty alcohol and PEG together.
  • the invention includes the knowledge that the polymeric solidifying agents also with a further mechanical compression of the anionic surfactants according to the invention (Extrusion etc.) have an advantageous effect and, for example, produce a lubricating effect.
  • the anionic surfactants can be used in the form of aqueous pastes or dry powders and then treated with the structure breakers and, if appropriate, the polymeric strengthening agents.
  • Anionic surfactants are usually reacted by reacting corresponding starting materials with sulfur trioxide or chlorosulfonic acid to give acidic half-esters of sulfuric acid or sulfonic acids, which are then neutralized with aqueous bases and optionally hydrolyzed.
  • the resulting aqueous pastes with a solids content of 5 to 65% by weight, based on the paste, are suitable starting materials for further processing in the sense of the invention.
  • aqueous pastes can also be used as spray-dried powders, as is the case with conventional ones Tower powder processes are accessible.
  • a variant is not to subject the aqueous, neutralized products to spray drying, but rather to spray the acidic sulfonation products together with aqueous bases and thus to neutralize and dry them in one step.
  • anionic surfactants in the form of spray-neutralized as well as spray-dried or steam-dried powders are suitable as starting materials.
  • the preferred starting materials are tallow alcohol sulfate in the form of aqueous pastes with a solids content of 5 to 65, preferably 50 to 65% by weight, or spray-neutralized or spray-dried powder.
  • the surfactant grain has to be structured, for which incorporation and homogeneous distribution of the optionally solidified structure breaker is required. This can be done in a variety of ways.
  • a particularly simple embodiment of the method consists in presenting the anionic surfactant in powder form and intimately mixing it with the required amount of the structure breaker which may have solidified.
  • Components such as paddle mixers from Lodige are used for this process or in particular spray mixers from Schugi are advantageous, in which the anionic surfactant is placed in the mixing chamber and the hydrophobic structure breaker is optionally sprayed on together with the polymeric solidifying agent. It is also possible to carry out the drying of the anionic surfactant pastes and the mixing simultaneously in a fluidized bed dryer. Dry, readily soluble powders are obtained which, if necessary, can be charged with further customary detergent additives and can be processed, for example, into detergent extrudates.
  • Zeolites, phosphates, polyacrboxylates, water glass, soda, sodium sulfate and the like can be considered as further detergent additives.
  • anionic surfactants can be so-called SKET granulation.
  • SKET granulation This is to be understood as granulation with simultaneous drying, which is preferably carried out batchwise or continuously in the fluidized bed.
  • the anionic surfactants can preferably be introduced into the fluidized bed at the same time or in succession via one or more nozzles in the form of aqueous pastes.
  • Fluidized bed apparatuses which are preferably used have base plates with dimensions of 0.4 to 5 m.
  • the SKET granulation is preferably carried out at fluidizing air speeds in the range from 1 to 8 m / s.
  • the granules are discharged from the fluidized bed preferably by means of a size classification of the granules.
  • the classification can take place, for example, by means of a sieve device or by means of an opposed air flow (sifting air) which is regulated in such a way that particles are only present Above a certain particle size removed from the fluidized bed and smaller particles are retained in the fluidized bed.
  • the inflowing air is usually composed of the heated or unheated classifier air and the heated soil air.
  • the soil air temperature is between 80 and 400, preferably 90 and 350 ° C.
  • a starting compound for example the powdered anionic surfactant, the hydrophobic structure breaker or a SKET granulate from an earlier test batch, is initially introduced at the start of the SKET granulation.
  • the water evaporates from the anionic surfactant paste, resulting in dried to dried germs which are coated with further amounts of anionic surfactant and structure breaker, granulated and again dried at the same time.
  • the result is an anionic surfactant grain which has been finely structured or segmented by the introduction of the structure breaker and is therefore particularly easily water-soluble.
  • the anionic surfactants are mixed in powder form with the optionally solidified structure breakers and the mixture is homogenized and solidified in a screw press.
  • the extrusion takes place via a perforated disk, so that press strands are formed which can be mechanically comminuted to extrudates or needles of the desired shape and dimension by known processes. Extrudates of this form show a particularly high dissolving speed and very good washing-up behavior in the washing machine.
  • anionic surfactants obtainable in the sense of the invention show a high solubility in cold water and easy washing-in behavior in the washing machine.
  • Another object of the invention therefore relates to solid washing, rinsing and cleaning agents which can contain 1 to 50, preferably 5 to 30% by weight, based on the agent, of the anionic surfactants according to the invention with improved solubility.
  • Another object of the invention finally relates to the use of the anionic surfactants according to the invention with improved solubility as raw materials for the production of solid washing, rinsing and cleaning agents in which they are present in amounts of 1 to 50, preferably 5 to 30,% by weight on the means - may be included.
  • Anionic surfactant content 54.1% by weight Unsulfated parts 1.5% by weight sodium sulfate 0.7% by weight water 43.7% by weight Ib
  • Anionic surfactant content 96.1% by weight Unsulfated parts 2.6% by weight Sodium sulfate 1.3% by weight II. Structure breaker
  • Talgal alcohol sulfate sodium salt paste (according to Ia) was granulated via a nozzle in a granulation drying system (AGT) from Glatt / FRG together with a mixture of nonionic surfactant and polymeric solidifying agent (according to II.f) and simultaneously dried.
  • AGT granulation drying system
  • TAS powder ex spray drying (Ic) with 2 kg of the structure breaker Il.f) were processed to a dry powder in a flight share mixer from Lodige.
  • nonionic surfactant tallow alcohol 40EO adduct
  • zeolite A 16% by weight sodium perborate
  • TAS-SKET granules were produced by simultaneous drying and granulation of 38 kg / h of talc alcohol sulfate sodium salt paste (according to I.a.) and 5 kg / h of soda.
  • nonionic surfactant tallow alcohol 40EO adduct

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Abstract

Des tensioactifs anioniques à solubilité améliorée s'obtiennent par traitement de tensioactifs anioniques choisis dans le groupe des sulfonates de benzène d'alkyle, sulfonates d'alcane, sulfonates d'oléfine, sulfonates d'alkyléther, sulfonates d'éther glycérique, sulfonates de α-méthyl ester, acides sulfoniques d'alkyle, sulfates d'alcool gras, sulfates d'éther d'alcool gras, sulfates d'éther glycérique, sulfates d'éther mélangé à de l'hydroxy, sulfates (d'éther) monoglycérique, sulfates (d'éther) d'amide d'acide gras, sulfosuccinates, sulfosuccinamates, sulfotriglycérides, savons amidés, acides carboxyliques éthériques, iséthionates, sarcosinates, taurides, sulfates d'alkyle oligoglucoside et phosphates d'alkyle (éther), conjointement avec un agent de rupture de structure hydrophobe et des stabilisants polymères choisis, pour former une poudre d'une manière connue en soi, ou bien par élaboration sous forme de morceaux. Ces produits présentent une excellente solubilité dans l'eau froide et s'utilisent pour fabriquer des agents tensioactifs solides.
PCT/EP1994/000207 1993-02-04 1994-01-26 Tensioactifs anioniques a solubilite amelioree WO1994018291A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP94906150A EP0682690B1 (fr) 1993-02-04 1994-01-26 Tensioactifs anioniques a solubilite amelioree
KR1019950703245A KR960701181A (ko) 1993-02-04 1994-01-26 용해도가 개선된 음이온계 계면활성제(anionic surfactants with improved solubility)
JP6517587A JPH08506366A (ja) 1993-02-04 1994-01-26 溶解性の改善されたアニオン性界面活性剤
DE59403312T DE59403312D1 (de) 1993-02-04 1994-01-26 Anionische tenside mit verbesserter löslichkeit

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4303211A DE4303211C2 (de) 1993-02-04 1993-02-04 Anionische Tenside mit verbesserter Löslichkeit
DEP4303211.7 1993-02-04

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JP (1) JPH08506366A (fr)
KR (1) KR960701181A (fr)
DE (2) DE4303211C2 (fr)
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WO (1) WO1994018291A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0716680B1 (fr) * 1993-09-02 1998-02-11 Henkel Kommanditgesellschaft auf Aktien Utilisation de melanges detergents aqueux
WO1998010051A1 (fr) * 1996-09-02 1998-03-12 Henkel Kommanditgesellschaft Auf Aktien Nouveaux agents aqueux pour nettoyer des surfaces dures
DE19946342A1 (de) * 1999-09-28 2001-04-05 Cognis Deutschland Gmbh Formkörper mit verbesserter Wasserlöslichkeit

Families Citing this family (6)

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Publication number Priority date Publication date Assignee Title
US5866530A (en) * 1995-11-25 1999-02-02 Henkel Kommanditgesellschaft Auf Aktien Non-aqueous liquid mixtures of alkyl polyglycoside and alkyl polyalkylene glycol ether useful in various detergent applications
DE19858886C2 (de) 1998-12-19 2002-10-31 Cognis Deutschland Gmbh Tensidgranulate
DE19911040A1 (de) * 1999-03-12 2000-09-21 Cognis Deutschland Gmbh Tensidgranulate
DE19941934A1 (de) * 1999-09-03 2001-03-15 Cognis Deutschland Gmbh Detergentien in fester Form
EP1690922A1 (fr) * 2005-02-11 2006-08-16 The Procter & Gamble Company Composition détergente solide
KR100771417B1 (ko) * 2007-02-15 2007-10-30 주식회사 에이엔디플러스 클린룸용 세정제 조성물

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US3803285A (en) * 1971-01-20 1974-04-09 Cpc International Inc Extrusion of detergent compositions
EP0208534A2 (fr) * 1985-07-09 1987-01-14 The Procter & Gamble Company Procédé de préparation de compositions détergentes granulaires séchées par atomisation
EP0352892A2 (fr) * 1988-07-28 1990-01-31 Kao Corporation Composition détergente concentrée granulaire à haute densité

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LU60943A1 (fr) * 1970-05-20 1972-02-23
JPS5241612A (en) * 1975-09-30 1977-03-31 Kao Corp Granular or powdered detergent compositions
DE4124701A1 (de) * 1991-07-25 1993-01-28 Henkel Kgaa Verfahren zur herstellung fester wasch- und reinigungsmittel mit hohem schuettgewicht und verbesserter loesegeschwindigkeit

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Publication number Priority date Publication date Assignee Title
US3803285A (en) * 1971-01-20 1974-04-09 Cpc International Inc Extrusion of detergent compositions
EP0208534A2 (fr) * 1985-07-09 1987-01-14 The Procter & Gamble Company Procédé de préparation de compositions détergentes granulaires séchées par atomisation
EP0352892A2 (fr) * 1988-07-28 1990-01-31 Kao Corporation Composition détergente concentrée granulaire à haute densité

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0716680B1 (fr) * 1993-09-02 1998-02-11 Henkel Kommanditgesellschaft auf Aktien Utilisation de melanges detergents aqueux
WO1998010051A1 (fr) * 1996-09-02 1998-03-12 Henkel Kommanditgesellschaft Auf Aktien Nouveaux agents aqueux pour nettoyer des surfaces dures
DE19946342A1 (de) * 1999-09-28 2001-04-05 Cognis Deutschland Gmbh Formkörper mit verbesserter Wasserlöslichkeit

Also Published As

Publication number Publication date
ES2105639T3 (es) 1997-10-16
EP0682690B1 (fr) 1997-07-09
DE4303211C2 (de) 1996-05-15
KR960701181A (ko) 1996-02-24
JPH08506366A (ja) 1996-07-09
DE4303211A1 (de) 1994-08-11
EP0682690A1 (fr) 1995-11-22
DE59403312D1 (de) 1997-08-14

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