WO1994018291A1

WO1994018291A1 - Anionic surfactants with improved solubility

Info

Publication number: WO1994018291A1
Application number: PCT/EP1994/000207
Authority: WO
Inventors: Karl Schmid; Andreas Syldath; Michael Neuss; Ditmar Kischkel; Thomas Krohnen; Hubert Pawelczyk
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1993-02-04
Filing date: 1994-01-26
Publication date: 1994-08-18
Also published as: KR960701181A; DE59403312D1; DE4303211A1; EP0682690B1; DE4303211C2; JPH08506366A; ES2105639T3; EP0682690A1

Abstract

Anionic surfactants with improved solubility are obtained by processing anionic surfactants selected from the group of alkylbenzenesulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerine ether sulfonate, α-methyl ester sulfonates, alkylsulfonic acids, fatty alcohol sulfates, fatty alcohol ether sulfates, glycerine ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, sulfosuccinates, sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids, isethionates, sarcosinates, taurides, alkyl oligoglucoside sulfates and alkyl (ether) phosphates, together with a hydrophobic structure breaker and selected polymer stabilizers to form a powder using per se known methods, or by working them into lumps. The products show excellent cold-water solubility and can be used in preparing solid surface active agents.

Description

Anionic surfactants with improved solubility

Field of the Invention

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.

State of the art

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.

In the past there has been no lack of approaches

To improve the problem of the poor solubility in cold water of anionic surfactants, in particular of alkylbenzenesulfonates, fatty alcohol sulfates and cx-methyl ester sulfonates. Two main concepts were pursued, namely

a) the concomitant use of hydrotropes and b) the surface enlargement of the surfactant grain.

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. In this context, we would like to refer to the overview of H.Steich in fats, soaps, paints. 71: 381 (1969).

However, the improvement in solubility in cold water, in particular of fatty alcohol sulfates, is usually achieved by adding surfactants with high HLB values, for example highly ethoxylated polyglycol ethers (tallow alcohol 40 EO adduct) or the like, as hydrotropes. The dissolution rates that can be achieved in this way, particularly in the case of fat However, alcohol sulfates are still unsatisfactory for a large number of technical applications.

A completely different approach to improving the solubility of anionic surfactants is described in German patent application DE-Al-40 30 688 (Henkel). Here it is proposed to dry aqueous surfactant pastes using hot steam. By condensing the superheated steam on the cooler feed and releasing the heat of condensation to the goods to be dried, the droplets of surfactant are spontaneously heated to the boiling point of the water. As a result, a multitude of fine channels form in the tenside grain when the water escapes. 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. Nevertheless, there is the disadvantage that the method described is associated with a high level of technical complexity.

According to the teaching of DE-A1 41 24 701 (Henkel), 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. According to embodiment 1, a detergent preparation containing Ci2 / i8 fatty alcohol sulfate, ^c ^12/18 ~ ^{fat lkono1} "" ⁵ EO- Cl6 18 ~ ^Tal 9 ^{fatty alcohol: lol,} " ⁵ EO adduct and - based on the nonionic surfactants - not less than 45

% By weight (!) Polyethylene glycol with a molecular weight of approx. 400 is disclosed, which extrudes and homogenizes after homogenization Granules are processed. However, the rate of dissolution of the resulting solid detergents is still unsatisfactory. In addition, the presence of the large amounts of polymer required is not desirable.

According to EP-A2 0 208 534, 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. However, 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. According to Example 6, compositions are disclosed which contain tallow alcohol sulfate, alkylbenzenesulfonate and polyethylene glycol with a molecular weight of approximately 20,000.

For further process developments that relate to the production of solid anionic surfactants, is at this point only marginally referred. For example, 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.

Description of the invention

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, alkyl sulfate and alkyl oligate glucos is formed, together with a hydrophobic structure breaker and a polymeric hardening agent selected from the group formed by bl) polyethylene glycol ether with an average molecular weight of 12,000 to 500,000, b2) esters of dicarboxylic acids with an average molecular weight of 400 to 20,000, b3) transesterification products of dialkyl carbonate with polyethylene glycol ether with an average molecular weight of 400 to 20,000 and b4) Oligosaccharides or polysaccharides with a degree of condensation of 5 to 1000,

processed into a powder in a manner known per se or brought into lumpy form.

Surprisingly, it was found that the 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. As a result, 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.

In view of a high dissolution rate, it has proven to be particularly advantageous to apply the principle underlying the invention to poorly soluble anionic surfactants of the fatty alcohol sulfate type which follow the formula (I)

R ¹ OS0 ₃ X (I)

in which 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, sucurate, urethane sulfate is formed sulfide and alkyl (ether) phosphates, together with a hydrophobic structure breaker and a polymeric solidifying agent selected from the group formed by

bl) polyethylene glycol ethers with an average molecular weight of 12,000 to 500,000, b2) esters of dicarboxylic acids with an average molecular weight of 400 to 20,000, b3) transesterification products of dialkyl carbonate with polyethylene glycol ethers with an average molecular weight of 400 to 20,000 and b4) Oligosaccharides or polysaccharides with a degree of condensation of 5 to 1000,

processed into a powder in a manner known per se or brought into lumpy form. Poorly soluble anionic surfactants

The anionic surfactants mentioned are all known substances. For their production, reference is made to the relevant standard works, for example J.Falbe (ed.) "Surfactants in consumer products", Springer Verlag, Berlin, 1987, pp. 54-85 or 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. This applies in particular to alkylbenzenesulfonates (dodecylbenzenesulfonates), o-methyl ester sulfonates and, above all, fatty alcohol sulfates, which should therefore be the focus of this patent application in the foregoing for the other species mentioned.

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)

RioSOs (I)

in which 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 Fettsäuremethylester¬ 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

C chain distribution Cιg: Ci8 ^on about 1: 1 or a Rapsalko¬ holsulfat with a C] _8 content of more than 95 wt .-%.

Hydrophobic structure breaker

Non-ionic surfactants which have an HLB value in the range from 0.5 to 10 are particularly suitable as hydrophobic structure breakers.

al) In detail, this includes, for example, fatty alcohols and / or fatty alcohol polyglycol ethers of the formula

(II),

CH ₃ IR ² 0- (CH ₂ CHO) _n (CH2CH2 ^θ ) III ^H (H)

in the R- for a linear or branched aliphatic hydrocarbon residue with 8 to 18 carbon atoms men and 0, 1, 2 or 3 double bonds, n is 0 or numbers from 1 to 3 and m is 0 or numbers from 1 to 10.

These are known surfactants which are produced industrially by propoxylation and / or ethoxylation of fatty alcohols. Typical examples of 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 Roelen's oxo synthesis are accessible. Adducts of 1 to 3 moles of ethylene oxide with technical C12 / 8- or ^C 12/14 ~ ^κ °] c ^os ι ^ett l] ς ^ono l ^sc * _. Nitte are preferably used.

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. However, this fact is in no way a disadvantage for the suitability of such surfactants. In the sense of a preferred embodiment, it has rather proven that the free fatty alcohols alone are extremely effective as structure breakers. For example, a product based on 90% by weight tallow alcohol sulfate and 10% by weight fatty alcohol - preferably Ci2 / 18 ~ ^DZW «Ci2 / i4 coconut oil alcohol ~ - shows a particularly high dissolution rate. The possibility that free fatty alcohols can also be used as structure breakers has been taken into account in the general formula (II) (n = 0, = 0).

a2) A_Ucyioligoglycosides of the formula (III) are also suitable as structure breakers,

_R 3_o_ [G] _p (III)

in which R3 is an alkyl radical having 12 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and 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. As a representative of the extensive literature, reference is made here to the documents EP-A1-0 301 298 and WO 90/3977 (Henkel).

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. The index number p in the general formula (III) indicates the degree of oligomerization (DP degree), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p in a given compound must always be an integer and here, above all, the values p = 1 to 6 can assume, the value p for a certain alkyl oligoglycoside is an analytically determined arithmetic quantity, which usually represents a fractional number. 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 radical R 1 can be derived from primary alcohols having 12 to 22, preferably 12 to 18 carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachyl alcohol and behenyl alcohol and their technical mixtures, such as those used in the hydrogenation of technical fatty acid methyl esters. Preferred are Alkyloligo¬ glucoside of chain length Ci2 ^_c 18 ^{(DP = 1 to 3)} ^{', which} may be produced on the basis of coconut oil, palm oil, palm stearin, palm kernel oil or beef tallow and a An¬ part of less than 10 wt .-% of shorter chain homologues include .

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.

a3) Fatty acid esters of the formula (IV) are also suitable as hydrotropic structure breakers,

R ⁴ CO-OR ⁵ (IV)

in which 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.

Typical examples are esters of palmitic acid, stearic acid, arachic acid and behenic acid and their technical mixtures with methanol, ethanol, propanol, butanol, glyeerin and technical oligoglycerol mixtures, which in turn can have an average degree of self-condensation of 2 to 10. As far as glyeerin or oligoglycerol esters are concerned, they can be present as full esters, but in particular as partial esters. Ci6 18 ~ ^Ta 19 ^ ^ettsauremetn yl ~ esters are preferably used.

a4) As a further possibility, dialkyl ethers of the formula (V) can also be used,

R ⁵ -0-R ⁶ (V) in which R ^ and R ^ independently of one another represent linear or branched alkyl radicals having 8 to 18 carbon atoms.

These are also known substances which can be obtained by the relevant methods of preparative organic chemistry. Processes for their preparation, for example by condensation of fatty alcohols in the presence of p-toluenesulfonic acid, are known, for example, from Bull.Soc. Chim.France, 333 (1949), DE-Al 40 39 950 (Hoechst) and DE-Al 41 03 489 (Henkel) are known. From an application point of view, symmetrical dialkyl ethers are preferred which have 8 to 12 carbon atoms in the alkyl radicals. Dialkyl ethers of the formula (V), in which R and R ^ are octyl and / or 2-ethylhexyl radicals, have a particularly rapid structuring capacity. The dialkyl ethers which are particularly preferred for the purposes of the invention are thus di-n-octyl ether and di-2-ethylhexyl ether.

a5) Fat ketones of the formula (VI) are also suitable as hydrophobic structure breakers,

R7-CO-CH ₂ R8 (VT)

in which 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.

a6) The substance classes suitable as structure breakers also include Guerbet alcohols of the formula (VII),

CH2OH

I.

CH ₃ CH ₂ (CH2) χCH- (CH ₂ ) _x _ ₂ CH2CH3 (VII)

where 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.

a7) Finally, 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.

Polymeric solidifying agents

If 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 .

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. bl) Polyethylene glycol ethers (PEG) with an average molecular weight of 10,000 to 500,000 are preferably considered as polymeric solidifying agents. 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.

b2) Other polymeric solidifying agents are esters of dicarboxylic acids of the formula (VTII)

HOOC- (CH2) yCOOH (VTII)

in which 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.

b3) Another group of suitable polymeric strengthening agents are 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.

b4) Finally, further 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. In the preferred embodiment, according to which 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.

In the event that a particularly high solidification of the non-ionic surfactants is required and the hydrophobic structure breakers must be prevented from bleeding out over a very long period of time, it has proven to be advantageous to add long-chain fatty acids with 16 to 22 carbon atoms to the polymeric solidification agents , for example Ci6 / 18 ~ ^Ta l9 ^ ^ett ~ acid to add.

Application form of the anionic surfactants

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.

The 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. For the purposes of the invention, anionic surfactants in the form of spray-neutralized as well as spray-dried or steam-dried powders are suitable as starting materials. For details of the spray drying or spray neutralization of surfactants, reference is made to ROEMPP Chemistry Lexicon, 9th edition, Thieme-Verlag, Stuttgart, 1992, p.4259 / 4260. As already stated, 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.

Manufacture of easily soluble products

To produce the readily soluble anionic surfactants, 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.

Another possibility is to subject the anionic surfactants to so-called SKET granulation. This is to be understood as granulation with simultaneous drying, which is preferably carried out batchwise or continuously in the fluidized bed. 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. Advantageously, 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. In the fluidized bed, 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.

In a preferred embodiment of the invention, 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. Industrial applicability

The 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.

The following examples are intended to explain the subject matter of the invention in more detail without restricting it.

Examples

I. Production of Talcs Alcohol Sulphate (TAS)

Ia Preparation of a Ci6 / i8 tallow alcohol sulfate paste. ^In a continuously working falling film reactor (length 120 cm, cross section 1 cm, educt throughput 600 g / h) with jacket cooling and lateral SO3 fumigation, 1300 (5 mol) of a technical tallow fatty alcohol (Stenol ( ^R ) 1618, sales product from Henkel KGaA, Düsseldorf, FRG) at 45 ° C with 420 g (5.25 mol) of gaseous sulfur trioxide (5 vol.% In air) - corresponding to a molar ratio of alcohol: SO3 = 1: 1.05. The acidic sulfonation product was continuously introduced at 80 ° C. into a 37% by weight aqueous sodium hydroxide solution and neutralized in the process. The reaction product was then adjusted to a pH of 10 using sodium hydroxide solution.

Characteristics of the product:

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 Production of a Ciß / ig tallow alcohol sulfate powder via spray neutralization. Manufacturing instruction Ia) was repeated. However, the acidic sulfonation product was sprayed together with 55% by weight sodium hydroxide solution at 70 ° C. through two separate nozzles into a reaction tube and simultaneously neutralized in a countercurrent of air and dried to a residual water content of <1% by weight.

Characteristics of the product:

Anionic surfactant content /, 95.7% by weight Unsulphated parts 2.4% by weight Sodium sulfate 1.9% by weight

I.e. Production of a Ci6 / i8 tallow alcohol sulfate powder via spray drying. The aqueous surfactant paste from I.a.) was sprayed in a spray tower from Niro-Atomizer in a manner known per se with air in countercurrent at 270 ° C. and dried to a residual water content of <1% by weight.

Characteristics of the product:

Anionic surfactant content 96.1% by weight Unsulfated parts 2.6% by weight Sodium sulfate 1.3% by weight II. Structure breaker

1000 g of C R2 / i4-coconut fatty alcohol-3EO adduct (dehydol ( ^R ) LS3, commercial product from Henkel KGaA, Düsseldorf / FRG) with 0 to 5% by weight polyethylene glycol with a molecular weight of 400 to 100,000 displaced. The solidification of the products was determined via the pour point (cf. Tab. 1):

Tab. 1: Pourpoints (Pp) of structure breakers

Legend: M (PEG) Average molecular weight of polyethylene glycol (PEG) c (PEG) Concentration PEG based on non-ionic surfactant III. Examples according to the invention

Production example St.

Production of a readily soluble TAS-SKET granulate. 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.

Characteristics of the process:

Fluidized bed,

- diameter 400 mm

- area 0.13 m ²

- Air speed 3.8 m / s

Temperature,

- Soil air 132 ° C

- Classification air 20 ° C

- Air outlet 73 ° C

Air flow 1300 m ³ / h

Air load 11 g H2θ / kg air

Throughput,

- Tallow alcohol sulfate paste ... 38 kg / h

- Structure crusher 2 kg / h

- Starting mass (SKET granulate). 20 kg Characteristics of the product:

Anionic surfactant content 86% by weight

Water content <1% by weight

Bulk density 620 g / 1

Sieve analysis

> 1.6 mm 9.8% by weight

0.8 mm 45.2% by weight

0.6 mm 22.1% by weight

0.4 mm 17.3% by weight

0.2 mm 4.8% by weight

<0.1 mm 0.8% by weight

A dust-free and non-sticky granulate with a high surfactant content was obtained.

Production example H2:

Production of a readily soluble TÄS powder. 20 kg of 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.

Production example H3:

Production of easily soluble TAS granules. A mixture of 90% by weight of tallow alcohol sulfate powder via spray neutralization (Ib) and 10% by weight of structure breaker, namely Ci2 / 14 ^_κ ° Kosfettalkohol (Lorol ( ^R ) Spezial, Henkel KGaA, Düsseldorf / FRG) extruded in a screw press through a perforated disc (diameter of the holes 1.1 mm) and then the resulting strands processed into granular granules.

Production example H4:

Production of easily soluble TAS detergent granules.

a) In a spray mixer from Schugi, 2 kg of the structure breaker Il.f were sprayed onto 20 kg of spray-neutralized tallow alcohol sulfate powder (I.b). The resulting mixture was used in the following universal detergent formulation.

b) A commercially available universal detergent formulation of the composition

22% by weight of TAS powder ex spray neutralization (I.b) / structure breaker (Il.f)

5% by weight nonionic surfactant (tallow alcohol 40EO adduct) 35% by weight zeolite A 16% by weight sodium perborate

7% by weight water glass 15% by weight auxiliaries

was extruded in a screw press, then extruded through a perforated disk (diameter of the holes 1.1 mm) and the resulting strands were then processed into granular granules. IV. Verσl eich products

Comparative product VP1:

Analogous to production example Hl, 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.

Comparative product VP2:

Tallow alcohol sulfate powder ex spray neutralization (I.b).

Comparative product VP3:

Analogous to preparation example H3, a tallow alcohol sulfate powder was extruded and granulated via spray neutralization.

Comparative product VP4:

Analogous to preparation example H4, a commercially available universal detergent formulation of the composition was used

22% by weight of TAS powder ex spray neutralization (I.b),

5% by weight nonionic surfactant (tallow alcohol 40EO adduct)

35% by weight of zeolite A

16% by weight sodium perborate

7% by weight water glass

15% by weight of auxiliaries

extruded and granulated. TV. Solicability investigations

To investigate the solubility, 10 g of the solids according to the invention or the comparison substances were dissolved or dispersed in 100 ml of water (30 ° C., 16 ° d). After 30, 120 and 300 s, the solutions or dispersions were filtered off, the residue was dried and weighed out. The results are summarized in Tab. 1:

Tab. 1: Solubility tests

Percentages in% by weight

Claims

1. Anionic surfactants with improved solubility, obtainable by selecting sparingly soluble anionic surfactants from the group consisting of alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkylethersulfonates, glycerolethersulfonates, o-methyl ester sulfonates, sulfofatty acids, fatty alcohol sulfates, fatty alcohols , Glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, sulfosuccinates, sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids, isethionates, sarcosinates, taurides, alkyl oligoglucoside sulfates and alkyl sulfate together with a hydrophobic structure breaker and a polymeric hardening agent selected from the group formed by

bl) polyethylene glycol ethers with an average molecular weight of 12,000 to 500,000, b2) esters of dicarboxylic acids with an average molecular weight of 400 to 20,000, b3) transesterification products of dialkyl carbonate with polyethylene glycol ethers with an average molecular weight of 400 to 20,000 and b4) oligo- or polysaccharides with a degree of condensation of 5 to 1000,

processed into a powder in a manner known per se or brought into lumpy form.

2. Anionic surfactants according to claim 1, characterized in that fatty alcohol sulfates of the formula (I) are used as the poorly soluble anionic surfactants,

RioSOsX (I)

in which R represents an alkyl and / or alkenyl radical having 12 to 22 carbon atoms and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.

3. 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, oc-methyl ester sulfonates, sulfofatty acids, fatty alcohol sulfates. Fatty alcohol ether sulfates, glycerin ether sulfates, hydroxymixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, sulfosuccinates, sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids, isethionates, sarcosinates, taurucosulfonate oligosulfonate, alkyl sulfide oligosulfurates, alkyl sulfides ¬ det, together with a hydrophobic structure breaker and a polymeric solidifying agent selected from the group formed by

processed into a powder in a manner known per se or brought into lumpy form.

4. The method according to claim 3, characterized in that fatty alcohol sulfates of the formula (I) are used as anionic surfactants,

Rl-OSOsX (I)

in which R ^ represents an alkyl and / or alkenyl radical having 12 to 22 carbon atoms and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.

5. Process according to claims 3 and 4, characterized gekenn¬ characterized in that fatty alcohol sulfates of the formula (I) are used in which R ^{1 is} an alkyl radical having 16 to 18 carbon atoms and X is sodium.

6. The method according to claims 3 to 5, characterized gekenn¬ characterized in that non-ionic surfactants are used with a HLB value in the range of 0.5 to 10 as a hydrophobic structure breaker.

7. Process according to Claims 3 to 5, characterized in that fatty alcohols and / or fatty alcohol polyglycol ethers of the formula (II) are used as the hydrophobic structure breaker,

CH ₃

I.

R ² 0- (CH ₂ CHO) _n (CH2CH2θ) ιιιH (II)

in which R ^{2 is} a linear or branched aliphatic hydrocarbon radical with 8 to 18 carbon atoms and 0, 1, 2 or 3 double bonds, n is 0 or numbers from 1 to 3 and m is 0 or numbers from 1 to 10 .

8. The method according to claims 3 to 5, characterized gekenn¬ characterized in that one uses as a hydrophobic structure breaker alkyl oligoglycosides of formula (III),

R ³ -0- [G] _p (III)

in which R ^{3 is} an alkyl radical having 12 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10.

9. Process according to Claims 3 to 5, characterized in that fatty acid esters of the formula (IV) are used as the hydrophobic structure breaker,

R ⁴ C0-0R ⁵ (TV) in which R ^ CO stands for an acyl radical with 16 to 22 carbon atoms and R- for an alkyl radical with 1 to 4 carbon atoms, a glycerol or oligoglycerol radical.

10. The method according to claims 3 to 5, characterized gekenn¬ characterized in that one uses as a hydrophobic structure breaker Dial¬ kylether of formula (V),

R5_ ₀ _R6 (V)

in which R ^ and R- independently of one another represent linear or branched alkyl radicals having 8 to 18 carbon atoms.

11. Process according to claims 3 to 5, characterized in that fat ketones of the formula (VT) are used as the hydrophobic structure breaker,

R7_ _C0 _ _CH2R 8 ( _VI )

in which R ⁷ and R ^ independently of one another represent alkyl radicals having 7 to 17 carbon atoms.

12. The method according to claims 3 to 5, characterized gekenn¬ characterized in that Guerbet alcohols of the formula (VII) are used as the hydrophobic structure breaker,

CH2OH

I.

CH ₃ CH ₂ (CH2) χCH- (CH2) _x _2CH2CH ₃ (VII) where x stands for numbers from 6 to 16.

13. The method according to claims 3 to 5, characterized gekenn¬ characterized in that saturated hydrocarbons are used as a hydrophobic structure breaker.

14. Process according to Claims 3 to 13, characterized in that the hydrophobic structure breakers are added to the anionic surfactants in amounts of 1 to 50% by weight, based on the mixture.

15. The method according to claims 3 to 14, characterized gekenn¬ characterized in that the polymeric solidifying agent used is polyethylene glycol ether with an average molecular weight of 10,000 to 500,000.

16. The method according to claims 3 to 14, characterized gekenn¬ characterized in that esters of dicarboxylic acids of the formula (VTII),

HOOC- (CH2) yCOOH (VIII)

in which y represents 0 or numbers from 1 to 12, with polyethylene glycol ethers which have an average molecular weight of 400 to 20,000.

17. Process according to claims 3 to 14, characterized in that transesterification products of dialkyl carbonate with polyethylene glycol ethers, which have an average molecular weight of 400 to 20,000, are used as the polymeric solidifying agent.

18. The method according to claims 3 to 14, characterized gekenn¬ characterized in that oligo- or polysaccharides with a degree of condensation of 5 to 1000 are used as the polymeric solidifying agent.

19. The method according to claims 3 to 18, characterized gekenn¬ characterized in that the nonionic surfactants, the polymeric solidifying agents in amounts of 1 to 50 wt .-% - based on the nonionic surfactants - is added.

20. The method according to claims 3 to 19, characterized gekenn¬ characterized in that the anionic surfactants in the form of aqueous pastes with a solids content of 5 to 65 wt .-% - based on the paste - used.

21. The method according to claims 3 to 19, characterized gekenn¬ characterized in that one uses the anionic surfactants in the form of spray-neutralized or spray-dried powder.

22. The method according to claims 3 to 19, characterized gekenn¬ characterized in that the anionic surfactants with the hydrophobic structure breakers and the polymeric solidifying agents are processed in a mixer to a dry powder.

23. The method according to claims 3 to 19, characterized gekenn¬ characterized in that the anionic surfactants with the hydrophobic structure breakers and the polymeric strengthening agents according to the SKET granulation process to dry granules.

24. The method according to claims 3 to 19, characterized gekenn¬ characterized in that the anionic surfactants with the hydrophobic structure breakers and the polymeric strengthening agents are processed in a screw press to a dry extrudate.

25. Solid washing, rinsing and cleaning agents containing 1 to 50% by weight, based on the agent, of anionic surfactants with improved solubility according to claim 1.

26. Use of anionic surfactants with improved solubility according to claim 1 as raw materials for the manufacture of solid washing, rinsing and cleaning agents.