EP0682690B1 - Anionische tenside mit verbesserter löslichkeit - Google Patents

Anionische tenside mit verbesserter löslichkeit Download PDF

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EP0682690B1
EP0682690B1 EP94906150A EP94906150A EP0682690B1 EP 0682690 B1 EP0682690 B1 EP 0682690B1 EP 94906150 A EP94906150 A EP 94906150A EP 94906150 A EP94906150 A EP 94906150A EP 0682690 B1 EP0682690 B1 EP 0682690B1
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Prior art keywords
fatty alcohol
sulfates
ether
alcohol sulfates
weight
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German (de)
English (en)
French (fr)
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EP0682690A1 (de
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Karl Schmid
Andreas Syldath
Michael Neuss
Ditmar Kischkel
Thomas Krohnen
Hubert Pawelczyk
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Henkel AG and Co KGaA
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
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    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/83Mixtures of non-ionic with anionic compounds
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    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
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    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707Polyethers, e.g. polyalkyleneoxides
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    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/04Carboxylic acids or salts thereof
    • C11D1/06Ether- or thioether carboxylic acids
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    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/04Carboxylic acids or salts thereof
    • C11D1/10Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates thereof
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    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/123Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
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    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/126Acylisethionates
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    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
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    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
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    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
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    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
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    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29Sulfates of polyoxyalkylene ethers
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    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/34Derivatives of acids of phosphorus
    • C11D1/345Phosphates or phosphites
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    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/662Carbohydrates or derivatives
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    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/667Neutral esters, e.g. sorbitan esters
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    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols
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    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/722Ethers 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 of the fatty alcohol sulfate type with improved solubility, and to a process for their preparation in which fatty alcohol sulfates are processed together with selected hydrophobic structure breakers and selected polymeric strengthening agents to form solid, easily water-soluble products.
  • Anionic surfactants are important components of detergents, dishwashing detergents and cleaning agents. In contrast to nonionic surfactants, which have an inverse solubility behavior and are more soluble in cold water as a result of hydrogen bonds than in warm ones, anionic surfactants behave conventionally; H. their solubility increases more or less linearly with temperature until the solubility product is reached.
  • H their solubility increases more or less linearly with temperature until the solubility product is reached.
  • hydrotropes are undoubtedly the short-chain alkylarylsulfonates, such as toluene, xylene or cumene sulfonate. They are suitable, for example, as solubilizers for anionic and nonionic surfactants in the production of liquid detergents.
  • solubilizers for anionic and nonionic surfactants in the production of liquid detergents.
  • the improved Solubility is probably due to advantageous mixed micelle formation.
  • solubility in cold water in particular of fatty alcohol sulfates
  • hydrotrope surfactants with high HLB values for example highly ethoxylated polyglycol ethers (tallow alcohol + 40EO adduct) or the like.
  • HLB values for example highly ethoxylated polyglycol ethers (tallow alcohol + 40EO adduct) or the like.
  • dissolution rates that can be achieved in this way are still unsatisfactory for a large number of technical applications.
  • German patent application DE-A1-4030688 (Henkel). It is proposed here to dry aqueous surfactant pastes using hot steam. Condensation of the superheated steam on the cooler feed and release of the heat of condensation to the material to be dried results in the surfactant droplets heating up spontaneously to the boiling point of the water. As a result, a multitude of fine channels form when the water escapes in the Tensidkom. The resulting high internal surface area - for example compared to conventional spray-dried products - leads to a significantly improved dissolution rate. Nevertheless, there is the disadvantage that the method described is associated with a high level of technical complexity.
  • solid detergents with high bulk density and improved solubility are obtained by adding mixtures of anionic and nonionic surfactants to polyethylene glycol ethers with a molecular weight in the range from 200 to 12,000, preferably 200 to 600, and then drying and / which brings in solid form.
  • a detergent preparation containing C 12/18 fatty alcohol sulfate, C 12-18 fatty alcohol + 5EO- / C 16/18 tallow fatty alcohol + 5EO adduct and - based on the nonionic surfactants - not less than 45% by weight % Disclosed polyethylene glycol with a molecular weight of about 400, which is extruded after homogenization and processed into granules. 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.
  • 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).
  • a mixture comprising alkylbenzenesulfonate and fatty alcohol sulfate is described, to which a C 12/13 oxo alcohol + 6.5EO 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 2124526 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, for example, from international patent application WO 92/09676 (Henkel), which can be obtained by treating aqueous alkyl sulfate pastes with soda and zeolites and then extruding them. The document does not reveal anything about the solids' dissolution rate.
  • the object of the invention was to provide fatty alcohol sulfates which are anionic even in cold water and whose production is free from the disadvantages described.
  • the invention relates to anionic surfactants with an improved dissolution rate, obtainable by sparingly soluble fatty alcohol sulfates of the formula (I) , R 1 OSO 3 X (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 glucammonium, together with a hydrophobic structural breaker selected from the group of fatty alcohols and / or fatty alcohol polyglycol ethers of the formula (II) , in which R 2 is a linear or branched aliphatic hydrocarbon radical having 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 and a polyethylene glycol ether an average molecular weight from 12,000 to 500,000 as a polymeric solidifying agent processed in a
  • the fatty alcohol sulfates according to the invention which have a content of selected 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 fatty alcohol sulfates with a minimum grain size required for good solubility.
  • commercially available fatty alcohol sulfates are too coarse-grained to be sufficiently soluble.
  • Another problem is also that even finely divided powders during solidification, e.g. B. by extrusion, again to coarse-grained and therefore less water-soluble material.
  • the inventive concept now consists in subsequently structuring the fatty alcohol sulfate com by introducing a hydrophobic structure breaker and in this way creating anion surfactant zones within the com which are separated from one another by the hydrophobic additive.
  • the conventional Grobkom so to speak the "single crystal” results in a conglomerate of fine grains, which are separated by the hydrophobic structure breaker and thus have a significantly improved solubility even after mechanical compression.
  • 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.
  • the invention further relates to a process for the preparation of anionic surfactants with an improved dissolution rate, in which poorly soluble fatty alcohol sulfates of the formula (I) , R 1 OSO 3 X (I) in which R 1 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, together with a hydrophobic structural breaker selected from the group of fatty alcohols and / or fatty alcohol polyglycol ethers of the formula (II) , in which R 2 is a linear or branched aliphatic hydrocarbon radical having 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 and a polyethylene glycol ether with an average molecular weight of 12,000 to 500,000 as a polymeric solid
  • Fatty alcohol sulfates are understood to be anionic surfactants which are usually prepared by sulfating alcohols with gaseous sulfur trioxide or chlorosulfonic acid and subsequent neutralization with bases.
  • Typical examples are the sulfates of lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol and erucyl alcohol, as well as their technical mixtures, such as those derived from the hydrogenation of aldehydes from the hydrogenation or the ethyl ether 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 C 16 : C 18 of approximately 1: 1 or a rapeseed alcohol sulfate with a C 18 content of more than 95% by weight.
  • Fatty alcohols and / or fatty alcohol polyglycol ethers are suitable as hydrophobic structure breakers. These are known surfactants which are produced on an industrial scale 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 context 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
  • Adducts of 1 to 3 moles of ethylene oxide with technical C 12/18 or C 12/14 coconut fatty alcohol cuts are preferably used.
  • the alkoxylation products can be a conventional, and in particular have a narrow homolog distribution.
  • this fact is in no way a disadvantage for the suitability of such surfactants.
  • a product based on 90% by weight tallow alcohol sulfate and 10% by weight fatty alcohol - preferably C 12/18 or C 12/14 coconut fatty alcohol - shows a particularly high dissolution rate.
  • the hydrophobic structure breakers can usually be added to the fatty alcohol sulfates in amounts of 1 to 50, preferably 2 to 15 and in particular 5 to 10% by weight, based on the mixture.
  • Polyethylene glycols with an average molecular weight of 12,000 to 500,000 come into consideration as polymeric solidifying agents which reliably prevent the " bleeding" of the liquid structure breakers at higher concentrations.
  • 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.
  • 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.
  • polymeric solidifying agents can be added to the hydrophobic structural breakers, with intimate mixing having to be ensured with stirring or kneading, if necessary with heating.
  • the mixture can also be generated in situ by alkoxylating a mixture of fatty alcohol and PEG together.
  • the invention includes the finding that the polymeric solidifying agents also have an advantageous effect in the case of a further mechanical compression of the fatty alcohol sulfates according to the invention (extrusion, etc.) and, for example, produce a lubricating effect.
  • a particularly high degree of solidification of the nonionic surfactants is required and the hydrophobic structure breakers have to be prevented from bleeding out over a very long period of time, it has proven to be proven to be advantageous to add long-chain fatty acids with 16 to 22 carbon atoms, for example C 16/18 tallow fatty acid, to the polymeric strengthening agents.
  • the fatty alcohol sulfates can be used in the form of aqueous pastes or dry powders and then treated with the structure breakers and the polymeric strengthening agents.
  • Fatty alcohol sulfates are usually converted by reacting appropriate fatty alcohols with sulfur trioxide or chlorosulfonic acid to form acidic half-esters of sulfuric acid or sulfonic acids, which are then neutralized with aqueous bases.
  • 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 can be obtained by conventional tower powder processes.
  • a variant is not to subject the aqueous, neutralized products to spray drying, but rather to spray the acidic sulfation products together with aqueous bases and thus to neutralize and dry them in one step.
  • fatty alcohol sulfates in the form of spray-neutralized as well as spray-dried or steam-dried powders are suitable as starting materials.
  • the preferred starting material is 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 core In order to produce the readily soluble fatty alcohol sulfates, the surfactant core must be structured, for which incorporation and homogeneous distribution of the 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 fatty alcohol sulfate in powder form and intimately mixing it with the required amount of the solidified structure breaker.
  • Components such as paddle mixers from Lödige or in particular spray mixers from Schugi are advantageous for this process, in which the anionic surfactant is placed in the mixing chamber and the hydrophobic structure breaker is sprayed together with the polymeric solidifying agent.
  • SKET granulation Another possibility is to subject the fatty alcohol sulfates to 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 fatty alcohol sulfates can be introduced into the fluidized bed, preferably in the form of aqueous pastes, simultaneously or in succession via one or more nozzles.
  • 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 preferably discharged from the fluidized bed via a size classification of the granules.
  • the classification can be carried out, for example, by means of a sieve device or by means of an opposed air flow (sight air) which is regulated in such a way that only particles of a certain particle size are 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 bottom air.
  • the soil air temperature is between 80 and 400, preferably 90 and 350 ° C.
  • a starting mass for example the powdered fatty alcohol sulfate, the hydrophobic structure breaker or a SKET granulate from an earlier test batch, is advantageously introduced at the beginning of the SKET granulation.
  • the water evaporates from the fatty alcohol sulfate paste, producing dried to dried germs, which are coated with further amounts of fatty alcohol sulfate and structure breaker, granulated and again dried at the same time.
  • the result is a fatty alcohol sulfate that has been finely structured or segmented by the introduction of the structure breaker and is therefore particularly easily water-soluble.
  • the fatty alcohol sulfates are mixed in powder form with the solidified structure breakers and the mixture is homogenized and solidified in a screw press.
  • extrusion is carried out via a perforated disc, 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.
  • the fatty alcohol sulfates obtainable in the sense of the invention show a high solubility in cold water and easy washing-in behavior in the washing machine. They are therefore suitable as raw materials for the production of solid washing, rinsing and cleaning agents, in which they can be present in amounts of 1 to 50, preferably 5 to 30% by weight, based on the agent.
  • Example 1.1 Production of a C 16/18 tallow alcohol sulfate powder via spray neutralization.
  • Example 1.1 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 at the same time neutralized in countercurrent air and dried to a residual water content of ⁇ 1% by weight.
  • the characteristics of the product are summarized in Table 1.
  • TAS-SKET granulate Production of a readily soluble TAS-SKET granulate.
  • Tallow alcohol sulfate sodium salt paste (according to 1.1) was granulated through a nozzle in a granulation drying system (AGT) from Glatt / FRG together with a mixture of nonionic surfactant and polymeric solidifying agent (according to 2.4) and dried at the same time.
  • a dust-free and non-sticky granulate with a high surfactant content was obtained.
  • the characteristics of the process and the product are summarized in Table 3.
  • a TAS-SKET granulate was produced by simultaneously drying and granulating 38 kg / h of tallow alcohol sulfate sodium salt paste (in accordance with 1.1) and 5 kg / h of soda.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
EP94906150A 1993-02-04 1994-01-26 Anionische tenside mit verbesserter löslichkeit Expired - Lifetime EP0682690B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4303211A DE4303211C2 (de) 1993-02-04 1993-02-04 Anionische Tenside mit verbesserter Löslichkeit
DE4303211 1993-02-04
PCT/EP1994/000207 WO1994018291A1 (de) 1993-02-04 1994-01-26 Anionische tenside mit verbesserter löslichkeit

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EP0682690A1 EP0682690A1 (de) 1995-11-22
EP0682690B1 true EP0682690B1 (de) 1997-07-09

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

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WO1995006702A1 (de) * 1993-09-02 1995-03-09 Henkel Kommanditgesellschaft Auf Aktien Wässrige detergensgemische
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
DE19635554C2 (de) * 1996-09-02 2001-05-31 Cognis Deutschland Gmbh Wäßrige Mittel für die Reinigung harter Oberflächen
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
DE19946342A1 (de) * 1999-09-28 2001-04-05 Cognis Deutschland Gmbh Formkörper mit verbesserter Wasserlöslichkeit
EP1690922A1 (en) * 2005-02-11 2006-08-16 The Procter & Gamble Company A solid laundry detergent composition
KR100771417B1 (ko) * 2007-02-15 2007-10-30 주식회사 에이엔디플러스 클린룸용 세정제 조성물

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LU60943A1 (es) * 1970-05-20 1972-02-23
US3803285A (en) * 1971-01-20 1974-04-09 Cpc International Inc Extrusion of detergent compositions
JPS5241612A (en) * 1975-09-30 1977-03-31 Kao Corp Granular or powdered detergent compositions
CA1293421C (en) * 1985-07-09 1991-12-24 Mark Edward Cushman Spray-dried granular detergent compositions containing nonionicsurfactant, polyethylene glycol, and polyacrylate
JPH0633439B2 (ja) * 1988-07-28 1994-05-02 花王株式会社 高密度粒状濃縮洗剤組成物
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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KR960701181A (ko) 1996-02-24
DE4303211C2 (de) 1996-05-15
EP0682690A1 (de) 1995-11-22
ES2105639T3 (es) 1997-10-16
DE59403312D1 (de) 1997-08-14
DE4303211A1 (de) 1994-08-11
JPH08506366A (ja) 1996-07-09
WO1994018291A1 (de) 1994-08-18

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