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EP0682691B2 - Procede de preparation d' agents de lavage solides et anhydres - Google Patents

Procede de preparation d' agents de lavage solides et anhydres Download PDF

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Publication number
EP0682691B2
EP0682691B2 EP94906151A EP94906151A EP0682691B2 EP 0682691 B2 EP0682691 B2 EP 0682691B2 EP 94906151 A EP94906151 A EP 94906151A EP 94906151 A EP94906151 A EP 94906151A EP 0682691 B2 EP0682691 B2 EP 0682691B2
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EP
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Prior art keywords
molecular weight
nonionic surfactants
average molecular
polyethylene glycol
formula
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German (de)
English (en)
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EP0682691B1 (fr
EP0682691A1 (fr
Inventor
Karl Schmid
Andreas Syldath
Ditmar Kischkel
Thomas Krohnen
Michael Neuss
Michael Langen
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BASF Personal Care and Nutrition GmbH
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Cognis Deutschland GmbH and Co KG
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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
    • 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
    • C11D1/66—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
    • 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 new solid anhydrous detergents, a process for their preparation in which mixtures made of fatty alcohol results and nonionic surfactants mixed with selected polymeric hardening agents and the use of the mixtures of fatty alcohol sulfates and nonionic surfactants and the polymer Solidifying agents as raw materials For the production of solid and bleeding-resistant detergents.
  • Solid detergents, dishwashing detergents and cleaning agents usually come onto the market in the form of powders, granules or extrudates.
  • surface-active constituents they generally contain combinations of anionic and nonionic surfactants, which ideally complement one another in terms of cleaning action and dirt- carrying capacity [Chemie luZeit, 26, 292 (1992)] .
  • anionic surfactants were present in excess in the past, there is now a need for recipes with an increased content of nonionic surfactants.
  • These are to be understood in particular as formulations in which the proportion of nonionic surfactants is 100 to 200% by weight compared to that of anionic surfactants.
  • alkylbenzene sulfonates and increasingly fatty alcohol sulfates have been in the foreground for anionic surfactants, the trend for non-ionic surfactants is towards lower alkoxylated fatty alcohol polyglycol ethers and alkyl oligoglucosides [Seifen- ⁇ le-Fette-Wwachs, 117 , 554 (1991)] .
  • Solid detergents, dishwashing detergents and cleaning agents of this type not only show excellent application technology Services, but also advantages in compacting for the production of heavy powders with bulk weights of 600 to 900 g / l.
  • the disadvantage is that the anionic surfactants together with the other solid formulation components have only a limited capacity to "soak up" the mostly liquid nonionic surfactants and to last to tie. This is precisely the case with the desired formulations with a particularly high non-ionic surfactant content Risk of "bleeding", d. H. the liquid nonionic surfactants become mixed from the present solid gradually released. The result is a decrease in the washing performance of the recipe and a gradual greasing commercial cardboard packaging; the latter can also be used as an indication of the degree of bleeding or the Bleeding resistance can be used.
  • 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 dries and / or solidifies.
  • the rate of dissolution of the resulting solid detergents is still unsatisfactory.
  • 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 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 C 12/13 -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.
  • the object of the invention was to provide processes for the production of solid water-free detergents with an increased nonionic content To provide surfactants that are permanently resistant to the bleeding of nonionic surfactants.
  • Non-surfactant-rich formulations lead to a solidification of the grain and permanent bleeding of liquid components and reliably prevented without the application performance of the recipes being shared the solidifying agent is adversely affected.
  • the invention has a special meaning for agents with high Content of nonionic surfactants; however, it is also possible to use compositions with a comparatively low nonionic content Stabilize surfactants against bleeding in the specified way.
  • the invention includes the finding that it is considered in view of the suitability of polyethylene glycol ethers polymeric strengthening agents with regard to the molecular weight there is a critical limit of 35,000. Below this area does not have the desired effect, the significant improvement in bleeding resistance reached.
  • Fatty alcohol sulfates follow formula (I) R 1 OSO 3 X in which R 1 represents a linear or branched 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. From the group of fatty alcohol sulfates, tallow alcohol sulfates are again of particular importance, in which R 1 in formula (I) represents an alkyl radical having 16 to 18 carbon atoms and X represents sodium.
  • nonionic surfactants are fatty alcohol polyglycol ethers of the formula (II) in which R 2 is a linear or branched aliphatic hydrocarbon radical having 6 to 18 carbon atoms and 0, 1, 2 or 3 double bonds, n is 0 or numbers from 1 to 3 and m is numbers from 1 to 10.
  • Typical examples are addition products of an average of 1 to 3 mol of propylene oxide and / or 1 to 10, preferably 2 to 7 mol, of ethylene oxide to capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol , Petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elasostearyl alcohol, arachyl alcohol, gadoleyl alcohol, erucyl alcohol and behenyl alcohol, and their technical mixtures, as obtained, for example, from high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis.
  • the adducts can have a conventional or narrow homolog distribution and, due to the production process, can also contain free fatty alcohol.
  • the use of addition products of an average of 2 to 7 moles of ethylene oxide with technical C 12/14 or C 12/18 coconut alcohol cuts is particularly preferred.
  • Suitable nonionic surfactants are also alkyl oligoglycosides of the formula (III) R 3 -O- [G] p in which R 3 is an alkyl radical having 6 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 that can be obtained by the relevant methods of preparative organic chemistry.
  • EP- A1-0 301 298 and WO 90/3977 are known substances that can be obtained by the relevant methods of preparative organic chemistry.
  • the alkyl oligoglycosides can differ from aldoses or ketoses with 5 or 6 carbon atoms, preferably that Derive glucose.
  • the preferred alkyl oligoglycosides are thus alkyl oligoglucosides.
  • Alkyl oligoglycosides are preferred with an average degree of oligomerization p of 1.1 to 3.0. From an application technology perspective, there are Alkyl oligoglycosides are preferred whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 lies.
  • the fatty alcohol sulfates of the formula I and nonionic surfactants can be in a weight ratio of 1: 1 to 1: 5, preferably 1: 1 to 1: 2 can be used.
  • the polymeric strengthening agents can contain the nonionic surfactants in amounts of 1 to 50, preferably 2 to 30 wt .-% - based on the nonionic surfactants - are added. Although it is basically possible to produce ternary mixtures of anionic surfactants, nonionic surfactants and polymeric strengthening agents, is it i. a. It is more advantageous to first add the polymeric solidifying agent to the nonionic surfactants and to further process this preformed mixture after hardening with the anionic surfactants.
  • the selected polymeric solidifying agents can be added to the nonionic surfactants, whereby intimate mixing with stirring or kneading, if necessary with heating, must be ensured.
  • the nonionic surfactant is a polyglycol ether and the polymeric solidifying agent is a PEG
  • the mixture can also be generated in-situ by combining a mixture of fatty alcohol and PEG alkoxylated.
  • the fatty alcohol sulfates of the formula I can be used in the form of aqueous pastes or dry powders and then with the solidified nonionic surfactants are treated.
  • Fatty alcohol sulfates are usually converted by reacting appropriate fatty alcohols with sulfur trioxide or chlorosulfonic acid to give acidic sulfuric acid semisters 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 for the purposes 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.
  • One 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.
  • fatty alcohol sulfates in the form of spray-neutralized as well as spray-dried or steam-dried powders are suitable as starting materials.
  • spray drying or spray neutralization of surfactants reference is made to ROEMPP Chemistry Lexicon , 9th edition, Thieme-Verlag, Stuttgart, 1992, p.4259 / 4260 .
  • 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, spray-dried or steam-dried powder.
  • the solid, water-free detergents can be produced in various ways.
  • a particularly simple embodiment of the method consists in presenting the fatty alcohol sulfate in powder form and intimately mixed with the required amount of the solidified nonionic surfactant.
  • components such as paddle mixers from Lödige or in particular spray mixers from Schugi advantageous in which the anionic surfactant is placed in the mixing chamber and the solidified nonionic surfactant aufdüst.
  • the fatty alcohol sulfates are subjected to so-called SKET granulation .
  • SKET granulation This is understood to mean granulation with simultaneous drying, which is preferably carried out batchwise or continuously in the fluidized bed.
  • the aqueous pastes of the anionic surfactants and the solidified nonionic surfactants can be introduced into the fluidized bed 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 take place, for example, by means of a screening device or by means of an opposed air flow (classifying 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 a SKET granulate from an earlier test batch, is advantageously introduced at the beginning of the SKET granulation.
  • the water evaporates from the anionic surfactant paste, producing dried to dried germs, which are coated with further amounts of anionic surfactant and solidified nonionic surfactant, granulated and again dried at the same time.
  • the fatty alcohol sulfates of the formula I are solidified in powder form with the non-ionic surfactants are mixed and the mixture is homogenized and solidified in a screw press.
  • the extrusion takes place via a perforated disc, so that press strands are formed which, according to known processes, produce extrudates or needles of the desired shape and size can be mechanically crushed. Extrudates of this form show a particularly high dissolving speed and very good washing-up behavior in the washing machine.
  • the solid, anhydrous can Detergents other conventional auxiliaries and additives, for example zeolites, phosphates, phosphonates, polycarboxyrates, Contain water glass, soda and borates, which are added to them before, during or after the solidification can.
  • auxiliaries and additives for example zeolites, phosphates, phosphonates, polycarboxyrates, Contain water glass, soda and borates, which are added to them before, during or after the solidification can.
  • solid water-free detergents based on fatty alcohol sulfates of the formula I and nonionic surfactants prepared according to the invention as well as polymeric strengthening agents are stable and show the non-ionic surfactants bleed out excellent detergent properties.
  • a universal detergent formulation with a high content of nonionic surfactants and without or with polymeric solidifying agents with a composition according to Table 1 was extruded over a screw roller and processed via a perforated disc (diameter of the openings: 0.9 mm) to form extrusions which continuously produce extrudates of a grain size of 0.9 mm were crushed.
  • Composition of the detergent formulations, percentages as% by weight of auxiliaries ad 100%.
  • components V1% B1% B2% tallow alcohol 10 10 10
  • coconut alcohol 3 EO 15 15 15 15 PEG-100000 0 3 5
  • the formulations B1 and B2 are according to the invention; Recipe V1 is used for comparison.
  • the bleeding behavior of the recipes was determined on unprinted cardboard with a thickness of 0.4 mm.
  • the cardboard was mounted horizontally on a vibrating base, 5 g of the fixed formulations V1, B1 and B2 each applied and fixed with the help of glass rings (diameter 5 cm).
  • the results are summarized in Tab. 2: Ausblut E.g.

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  • Engineering & Computer Science (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
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Claims (9)

  1. Procédé de fabrication d'agents de lavage, solides, anhydres, par granulation selon le procédé SKET, dans lequel on additionne des mélanges de sulfates d'alcool gras de formule I R1OSO3X dans laquelle R1 représente un reste alkyle et/ou alkényle, linéaire ou ramifié, ayant de 12 à 22 atomes de carbone et X représente un métal alcalin et/ou alcalino-terreux, un ammonium, un alkylammonium, un alkanolammonium ou un glucammonium, et des agents tensioactifs non ioniques dans un rapport en poids allant de 9 :1 à 1 :9, avec de 1 à 50 % en poids - rapporté aux agents tensioactifs non ioniques - d'agents de solidification polymères choisis dans le groupe formé par :
    b1) éthers de polyéthylèneglycol ayant un poids moléculaire moyen allant de 35 000 à 500 000,
    b2) esters d'acides dicarboxyliques ayant un poids moléculaire moyen de 400 à 20 000,
    b3) produits de transestérification de carbonate de dialkyle avec des éthers de polyéthylèneglycol ayant un poids moléculaire moyen allant de 400 à 20 000 et
    b4) des oligo- ou des polysaccharides ayant un degré de condensation allant de 5 à 1000.
  2. Procédé selon la revendication 1,
    caractérisé en ce qu'
    on met en oeuvre des sulfates d'alcool gras de la formule (I) dans laquelle R1 représente un radical alkyle ayant de 16 à 18 atomes de carbone et X du sodium.
  3. Procédé selon les revendications là 2,
    caractérisé en ce qu'
    on met en oeuvre comme tensioactifs non ioniques des éthers d'alcools gras de polyglycol de la formule (II),
    Figure 00150001
    dans laquelle R2 représente un radical hydrocarbure linéaire ou ramifié, aliphatique ayant de 6 à 18 atomes de carbone et 0,1,2 ou 3 doubles liaisons, n représente 0 ou des nombres de 1 à 3 et m des nombres de 1 à 10.
  4. Procédé selon les revendications 1 à 2,
    caractérisé en ce qu'
    on met en oeuvre comme tensioactifs non ioniques des alkyloligoglycosides de la formule (III), R3 -O- [G]p dans laquelle R3 représente un radical alkyle avec de 6 à 22 atomes de carbone, G un radical sucre ayant 5 ou 6 atomes de carbone et p un nombre de 1 à 10.
  5. Procédé selon les revendications 1 à 2,
    caractérisé en ce qu'
    on met en oeuvre comme agents de stabilisation polymères des éthers de polyéthylèneglycol ayant un poids moléculaire moyen de 35 000 à 100 000.
  6. Procédé selon les revendications 1 à 2,
    caractérisé en ce qu'
    on met en oeuvre comme agents de stabilisation polymères des esters d'acides dicarboxyliques de la formule (IV), HOOOC- (CH2)yCOOH dans laquelle y représente 0 ou des nombres de 1 à 12, avec des éthers de polyéthylèneglycol, qui ont un poids moléculaire moyen de 400 à 20 000.
  7. Procédé selon les revendications 1 à 2,
    caractérisé en ce qu'
    on met en oeuvre comme agents de stabilisation polymères des produits de transestérification de carbonate de dialkyle avec des éthers de polyéthylèneglycol, qui ont un poids moléculaire moyen de 400 à 20 000.
  8. Procédé selon les revendications 1 à 2,
    caractérisé en ce qu'
    on met en oeuvre comme agents de stabilisation polymères des oligo- ou polysaccharides ayant un degré de condensation de 5 à 1000.
  9. Utilisation de mélanges obtenus selon le procédé d'après les revendications 1 à 8 en tant que matières premières pour la fabrication d'agents de lavage solides, anhydres.
EP94906151A 1993-02-04 1994-01-26 Procede de preparation d' agents de lavage solides et anhydres Expired - Lifetime EP0682691B2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4303176 1993-02-04
DE4303176A DE4303176C2 (de) 1993-02-04 1993-02-04 Feste Wasch-, Spül- und Reinigungsmittel
PCT/EP1994/000208 WO1994018293A1 (fr) 1993-02-04 1994-01-26 Agents de lavage, de rinçage et nettoyants solides

Publications (3)

Publication Number Publication Date
EP0682691A1 EP0682691A1 (fr) 1995-11-22
EP0682691B1 EP0682691B1 (fr) 1997-04-09
EP0682691B2 true EP0682691B2 (fr) 2004-01-14

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JP (1) JPH08506367A (fr)
KR (1) KR960700333A (fr)
DE (2) DE4303176C2 (fr)
ES (1) ES2100697T3 (fr)
WO (1) WO1994018293A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USH1514H (en) * 1994-06-01 1996-01-02 The Procter & Gamble Company Detergent compositions with oleoyl sarcosinate and polymeric dispersing agent
TW326472B (en) * 1994-08-12 1998-02-11 Kao Corp Method for producing nonionic detergent granules
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
GB2314563B (en) * 1996-06-28 2000-03-29 Laporte Esd Ltd Surfactant compositions
DE19635555C2 (de) 1996-09-02 2000-06-08 Cognis Deutschland Gmbh Wäßrige Handgeschirrspülmittel
DE19719606C2 (de) * 1997-05-09 1999-02-18 Henkel Kgaa Feststoffzubereitungen
DE19858886C2 (de) 1998-12-19 2002-10-31 Cognis Deutschland Gmbh Tensidgranulate
DE19911040A1 (de) 1999-03-12 2000-09-21 Cognis Deutschland Gmbh Tensidgranulate

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1402403A (en) † 1972-10-31 1975-08-06 Procter & Gamble Detergent compositions
EP0118191A1 (fr) † 1983-02-03 1984-09-12 The Procter & Gamble Company Compositions additives pour le linge
EP0402112B1 (fr) † 1989-06-09 1996-08-14 The Procter & Gamble Company Formation de granules de détergent discrets à haute activité utilisant un système de neutralisation continu

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LU60943A1 (fr) * 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
DE3424317A1 (de) * 1984-07-02 1986-01-23 Henkel KGaA, 4000 Düsseldorf Mittel zur toilettenreinigung
CA1293421C (fr) * 1985-07-09 1991-12-24 Mark Edward Cushman Compositions detergentes granulaires, sechees par pulverisation, a base de surfactif non ionique, de polyethylene glycol et de polyacrylate
DE4124701A1 (de) * 1991-07-25 1993-01-28 Henkel Kgaa Verfahren zur herstellung fester wasch- und reinigungsmittel mit hohem schuettgewicht und verbesserter loesegeschwindigkeit

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1402403A (en) † 1972-10-31 1975-08-06 Procter & Gamble Detergent compositions
EP0118191A1 (fr) † 1983-02-03 1984-09-12 The Procter & Gamble Company Compositions additives pour le linge
EP0402112B1 (fr) † 1989-06-09 1996-08-14 The Procter & Gamble Company Formation de granules de détergent discrets à haute activité utilisant un système de neutralisation continu

Also Published As

Publication number Publication date
KR960700333A (ko) 1996-01-19
EP0682691B1 (fr) 1997-04-09
JPH08506367A (ja) 1996-07-09
DE59402383D1 (de) 1997-05-15
ES2100697T3 (es) 1997-06-16
EP0682691A1 (fr) 1995-11-22
DE4303176C2 (de) 1997-07-31
DE4303176A1 (de) 1994-08-11
WO1994018293A1 (fr) 1994-08-18

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