EP1141186A2 - Granules tensioactifs - Google Patents

Granules tensioactifs

Info

Publication number
EP1141186A2
EP1141186A2 EP99968345A EP99968345A EP1141186A2 EP 1141186 A2 EP1141186 A2 EP 1141186A2 EP 99968345 A EP99968345 A EP 99968345A EP 99968345 A EP99968345 A EP 99968345A EP 1141186 A2 EP1141186 A2 EP 1141186A2
Authority
EP
European Patent Office
Prior art keywords
weight
fatty alcohol
sulfate
acid
contain
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP99968345A
Other languages
German (de)
English (en)
Other versions
EP1141186B1 (fr
Inventor
Ditmar Kischkel
Jutta Stute
Manfred Weuthen
Stefan Podubrin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Personal Care and Nutrition GmbH
Original Assignee
Cognis Deutschland GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cognis Deutschland GmbH and Co KG filed Critical Cognis Deutschland GmbH and Co KG
Publication of EP1141186A2 publication Critical patent/EP1141186A2/fr
Application granted granted Critical
Publication of EP1141186B1 publication Critical patent/EP1141186B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • 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
    • C11D1/37—Mixtures of compounds all of which are anionic
    • 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
    • C11D1/143—Sulfonic acid 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
    • C11D1/02—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
    • C11D1/146—Sulfuric acid esters

Definitions

  • the invention relates to surfactant granules from fatty alcohol sulfates and olefin sulfonates, a process for their preparation and the use of olefin sulfonates to improve the cold water solubility of fatty alcohol sulfate granules.
  • Anionic surfactants in particular alkyl sulfates or fatty alcohol sulfates, are important components of detergents, dishwashing detergents and cleaning agents. Due to their manufacture, they are obtained as aqueous pastes with water contents of 30 to 75% by weight. In order to obtain solid products, the aqueous pastes are dried, for example, in the spray tower or by drying and simultaneous granulation, in particular in the fluidized bed. For example, it is known from European Patent EP 0603207 B that aqueous pastes of alkyl sulfates in the continuous fluidized bed can be converted into granules with a high bulk density by drying and simultaneous granulation. According to this method, it is also possible to mix inorganic or organic carrier materials.
  • Ci6 / 18 fatty alcohol sulfate granules which are produced by drying and simultaneous granulation, show inadequate solubility and dispersibility at low temperatures. Since the solution to this problem is of great importance for cold washing processes, the object of the present invention was to improve the dissolving and dispersing behavior of Ci6 / i8 fatty alcohol sulfates in a granular structure at low temperatures.
  • the invention relates to surfactant granules consisting of
  • the invention further relates to a process for the production of surfactant granules, in which the aqueous paste of component (a) is subjected to drying with simultaneous granulation in the presence of component (b).
  • An additional object of the invention is the use of olefin sulfonates in amounts of 3 to 25 wt .-% to improve the cold water solubility of fatty alcohol sulfate granules.
  • olefin sulfonates even in small amounts, improve the dissolving and dispersing behavior of C16 / 18 fatty alcohol sulfates in a granular structure, even at low temperature ranges. It is therefore advantageous to use olefin sulfonate fatty alcohol sulfate granules for washing processes at low temperatures.
  • Fatty alcohol sulfates which form component (a) are to be understood as meaning alkyl sulfates of the formula (I)
  • R 1 is a linear or branched, saturated or unsaturated hydrocarbon radical having 6 to 18 carbon atoms and X is an alkali or alkaline earth metal, ammonium, alkylammonium, alkanolammonum or glucammonium.
  • Fatty alcohol sulfates are known anionic surfactants, which are preferably obtained by sulfating native fatty alcohols or synthetic oxo alcohols and subsequent neutralization.
  • fatty alcohol sulfates are the sodium salts of sulfation of Capronalkohols, Caprylalkohols, 2-Ethylhexylalkohols, Caprinalkohois, lauryl alcohol, isotridecyl alcohol, Myristylalkohols, cetyl alcohol, Palmoleylalkohols, stearyl alcohol, Isostearylalkohols, oleyl alcohol, Elaidylalkohols, Petroselinylalkohols, Linolylalkohols, Linolenylalkohols and Elaeostearylalkohols and technical mixtures thereof, which occur, for example, in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols.
  • the agents according to the invention contain, as further constituent (b), olefin sulfonates which are usually obtained by addition of SO3 onto olefins of the formula (II) and subsequent hydrolysis and neutralization,
  • R 2 and R 3 independently of one another represent H or alkyl radicals having 1 to 20 carbon atoms, with the proviso that R 2 and R 3 together have at least 6 and preferably 10 to 16 carbon atoms.
  • olefin sulfonates but preferably ⁇ -olefin sulfonates, can be used, which result when R 2 or R 3 is hydrogen.
  • Typical examples of olefin sulfonates used are the sulfonation products which are obtained by treating SO3 with 1-, 2-, 3-, 4-octene, 1-, 2-, 3-, 4-, 5- decene, 1-, 2 -, 3-, 4-, 5-, 6- dodecene, 1-, 2-, 3-, 4-, 5-, 6-, 7-tetradecene, 1-, 2-, 3-, 4-, 5 -, 6-, 7-, 8-hexadecene, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-octadecene, 1-, 2-, 3- , 4-, 5-, 6-, 7-, 8-, 9-, 10-eicosen and 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10- and / or
  • hydrolysis and neutralization are carried out, after which the olefin sulfonate is present in the mixture as alkali metal, alkaline earth metal, ammonium, alkyl ammonium, alkanol ammonium, glucammonium, preferably as sodium salt.
  • the hydrolyzed ⁇ -olefin sulfonation product, ie the ⁇ -olefin sulfonates is advantageously composed of approximately 60% by weight alkanesulfonates and approximately 40% by weight hydroxyalkanesulfonates; of these are preferably 80 to 85% by weight of mono- and 15 to 20% by weight of disulfonates.
  • Both olefin sulfonates can be used as an aqueous paste, for example sodium olefin sulfonate (C ⁇ -Ci6), Elfan® OS 46 A (Akzo Nobel), and as anhydrous products, for example sodium olefin sulfonate (C14-C16), Eifan® OS 46 P (company Akzo Nobel).
  • aqueous paste for example sodium olefin sulfonate (C ⁇ -Ci6), Elfan® OS 46 A (Akzo Nobel)
  • anhydrous products for example sodium olefin sulfonate (C14-C16), Eifan® OS 46 P (company Akzo Nobel).
  • the invention further relates to a process for the preparation of surfactant granules according to claim 1, in which the aqueous paste of component (a) is subjected to drying with simultaneous granulation in the presence of component (b).
  • a preferred possibility is to subject the aqueous surfactant paste to so-called SKET granulation.
  • SKET granulation This is to be understood as a granulation with simultaneous drying, which preferably carried out batchwise or continuously in the fluidized bed.
  • the aqueous paste of component (a), for example a 30 to 65% strength by weight surfactant paste, and component (b) can be introduced into the fluidized bed simultaneously or in succession via one or more nozzles. If component (b) is in the form of a solid, it is advisable to add it to the fluidized bed apparatus by metering in the solid.
  • 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 sieving device or by means of an opposed air flow (classifier 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 fatty alcohol sulfate paste, producing dried to dried germs, which are coated with further amounts of fatty alcohol surfactants and with olefin sulfonates, granulated and again dried at the same time.
  • German patent applications DE 4303211 A1 and DE 4303176 A1 the content of which is hereby expressly included.
  • the simultaneous drying and granulation can also be carried out in a horizontally arranged thin-film evaporator with rotating internals, as is sold, for example, by the VRV company under the name "Flash Dryer".
  • Flash Dryer This is a pipe that can be heated to different temperatures across several zones.
  • the paste-like feed material which is metered in via a pump, is flung against the heated wall by means of one or more shafts, which are provided with blades or shares of flies as rotating internals, on which the drying takes place in a thin layer, typically 1 to 10 mm thick he follows. It has proven to be advantageous to apply a temperature gradient from 170 (product inlet) to 20 ° C. (product discharge) to the thin-film evaporator.
  • the first two zones of the evaporator can be heated to 160 ° C and the last can be cooled to 20 ° C.
  • Higher drying temperatures have not proven to be advantageous with regard to the thermal lability of the starting materials.
  • the thin film evaporator is operated at atmospheric pressure and gassed in countercurrent with air (throughput 50 to 150 m 3 / h).
  • the gas inlet temperature is usually 20 to 30 ° C, the outlet temperature 90 to 110 ° C.
  • the acid and a highly concentrated aqueous sodium hydroxide solution are separately charged with a gaseous medium, then combined in stoichiometric amounts, neutralized in a multi-component nozzle and sprayed into the drying or granulating plants at a high propellant gas pressure.
  • An advantage of the granules is that they are not sticky and have high bulk densities in the range from 300 to 1200 and preferably 500 to 800 g / l.
  • Another possibility for producing the surfactant granules according to the invention is to subject the aqueous surfactant pastes from components (a) and (b) to vacuum drying.
  • the aqueous pastes from the surfactants according to the invention for example a 30 to 65% strength by weight surfactant paste, are completely evaporated and the anhydrous residue is then ground to give granules.
  • the granules according to the invention consist of components (a) and (b) in the following amounts, based on the solids content:
  • the granules according to the invention can still have residual amounts of water, preferably below 5% by weight, based on the granules.
  • the cold water solubility of the fatty alcohol sulfate granules can be considerably improved by adding the olefin sulfonates. Accordingly, the present invention furthermore relates to the use of olefin sulfonates in amounts of 3 to 25% by weight to improve the cold water solubility of fatty alcohol sulfate granules.
  • the olefin sulfonate fatty alcohol sulfate granules produced according to the invention are used according to another object of the invention for the production of detergents, dishwashing detergents and cleaning agents. They can be present in conventional amounts, preferably in the range from 0.1 to 30% by weight, based on.
  • the washing, rinsing and cleaning agents can also contain other typical ingredients, such as, for example, anionic surfactants, nonionic surfactants, builders, bleaching agents, bleach activators, detergency boosters, enzymes, enzyme stabilizers, graying inhibitors, optical brighteners, soil repellants, foam inhibitors, inorganic salts and also Contain fragrances and dyes.
  • anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, alkyl ether sulfonates, glycerol ether sulfonates, ⁇ -methyl ester sulfonates, sulfofatty acids, fatty alcohol ether sulfates, glycerin ether sulfates, fatty acid ether sulfates, hydroxymixed ether sulfates, monoglycerol sulfate fatty acids, sulfonate sulfate amine sulfonate sulfate amine sulfate amide sulfate amate sulfate amate sulfate amate sulfate amate sulfate amine sulfate amine sulfate amate sulfate amate sulfate amate sulfate amate sulfate amine sulfate
  • anionic surfactants contain polyglycol ether chains, these can have a conventional, but preferably a narrow, homolog distribution.
  • Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, optionally partially oxidized alk (en) yl oligoglycoside derivatives, fatty acid glucoride acid derivatives, and glucoramide acid derivatives, especially vegetable products based on wheat), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
  • finely crystalline, synthetic and bound water-containing zeolite such as zeolite NaA in detergent quality is used as the solid builder.
  • zeolite NaX and mixtures of NaA and NaX are also suitable.
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture.
  • small additions-C ⁇ s fatty alcohols Ci2 can nonionic surfactants contain as stabilizers, 'for example, 1 to 3 wt .-%, based on zeolite, of ethoxylated with 2 to 5 Ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable Nete zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22, in particular 20 to 22% by weight of bound water.
  • Suitable substitutes or partial substitutes for zeolites are crystalline, layered sodium silicates of the general formula NaMSi ⁇ 2x + ryH2 ⁇ , where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x is 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP 0164514 A.
  • Preferred crystalline layered silicates are those in which M in the general formula stands for sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si2 ⁇ 5 yH2 ⁇ are preferred, with ⁇ -sodium disilicate being able to be obtained, for example, by the process described in international patent application WO 91/08171.
  • the powder detergents according to the invention preferably contain 10 to 60% by weight of zeolite and / or crystalline layered silicates as solid builders, mixtures of zeolite and crystalline layered silicates in any ratio being particularly advantageous.
  • the agents contain 20 to 50% by weight of zeolite and / or crystalline layered silicates.
  • agents contain up to 40% by weight of zeolite and in particular up to 35% by weight of zeolite, in each case based on anhydrous active substance.
  • Other suitable ingredients of the agents are water-soluble amorphous silicates; they are preferably used in combination with zeolite and / or crystalline layered silicates.
  • Particularly preferred are agents which contain, above all, sodium silicate with a molar ratio (module) Na ⁇ O: SiO ⁇ of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5.
  • the content of amorphous sodium silicates in the agents is preferably up to 15% by weight and preferably between 2 and 8% by weight.
  • Phosphates such as tripolyphosphates, pyrophosphates and orthophosphates can also be present in small amounts in the compositions.
  • the content of the phosphates in the compositions is preferably up to 15% by weight, but in particular 0 to 10% by weight.
  • the agents can also contain layered silicates of natural and synthetic origin. Layered silicates of this type are known, for example, from patent applications DE 2334899 B, EP 0026529 A and DE 3526405 A. Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here. Suitable layered silicates, which belong to the group of water-swellable smectites, are, for example, those of the general formulas
  • the layered silicates can contain hydrogen, alkali, alkaline earth ions, in particular Na and Ca 2+ .
  • the amount of water of hydration is usually in the range from 8 to 20% by weight and is depending on the source state or the type of processing.
  • Useful sheet silicates are known, for example, from US 3,966,629, US 4,062,647, EP 0026529 A and EP 0028432 A.
  • Layer silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.
  • Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons. and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. The use of polymeric polycarboxylates is not absolutely necessary.
  • agents are preferred which are biodegradable polymers, for example terpolymers, the monomers acrylic acid and maleic acid or salts thereof, and vinyl alcohol or vinyl alcohol derivatives or the monomers acrylic acid and 2-alkylallylsulfonic acid or containing their salts and sugar derivatives.
  • terpolymers which are obtained according to the teaching of German patent applications DE 4221381 A and DE 4300772 A are particularly preferred.
  • Further suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP 0280223 A.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other bleaching agents are, for example, peroxy carbonate, citrate perhydrates and salts of peracids, such as perbenzoates, peroxyphthalates or diperoxydodecanedioic acid. They are usually used in amounts of 8 to 25% by weight.
  • the use of sodium perborate monohydrate in amounts of 10 to 20% by weight and in particular 10 to 15% by weight is preferred. Due to its ability to bind free water with the formation of the tetrahydrate, it contributes to increasing the stability of the agent.
  • bleach activators can be incorporated into the preparations.
  • these are N-acyl or O-acyl compounds which form organic peracids with hydrogen peroxide, preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate.
  • the bleach activators contain bleach activators in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.
  • Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylenediamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Their proportion can be about 0.2 to about 2% by weight. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. In addition to the mono- and polyfunctional alcohols and the phosphonates, the agents can contain further enzyme stabilizers.
  • sodium formate 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • boron compounds for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H3BO3), metaboric acid (HBO2) and pyroboric acid of (tetraboric H2B 4: 0).
  • Graying inhibitors have the task of keeping the dirt detached from the fibers suspended in the liquor and thus preventing graying.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and also polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition.
  • the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the morpho- linino group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenylstyrene type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl , or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.
  • Uniformly white granules are obtained if, in addition to the usual brighteners, the agents are present in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, and also in small amounts, for example Contain 10- 6 to 10- 3 wt .-%, preferably by 10- 5 wt .-%, of a blue dye.
  • a particularly preferred dye is Tinolux® (commercial product from Ciba-Geigy).
  • Dirt-repellent polymers (“should repellants”) are substances which preferably contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, the molar ratio of ethylene terephthalate to polyethylene glycol terephthalate being in the range from 50:50 to 90:10.
  • the molecular weight of the linking polyethylene glycol units in particular in the range from 750 to 5000, ie the degree of ethoxylation of the polymers containing polyethylene glycol groups can be approximately 15 to 100.
  • the polymers are distinguished by an average molecular weight of approximately 5000 to 200,000 and can have a block, but preferably a random structure
  • Preferred polymers are those with molar ratios of ethylene terephthalate / polyethylene glycol terephthalate from about 65:35 to about 90:10, preferably from about 70:30 to 80:20.
  • Examples of commercially available polymers are the products Milease® T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc).
  • foam inhibitors When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents.
  • Soaps of natural or synthetic origin with a high content of Ci8-C24 fatty acids are suitable.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally signed silica, and paraffins, waxes, microcrystalline waxes and their mixtures with signed silica or bistearylethylenediamide.
  • Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
  • the foam inhibitors, in particular silicone or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred. Examples
  • Aqueous pastes made from C16 / 18 fatty alcohol sulfates and various amounts of ⁇ -olefin sulfonate [sodium olefin sulfonate (Cw-Cie), Elfan® OS 46, from Akzo Nobel, 1], C12 / 14 fatty alcohol sulfate sodium salt (V1) and ocenol sulfate Sodium salt (V2) was subjected to vacuum drying and then ground to granules. The solubility of these granules was examined in a hand wash test and the amount of residue in% by weight (Table 1) was determined.
  • the ⁇ -olefin sulfonate (1) improves the dissolving and dispersing properties even when 5% added to the C16 / 18 fatty alcohol sulfate compared to V1 and V2.
  • aqueous pastes 1 to 3 according to the invention and the comparison pastes V1 to V6 were each injected into the fluidized bed system in different test batches.
  • Air outlet temperature 80 to 85 ° C
  • Residual moisture 2.0 to 3.0% by weight

Landscapes

  • Chemical & Material Sciences (AREA)
  • 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)
  • Detergent Compositions (AREA)
  • Fats And Perfumes (AREA)

Abstract

L'invention concerne des granulés tensioactifs, comprenant (a) 75 à 97 % en poids de sulfates d'alcools gras et (b) 3 à 25 % en poids de sulfonates d'oléfine, les deux quantités se complétant de façon à donner 100 % en poids.
EP99968345A 1998-12-19 1999-12-10 Granules tensioactifs Expired - Lifetime EP1141186B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19858886A DE19858886C2 (de) 1998-12-19 1998-12-19 Tensidgranulate
DE19858886 1998-12-19
PCT/EP1999/009739 WO2000037593A2 (fr) 1998-12-19 1999-12-10 Granules tensioactifs

Publications (2)

Publication Number Publication Date
EP1141186A2 true EP1141186A2 (fr) 2001-10-10
EP1141186B1 EP1141186B1 (fr) 2003-11-05

Family

ID=7891856

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99968345A Expired - Lifetime EP1141186B1 (fr) 1998-12-19 1999-12-10 Granules tensioactifs

Country Status (5)

Country Link
US (1) US6780829B1 (fr)
EP (1) EP1141186B1 (fr)
DE (2) DE19858886C2 (fr)
ES (1) ES2211225T3 (fr)
WO (1) WO2000037593A2 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10031619A1 (de) * 2000-06-29 2002-01-10 Cognis Deutschland Gmbh Tensidgranulate mit verbesserter Auflösegeschwindigkeit
EP1352951A1 (fr) * 2002-04-11 2003-10-15 The Procter & Gamble Company Granulé détergent comprenant un tensioactif nonionique et une hydrotrope
DE102004034141A1 (de) * 2004-07-15 2006-02-09 Cognis Ip Management Gmbh Verwendung von Lithiumsalzen von Fettalkoholsulfaten zum Reinigen von Bohrlöchern, Bohrgeräten oder Bohrklein
JP5020482B2 (ja) * 2005-01-13 2012-09-05 花王株式会社 アニオン界面活性剤粉粒体
WO2014072840A1 (fr) 2012-11-12 2014-05-15 Galaxy Surfactants Ltd. Sulfates d'alkyle gras aqueux hautement actifs fluides

Family Cites Families (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2016962A (en) 1932-09-27 1935-10-08 Du Pont Process for producing glucamines and related products
US1985424A (en) 1933-03-23 1934-12-25 Ici Ltd Alkylene-oxide derivatives of polyhydroxyalkyl-alkylamides
US2703798A (en) 1950-05-25 1955-03-08 Commercial Solvents Corp Detergents from nu-monoalkyl-glucamines
ZA734721B (en) 1972-07-14 1974-03-27 Procter & Gamble Detergent compositions
GB1455873A (en) 1973-08-24 1976-11-17 Procter & Gamble Textile-softening detergent compositions
JPS52154810A (en) * 1976-06-18 1977-12-22 Lion Corp Granulated detergent composition
US4129526A (en) * 1977-07-14 1978-12-12 The Lion Fat & Oil Co., Ltd. Granular detergent compositions and a process for producing same
DE3069768D1 (en) 1979-09-29 1985-01-17 Procter & Gamble Ltd Detergent compositions
ATE5896T1 (de) 1979-11-03 1984-02-15 The Procter & Gamble Company Granulare waschmittelzusammensetzungen.
US4534879A (en) 1983-06-29 1985-08-13 The Procter & Gamble Company Synthetic surfactant flakes and process for making them
DE3413571A1 (de) 1984-04-11 1985-10-24 Hoechst Ag, 6230 Frankfurt Verwendung von kristallinen schichtfoermigen natriumsilikaten zur wasserenthaertung und verfahren zur wasserenthaertung
JPS61148298A (ja) 1984-12-21 1986-07-05 ライオン株式会社 洗浄剤組成物
DE3526405A1 (de) 1985-07-24 1987-02-05 Henkel Kgaa Schichtsilikate mit beschraenktem quellvermoegen, verfahren zu ihrer herstellung und ihre verwendung in wasch- und reinigungsmitteln
DE3706036A1 (de) 1987-02-25 1988-09-08 Basf Ag Polyacetale, verfahren zu deren herstellung aus dialdehyden und polyolcarbonsaeuren und verwendung der polyacetale
DE3741401A1 (de) 1987-12-07 1989-06-15 Henkel Kgaa Verfahren zur herstellung von festen oder pastenfoermigen produkten
YU221490A (sh) 1989-12-02 1993-10-20 Henkel Kg. Postupak za hidrotermalnu izradu kristalnog natrijum disilikata
DE4127323A1 (de) 1991-08-20 1993-02-25 Henkel Kgaa Verfahren zur herstellung von tensidgranulaten
DE4221381C1 (de) 1992-07-02 1994-02-10 Stockhausen Chem Fab Gmbh Pfropf-Copolymerisate von ungesättigten Monomeren und Zuckern, Verfahren zu ihrer Herstellung und ihre Verwendung
DE4203031A1 (de) 1992-02-04 1993-08-05 Henkel Kgaa Verfahren zur herstellung fester wasch- und reinigungsmittel mit hohem schuettgewicht und verbesserter loesegeschwindigkeit
DE4300772C2 (de) 1993-01-14 1997-03-27 Stockhausen Chem Fab Gmbh Wasserlösliche, biologisch abbaubare Copolymere auf Basis von ungesättigten Mono- und Dicarbonsäuren, Verfahren zu ihrer Herstellung und ihre Verwendung
DE4303176C2 (de) 1993-02-04 1997-07-31 Henkel Kgaa Feste Wasch-, Spül- und Reinigungsmittel
DE4303211C2 (de) 1993-02-04 1996-05-15 Henkel Kgaa Anionische Tenside mit verbesserter Löslichkeit
US5417893A (en) * 1993-08-27 1995-05-23 The Procter & Gamble Company Concentrated liquid or gel light duty dishwashing detergent compositions containing calcium ions and disulfonate surfactants
CZ76096A3 (en) 1993-09-14 1996-08-14 Procter & Gamble Slightly foamy liquid or gel-like protease-containing detergent for washing-up
US5714451A (en) * 1996-03-15 1998-02-03 Amway Corporation Powder detergent composition and method of making
DE19700776A1 (de) 1997-01-13 1998-07-16 Henkel Kgaa Granulares Waschmittel mit verbessertem Fettauswaschvermögen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0037593A2 *

Also Published As

Publication number Publication date
WO2000037593A3 (fr) 2000-11-23
DE19858886C2 (de) 2002-10-31
ES2211225T3 (es) 2004-07-01
WO2000037593A2 (fr) 2000-06-29
US6780829B1 (en) 2004-08-24
DE19858886A1 (de) 2000-06-21
DE59907660D1 (de) 2003-12-11
EP1141186B1 (fr) 2003-11-05

Similar Documents

Publication Publication Date Title
EP0603207B1 (fr) Procede de fabrication de granulats tensioactifs
EP0642576B1 (fr) Procede de fabrication continue d'un detergent et/ou d'un nettoyant granulaire
EP0228011B1 (fr) Détergent granulaire à teneur en phosphates réduite
WO1995022592A1 (fr) Produit de lavage a adjuvants au silicate amorphes
EP0757094A2 (fr) Composition détergente contenant des disuccinates d'imine
EP0859827A1 (fr) Procede de production d'un silicate alcalin amorphe avec impregnation
CH625550A5 (en) Flowable detergents and cleaners containing non-ionic surfactants, and process for their production
EP0683814B1 (fr) Procede de production d'agents tensio-actifs granules
EP0804529B1 (fr) Compose silicate alcalin amorphe
DE60023470T3 (de) Waschpulver
EP0682692A1 (fr) Adjuvant pour detergents ou nettoyants.
DE19858886C2 (de) Tensidgranulate
WO1994013771A1 (fr) Detergents et nettoyants granulaires a haute teneur en tensioactifs
EP1043387B1 (fr) Granules d'alkylbenzènesulfonate
DE60023024T2 (de) Verfahren zur herstellung granularer waschmittelzusammensetzungen
EP0804535B1 (fr) Detergents et nettoyants de blanchiment sous forme de granulats
EP0647261B1 (fr) Granule de lavage et de nettoyage
EP0799302A1 (fr) Silicate alcalin amorphe contenant des substances impregnees
WO1999010471A1 (fr) Detergents solides contenant des sulfates d'ester de polyglycol d'acide gras et adjuvants solides
EP0845028A1 (fr) Procede de production d'un silicate alcalin amorphe soumis a une impregnation
EP1123372B1 (fr) Melanges de tensioactifs non ioniques
WO1997034991A1 (fr) Procede de production de detergents ou de nettoyants granulaires coulants
EP0936267A2 (fr) Composé de silicate de métal alcalin / tensioactif nonionique
EP1123373A1 (fr) Melanges de tensioactifs non ioniques
WO1998055568A1 (fr) Agents de lavage ou de nettoyage a pouvoir nettoyant eleve

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20010609

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

17Q First examination report despatched

Effective date: 20011212

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: COGNIS DEUTSCHLAND GMBH & CO. KG

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE ES FR GB IT

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REF Corresponds to:

Ref document number: 59907660

Country of ref document: DE

Date of ref document: 20031211

Kind code of ref document: P

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: GERMAN

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20040216

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2211225

Country of ref document: ES

Kind code of ref document: T3

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20040806

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20090514 AND 20090520

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 17

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 18

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20181221

Year of fee payment: 20

Ref country code: FR

Payment date: 20181231

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20181220

Year of fee payment: 20

Ref country code: DE

Payment date: 20190228

Year of fee payment: 20

Ref country code: ES

Payment date: 20190131

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 59907660

Country of ref document: DE

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20191209

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20191209

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20200723

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20191211