EP0853117B1 - Détergent granulaire pour une meilleure élimination des salissures grasses - Google Patents

Détergent granulaire pour une meilleure élimination des salissures grasses Download PDF

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Publication number
EP0853117B1
EP0853117B1 EP97122476A EP97122476A EP0853117B1 EP 0853117 B1 EP0853117 B1 EP 0853117B1 EP 97122476 A EP97122476 A EP 97122476A EP 97122476 A EP97122476 A EP 97122476A EP 0853117 B1 EP0853117 B1 EP 0853117B1
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EP
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Prior art keywords
weight
mixture
surfactant
acid
solids
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German (de)
English (en)
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EP0853117A1 (fr
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Hans-Josef Dr. Beaujean
Monika Dr. Böcker
Fred Dr. Schambil
Thomas Dr. Holderbaum
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D17/065—High-density particulate detergent compositions
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-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
    • C11D1/22—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
    • C11D1/66—Non-ionic compounds

Definitions

  • the present invention relates to a process for the preparation of anionic surfactant detergent granules which are active in washing and cleaning, and anionic surfactant-containing granules containing such granules
  • Detergent and cleaning agent compositions that have a high bulk density, very good solubility and very good primary and secondary washing power, in particular have a high fat washability.
  • the invention relates Detergent compositions with high bulk density, which can be found both in the induction channel commercial washing machines as well as, for example, in the hand wash basin dissolve quickly and residue-free and in the shortest time without clumping or gelling Time to form a wash liquor, which is characterized by an excellent cleaning effect distinguished.
  • Detergent compositions are known from European Patent EP-B-0 698 658 (Procter & Gamble) known that have an improved fat and oil washability. These compositions contain 1 to 90% by weight of an anionic alkylbenzenesulfonate free surfactant system from at least 30% by weight of an alkoxylated alkyl sulfate with an average degree of alkoxylation of 0.1 to 10, with defined Weight ratios of mono-, di-, tri- and higher alkylated fatty alcohol sulfates are present.
  • EP-B-0 698 659 (Procter & Gamble) extends this to be used Surfactant system for the use of less than 40 wt .-% alkylbenzenesulfonate (ABS).
  • ABS-containing detergent composition also has an improved wash-out capacity for oil and grease stains.
  • EP-A-0 506 108 (Unilever) describes a one-step process for producing a granular detergent composition, wherein 20 to 45 wt .-% of an anionic surfactant acid with at least equivalent amounts of a water-soluble alkaline inorganic Material neutralized and granulated. The addition of nonionic surfactants and other detergent ingredients in the mixing granulator are also disclosed.
  • a spray-dried alkylbenzenesulfonate (ABS) is used to carry out the process according to the invention. and / or compound containing fatty alcohol sulfate (FAS) (component a)) in a mixing granulator with builders, other optional ingredients and one Granulating liquid (anionic surfactant / neutralizing agent / nonionic surfactant mixture) granulated.
  • FAS fatty alcohol sulfate
  • the wet granules obtained are dried in a fluidized bed dryer and has a total surfactant content of over 40% by weight after drying (code b)).
  • the dried granules can then be mixed with other detergent ingredients be mixed to the finished product.
  • the spray-dried compound a which contains ABS and / or FAS, is made according to the usual State of the art method.
  • air and an inert gas such as nitrogen or superheated steam as the hot gas drying medium serve.
  • Examples of high-speed mixers are the Lödige® CB 30 recycler (trademark of Lödige Maschinenbau GmbH, Paderborn), the Fukae® FS-G mixer (trademark of Fukae Powtech, Kogyo Co., Japan), the Eirich® mixer type R (trademark of the machine factory Gustav Eirich, Hardheim) or the Drais® K-TTP 80 (trademark of Drais-Werke GmbH, Mannheim), Examples of slow-speed mixing granulators are the Drais® K-T 160 (trademark Drais-Werke GmbH, Mannheim) and Lödige® KM 300 (trademark Lödige Maschinenbau GmbH, Paderborn).
  • Fluidized bed dryers their base plates, are particularly preferred Have a diameter of at least 0.4 meters.
  • fluidized bed apparatus which is a base plate with a diameter between 0.4 and 5 m, for example 1.2 m or 2.5 m.
  • base plate is preferred a perforated base plate or a Conidur plate (commercial product of the company Hein & Lehmann) used.
  • at swirl air speeds between 1 and 8 m / s and in particular between 1.5 and 5.5 m / s worked.
  • the discharge of the Granules from the fluidized bed are advantageously made using a size classification the granules.
  • This classification can, for example, by means of a screening device or by an opposite air flow (classifier air), which is regulated so that only particles above a certain particle size are discharged from the fluidized bed.
  • classifier air which is regulated so that only particles above a certain particle size are discharged from the fluidized bed.
  • the granules in the fluidized bed can also contain surfactants or surfactant-free solutions are sprayed, the liquid evaporating and the solutes are applied to the grain.
  • the surfactant content is allowed the granules discharged from the fluidized bed do not fall below 40% by weight.
  • the high tenside granules obtained in this way can be combined with other Detergent ingredients are mixed to the finished product.
  • a partially to completely neutralized anionic surfactant acid is used as the granulating liquid, which may additionally contain optional components such as nonionic surfactants or other common ingredients of detergents and cleaning agents.
  • Alkylbenzenesulfonic acids are preferably suitable as anionic surfactant acid which is reacted with a basic, inorganic or organic neutralization medium.
  • This alkylbenzenesulfonate used as acid or optionally in the form of an alkali salt has an alkyl chain length of 8 to 14 carbon atoms, C 9-13 -alkylbenzenesulfonates being preferred.
  • Dodecylbenzenesulfonate has an outstanding position among alkylbenzenesulfonates because it not only has excellent application properties, but also has a high level of environmental compatibility.
  • an alkylbenzenesulfonic acid / sodium hydroxide solution / nonionic surfactant mixture is used as the granulating liquid, and at least 30% by weight of the total alkylbenzenesulfonate of the agent is introduced into the process by this mixture containing anionic surfactants.
  • the partially to completely neutralized mixture containing anionic surfactants can be at room temperature be solid or liquid to pasty. With high viscosities, the introduction can into the process at elevated temperature so as to create a flowable "granulating liquid" to have available.
  • the solid mixture in the mixer contains a spray-dried alkylbenzenesulfonate and / or compound containing fatty alcohol sulfate. This is preferably in Amounts of 2 to 20 wt .-%, in particular from 5 to 15 wt .-%, based on the resulting Granules.
  • the solid mixture can contain other ingredients of washing and cleaning agents, For example, other surfactants, builder substances, bleaches and Contain bleach activators, enzymes, dyes, perfumes, etc. The amounts in which such substances are used, vary within wide limits and depend on the Intended purpose of the surfactant granules to be produced.
  • the nonionic surfactants optionally used preferably with processed the anionic surfactant acid / neutralizing agent mixture in the granulation step become.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • the surfactants of the sulfonate type are preferably olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from C 12-18 monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the Receives sulfonation products.
  • alkanesulfonates obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
  • fatty acid glycerol esters the mono-, di- and triesters and their mixtures are to be understood as they in the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or obtained in the transesterification of triglycerides with 0.3 to 2 mol of glycerol.
  • Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated Fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, Capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin.
  • alk (en) yl sulfates the alkali and in particular the sodium salts of the sulfuric acid semi-esters of the C 12-18 fatty alcohols, for example, from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10-20 oxo alcohols and those half esters of secondary alcohols this chain length preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • C 16-18 alk (en) yl sulfates are particularly preferred for reasons of washing technology. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use C 16 -C 18 alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and relatively low ones Washing temperatures of, for example, room temperature to 40 ° C. show a low tendency to crystallize.
  • the agents therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably C 12-18 fatty alkyl sulfates or mixtures of C 12-14 fatty alkyl sulfates or C 12-18 fatty alkyl sulfates with C 16-18 fatty alkyl sulfates and in particular C 12-16 fatty alkyl sulfates with C 16-18 fatty alkyl sulfates.
  • not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C 16 to C 22 are used.
  • the sulfuric acid monoesters of the straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C 12-24 fatty acid soaps and 0 to 50% by weight of oleic acid soap.
  • the anionic surfactants including the soaps can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono- or dioder Triethanolamine.
  • the anionic surfactants are preferably in the form their sodium or potassium salts, especially in the form of the sodium salts.
  • non-ionic, cationic, zwitterionic or amphoteric surfactants are used.
  • nonionic surfactants which are preferably used together with the Anionic surfactant acid / neutralizing agent mixture in the granulation step in the process be introduced.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • alkyl glycosides of the general formula RO (G) X can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants either as the sole nonionic surfactant or in combination with other nonionic surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, such as those found in Japanese Patent application JP 58/217598 are described or which are preferably according to the in the international patent application WO-A-90/13533 become.
  • nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of it.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I), in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C 1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated Derivatives of this remainder.
  • R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 represents a linear, branched or cyclic alkyl radical or an aryl
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy or N-aryloxy substituted compounds can then, for example according to the teaching of international application WO-A-95/07331 by implementation with Fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxy fatty acid amides are transferred.
  • those according to the process of the invention manufactured surfactant granules also builder substances and other ingredients from Contain detergents such as bleach. These substances are preferred incorporated into the surfactant granules via the solid mixture introduced in the mixer.
  • bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
  • the content of peroxy bleaching agents in the compositions is preferably 1 to 40% by weight and in particular 10 to 20% by weight, based on the weight of the granules formed, advantageously using perborate monohydrate or percarbonate.
  • the production of surfactant granules which contain sodium percarbonate as the sole bleaching agent is preferred.
  • the bleaching agents used can advantageously be coated with a wrapping material, it being possible for all common wrapping materials and coating processes to be used.
  • bleach activators can be incorporated into the preparations.
  • Bleach activators can be compounds that are aliphatic under perhydrolysis conditions
  • Peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid can be used.
  • Substances containing O and / or N-acyl groups of the number of carbon atoms mentioned are suitable and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, in particular Triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and those from the German patent applications DE 196 16 693 and DE
  • German patent application DE 196 16 769 known hydrophilically substituted acylacetals and in German patent application DE 196 16 770 and international patent application Acyl lactams described in WO 95/14075 are also preferably used.
  • Such peracid bleach precursors are in the usual range of amounts, preferably in amounts above 0.5% by weight, in particular from 1% by weight to 10% by weight, in particular 2% by weight to 8 wt .-%, based on the resulting granules.
  • the transition metal compounds in question include in particular known from the German patent application DE 195 29 905 manganese, iron, Cobalt, ruthenium or molybdenum salt complexes and those from the German patent application DE 196 20 267 known N-analog compounds, which from the German Patent application DE 195 36 082 known manganese, iron, cobalt, ruthenium or Molybdenum-carbonyl complexes, which are described in German patent application DE 196 05 688 manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and Copper complexes with nitrogen-containing tripod ligands resulting from the German patent application DE 196 20 411 known cobalt, iron, copper and ruthenium amine complexes, those described in German patent application DE 44 16 438 Manganese, copper and cobalt complexes described in the European patent application Cobalt complexes described in EP 0 272 030, which result from the European patent application EP 0 693 550 known
  • Combinations of bleach activators and transition metal bleaching catalysts are, for example, from the German patent application DE 196 13 103 and the international patent application WO 95/27775 known.
  • Bleach-enhancing transition metal complexes especially with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru are used in conventional amounts, preferably in an amount up to 1% by weight, in particular from 0.0025% by weight to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the resulting surfactant granules.
  • builders and cobuilder substances can be used as builders in the Detergent compositions. These include in particular zeolites, Citrates and polymeric polycarboxylates. These builder substances described in more detail below are preferably in amounts above 15 wt .-%, based on the resulting surfactant granules used as part of the solid mixture.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + 1 .yH 2 O, 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 2, 3 or 4.
  • M sodium or hydrogen
  • x is a number from 1.9 to 4
  • y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 .yH 2 O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • the term “amorphous” also means “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP (R) (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production.
  • the zeolite in the event that the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • the sodium salts of the orthophosphates are particularly suitable, the pyrophosphates and especially the tripolyphosphates.
  • Their salary is generally not more than 25% by weight, preferably not more than 20% by weight, in each case on the finished product.
  • tripolyphosphates in particular even in small quantities up to a maximum of 10% by weight, based on the finished product Medium, in combination with other builder substances for a synergistic improvement of secondary washing power.
  • Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, Glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if 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 from these.
  • the acids themselves can also be used.
  • the acids have a builder effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of washing or Detergents.
  • citric acid succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000.
  • DE dextrose equivalent
  • Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 can be used.
  • a preferred dextrin is described in British patent application 94 19 091.
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 and international patent applications WO- A-92/18542, WO-A-93/08251, WO-A-94/28030, WO-A-95/07303, WO-A-95/12619 and WO-A-95/20608 are known.
  • a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
  • Suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate.
  • ethylenediamine disuccinate preferably ethylenediamine disuccinate.
  • glycerol disuccinates and glycerol trisuccinates as described, for example, in US Pat U.S. Patents US 4,524,009, US 4,639,325, in European Patent application EP-A-0 150 930 and Japanese patent application JP 93/339896 to be discribed.
  • Suitable amounts are those containing zeolite and / or silicate Formulations at 3 to 15% by weight.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be present in lactone form and which have at least 4 carbon atoms and at least one hydroxy group as well contain a maximum of two acid groups.
  • Such cobuilders are used, for example, in the international patent application WO-A-95/20029.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight from 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are especially those of acrylic acid with methacrylic acid and acrylic acid or Methacrylic acid with maleic acid. Copolymers of Acrylic acid with maleic acid, 50 to 90 wt .-% acrylic acid and 50 to 10 % By weight of maleic acid.
  • Their relative molecular mass, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120,000, and in particular 50000 to 100000.
  • the (co) polymeric polycarboxylates can either be as a powder or as an aqueous solution are used, 20 to 55% by weight aqueous solutions being preferred.
  • biodegradable polymers made from more than two different ones Monomer units, for example those which according to DE-A-43 00 772 as Monomeric salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomer salts of acrylic acid and the 2-alkylallylsulfonic acid and sugar derivatives.
  • copolymers are those described in the German patent applications DE-A-43 03 320 and DE-A-44 17 734 are described and preferably as monomers Have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • Preferred amounts of the polycarboxylates, which over the submitted in the mixer Solid mixture are introduced into the process, are above 1 wt .-%, based on the resulting surfactant granules.
  • Suitable builder substances are oxidation products of carboxyl-containing ones Polyglucosans and / or their water-soluble salts, such as, for example be described in international patent application WO-A-93/08251 or their Manufactured, for example, in international patent application WO-A-93/16110 is described.
  • Oxidized oligosaccharides according to the older ones are also suitable German patent application P 196 00 018.1.
  • further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors.
  • Polyaspartic acids are particularly preferred or their salts and derivatives, of which in the German patent application P 195 40 086.0 discloses that, in addition to cobuilder properties, it also has a have a bleach-stabilizing effect.
  • polyacetals which are obtained by converting Dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl groups have, for example, as in European patent application EP-A-0 280 223 can be obtained.
  • Preferred polyacetals are made from Dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • the agents can also contain components that make the oil and fat washable made of textiles. This effect is particularly evident if a textile is soiled, which has previously been repeatedly with an inventive Detergent containing this oil and fat-dissolving component is washed has been.
  • the preferred oil and fat-dissolving components include, for example non-ionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, and the polymers of phthalic acid and / or of the known from the prior art Terephthalic acid or its derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified Derivatives of these.
  • the sulfonated ones are particularly preferred Derivatives of phthalic acid and terephthalic acid polymers.
  • alkali carbonates also by sulfur-free, 2 to 11 carbon atoms and optionally one further carboxyl and / or amino group-containing amino acids and / or by their Salts to be replaced.
  • the agents can be known, usually in detergents additives used, for example foam inhibitors, salts of citric acid, Salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, small amounts of neutral filling salts as well as colors and fragrances, opacifiers or pearlescent agents.
  • detergents additives for example foam inhibitors, salts of citric acid, Salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, small amounts of neutral filling salts as well as colors and fragrances, opacifiers or pearlescent agents.
  • the detergent granules that are active in washing and cleaning, produced by the process contain at least 40% by weight of surfactant (s), preferably 1 to 40% by weight of peroxy bleach, and preferably above 15% by weight of one or more builder substances.
  • the bulk density of the granules is in a known manner depending on the used mixer and granulator and the operating conditions of the mixer and Granulators generally between 600 and 1300 g / l, preferably between 700 and 1100 g / l, with values above 700 g / l being particularly preferred.
  • the surfactant granules produced by the process according to the invention are suitable because of its excellent solubility and its high fat washability are very good for Training in detergents and cleaning agents. It is preferred that the through Mixture of washing and cleaning agents obtained according to the invention Processed surfactant granules in amounts of more than 50 wt .-%, based on the entire average.

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  • 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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (13)

  1. Procédé pour la préparation de produits de granulation tensioactifs possédant une activité de lavage et de nettoyage, dans un mélangeur, par transformation en granulés d'un mélange contenant un agent tensioactif anionique, que l'on prépare par neutralisation partielle à complète d'un ou de plusieurs agents tensioactifs anioniques sous leur forme acide avec un milieu de neutralisation inorganique ou organique rendant basique, dans lequel on dépose au préalable, dans le mélangeur, une substance solide ou un mélange de substances solides et on ajoute le mélange contenant un agent tensioactif anionique à cette substance solide ou à ce mélange de substances solides, caractérisé en ce que
    a) à titre de substance solide, on dépose au préalable une composition séchée par pulvérisation contenant un alkylbenzènesulfonate et/ou un sulfate d'alcool gras, ainsi que le cas échéant d'autres substances solides qui représentent des constituants habituels de produits de lavage et de nettoyage, et
    b) on ajoute le mélange contenant un agent tensioactif anionique, qui a été soumis à une neutralisation partielle ou complète, le cas échéant à température élevée, sous la forme d'un liquide de granulation, à la substance solide ou au mélange de substances solides déposé au préalable, et
    c) on règle la granulation de telle sorte que la teneur totale en agent tensioactif, rapportée au produit de granulation séché obtenu, est supérieure à 40 % en poids.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on règle la granulation de telle sorte que l'on obtient des densités apparentes supérieures à 700 g/litre.
  3. Procédé selon l'une quelconque des revendications 1 ou 2, caractérisé en ce que le mélange contenant un agent tensioactif anionique ajouté à l'étape b) est un mélange d'acide alkylbenzènesulfonique / lessive de soude / agent tensioactif non ionique et on incorpore dans le procédé au moins 30 % en poids de la teneur totale de l'agent en alkylbenzènesulfonate via ce mélange contenant un agent tensioactif anionique.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce qu'on dépose au préalable la composition a) qui a été soumise à un séchage par pulvérisation dans des quantités de 2 à 20 % en poids, de préférence de 5 à 15 % en poids, rapportés au produit de granulation obtenu.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le mélange de substances solides contient en outre un agent de blanchiment de type peroxy à concurrence de 1 à 40 % en poids, rapportés au poids du produit de granulation obtenu.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le mélange de substances solides contient en outre une quantité supérieure à 0,5 % en poids, en particulier une quantité de 1 à 10 % en poids et de manière spécifique une quantité de 2 à 8 % en poids d'un précurseur d'agent de blanchiment à base d'un peracide, rapportés au poids du produit de granulation obtenu.
  7. Procédé selon l'une quelconque des revendications 5 à 6, caractérisé en ce que l'agent de blanchiment mis en oeuvre est enrobé d'une matière d'enveloppement.
  8. Procédé selon l'une quelconque des revendications 5 à 7, caractérisé en ce qu'on met en oeuvre, à titre d'agent de blanchiment unique, du percarbonate de sodium.
  9. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que le mélange contenant un agent tensioactif anionique, que l'on ajoute à l'étape b), contient des composants supplémentaires d'agents de lavage et de nettoyage.
  10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que le mélange de substances solides déposé au préalable dans le mélangeur contient un adjuvant de lavage à concurrence de plus de 15 % en poids rapportés au poids du produit de granulation obtenu contenant un agent tensioactif.
  11. Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce que le mélange de substances solides déposées au préalable dans le mélangeur contient en outre un polycarboxylate à concurrence de plus de 1 % en poids rapporté au poids du produit de granulation obtenu.
  12. Produit de granulation contenant un agent tensioactif, que l'on obtient conformément à l'une quelconque des revendications 1 à 11, caractérisé en ce qu'il présente une densité apparente supérieure à 700 g/litre.
  13. Agent de lavage et de nettoyage contenant un produit de granulation tensioactif à concurrence d'au moins 50 % en poids qui a été obtenu conformément à l'une quelconque des revendications 1 à 11.
EP97122476A 1997-01-13 1997-12-19 Détergent granulaire pour une meilleure élimination des salissures grasses Revoked EP0853117B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19700776 1997-01-13
DE19700776A DE19700776A1 (de) 1997-01-13 1997-01-13 Granulares Waschmittel mit verbessertem Fettauswaschvermögen

Publications (2)

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EP0853117A1 EP0853117A1 (fr) 1998-07-15
EP0853117B1 true EP0853117B1 (fr) 2003-09-03

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EP97122476A Revoked EP0853117B1 (fr) 1997-01-13 1997-12-19 Détergent granulaire pour une meilleure élimination des salissures grasses

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EP (1) EP0853117B1 (fr)
AT (1) ATE248908T1 (fr)
DE (2) DE19700776A1 (fr)
ES (1) ES2206646T3 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19858859A1 (de) * 1998-12-19 2000-06-21 Henkel Kgaa Verfahren zur Herstellung wasch- oder reinigungsaktiver Granulate
DE19858886C2 (de) 1998-12-19 2002-10-31 Cognis Deutschland Gmbh Tensidgranulate
NZ768996A (en) 2016-07-15 2024-08-30 Ecolab Usa Inc Aluminum safe degreasing and pre-soak technology for bakery and deli wares and use thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IN170991B (fr) * 1988-07-21 1992-06-27 Lever Hindustan Ltd
GB8922018D0 (en) * 1989-09-29 1989-11-15 Unilever Plc Detergent compositions and process for preparing them
GB9001285D0 (en) * 1990-01-19 1990-03-21 Unilever Plc Detergent compositions and process for preparing them
EP0555622B1 (fr) * 1992-02-14 1997-07-09 The Procter & Gamble Company Procédé pour la production de granules de détergent par neutralisation des acides sulfoniques
DE4216774A1 (de) * 1992-05-21 1993-11-25 Henkel Kgaa Verfahren zur kontinuierlichen Herstellung eines granularen Wasch und/oder Reinigungsmittels

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ES2206646T3 (es) 2004-05-16
ATE248908T1 (de) 2003-09-15
DE19700776A1 (de) 1998-07-16
DE59710690D1 (de) 2003-10-09
EP0853117A1 (fr) 1998-07-15

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