EP0799302B1 - Amorphes alkalisilikat mit imprägnierung - Google Patents

Amorphes alkalisilikat mit imprägnierung Download PDF

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Publication number
EP0799302B1
EP0799302B1 EP95942157A EP95942157A EP0799302B1 EP 0799302 B1 EP0799302 B1 EP 0799302B1 EP 95942157 A EP95942157 A EP 95942157A EP 95942157 A EP95942157 A EP 95942157A EP 0799302 B1 EP0799302 B1 EP 0799302B1
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Prior art keywords
alkali metal
impregnated
silicate
weight
metal silicate
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German (de)
English (en)
French (fr)
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EP0799302A1 (de
Inventor
Rene-Andres Artiga Gonzalez
Volker Bauer
Katrin Erbs
Manfred Greger
Beatrix Kottwitz
Peter Krings
Hans-Friedrich Kruse
Peter Sandkühler
Kathrin Schnepp
Wolfgang Seiter
Wilfried Rähse
Ansgar Behler
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • 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
    • C11D17/0034—Fixed on a solid conventional detergent ingredient

Definitions

  • the invention relates to an amorphous alkali silicate with secondary washing power, that as a water-soluble builder substance in detergents or cleaning agents can be used and with ingredients of washing or cleaning agents is impregnated, the use of such impregnated alkali silicates in washing or cleaning agents, extruded washing or Detergents and a process for their preparation.
  • Modern, compressed washing or cleaning agents generally have the Disadvantage that they have a poorer because of their compact structure Dissolving behavior in aqueous liquor is shown, for example, as lighter one spray-dried washing or cleaning agents of the prior art. Washing or cleaning agents generally tend to do so poorer dissolving speed in water, the higher their degree of compaction is. Zeolites used in detergents or cleaning agents as builders are usually included due to their water insolubility in addition to the worsened dissolving behavior.
  • a water-soluble alternative for the zeolite are amorphous alkali silicates with secondary washing ability.
  • Alkali silicates in granular form with higher bulk densities can according to the teaching of European patent application EP-A-0 526 978, whereby an alkali silicate solution with a solids content between 30 and introduces 53% by weight into a heated drum, one in the longitudinal axis Shaft with a variety of close to the inner surface of the drum Arms rotates, the drum wall having a temperature between 150 and 200 ° C and the drying process by a fed into the drum Supported gas with a temperature between 175 and about 250 ° C becomes. According to this process, a product is obtained, the middle one Particle size is in the range between 0.2 and 2 mm. A preferred one Drying gas is heated air.
  • European patent application EP-A-0 542 131 describes a process in which a product which is completely soluble in water at room temperature and has a bulk density of between 500 and 1200 g / l is obtained. Drying is preferably carried out using heated air.
  • a cylindrical dryer with a heated wall 160 to 200 ° C.
  • a rotor with blade-shaped blades rotates at such a speed that the silicate solution has a solids content of between 40 and 60% by weight pseudoplastic mass with a free water content between 5 and 12 wt .-% arises. Drying is supported by a hot air stream (220 to 260 ° C).
  • Granular amorphous sodium silicates which by spray drying aqueous Water glass solutions, subsequent grinding and subsequent compacting and Rounding can be obtained with additional removal of water from the ground material, are the contents of US Pat. Nos. 3,912,649, 3,956,467, 3,838,193 and 3,879,527.
  • the water content of the products obtained is at about 18 to 20 wt .-% with bulk weights well above 500 g / l.
  • EP-A-0 561 656 and EP-A-0 488 868 are known. These are compounds of alkali silicates with certain Q distributions and alkali carbonates.
  • the international patent application WO-A-93/04153 describes a method for producing a machine dishwashing detergent which contains alkali silicate particles impregnated with nonionic surfactants.
  • the silicate particles described have an average particle diameter between 300 and 900 ⁇ m.
  • a method is known from international patent application W0-A-91/02047 known for the production of extrudates with high density, a solid and free-flowing premix is pressed in the form of a rod under pressure.
  • the solid and free-flowing premix contains a plasticizer and / or Lubricant, which causes the premix under the pressure or Entry of specific work plastically softened and thus extrudable becomes. After exiting the hole shape, there are no effects on the system Shear forces increase and the viscosity of the system increases as a result assumes that the extruded strand has predetermined extrudate dimensions can be cut.
  • detergents or cleaning agents have dilatant properties; they are used as a builder and as a phosphate substitute water-insoluble aluminosilicates such as zeolite.
  • W0-A-94/09111 are extruded washing or Detergent known, which 19 wt .-% zeolite (based on anhydrous active substance) and 12.5% by weight sodium carbonate and 2.2 % By weight of amorphous sodium silicate; however, it was not known that From a process engineering point of view, zeolite partially or even completely water-soluble inorganic builder substances such as amorphous alkali silicates can be replaced if they are used in a certain form. It now even showed in some cases that amorphous and crystalline Silicates with secondary washing capacity per extrusion and granulation of this secondary washing ability partially or even entirely lose if they are not used in a very special form of supply become.
  • An object of the invention was to provide water-soluble builder substances for the partial or complete replacement of zeolite in washing or Provide cleaning agents. Another object of the invention was therein extruded washing or cleaning agents as well as a process to provide for their preparation, which the water-soluble builder substances included to the extent that on zeolite not only for technical reasons but also partially from a procedural point of view or can be dispensed with entirely.
  • Sodium and / or potassium silicate are particularly suitable here. Sodium silicates are preferred for economic reasons. However, if, for reasons of application technology, a particularly high dissolution rate in water is important, it is advisable to replace sodium at least partially with potassium.
  • the composition of the alkali silicate can be chosen so that the silicate has a potassium content, calculated as K 2 O, of up to 5% by weight.
  • Preferred alkali silicates are in granular form and / or as a compound with alkali carbonate, preferably sodium and / or potassium carbonate, and / or have a bulk density between 300 and 1200 g / l, in particular from 350 to 800 g / l.
  • the water content of these preferred amorphous alkali silicates or of the compounds which contain the amorphous alkali silicates is advantageously between 10 and 22% by weight, in particular between 12 and 20% by weight. Water contents of 14 to 18% by weight can be particularly preferred.
  • amorphous alkali silicates of the specified module and in particular those which have a bulk density of at least 300 g / l before being impregnated with ingredients of detergents or cleaning agents are suitable starting materials for the purposes of this invention.
  • These silicates can have been produced by spray drying, granulation and / or compacting, for example by roller compacting.
  • Granules containing carbonate and silicate can also be produced by spray drying, granulating and / or compacting, for example by roller compacting.
  • Preferred carbonate-silicate compounds are those which have a weight ratio of carbonate to silicate of 3: 1 to 1: 9 and in particular of 2.5: 1 to 1: 5.
  • amorphous silicates which according to the above-mentioned US patents by spray drying or in granulators of the turbo dryer type for example from Vomm, Italy suitable and absolutely preferred starting materials with advantageous properties.
  • silicate raw materials are made with ingredients in the usual way of detergents or cleaning agents, preferably in amounts of 3 to 15 wt .-% and in particular from 5 to 12 wt .-%, each based on the non-impregnated silicate carrier, impregnated.
  • an impregnation agent are especially liquid up to the processing temperature gel-like or waxy ingredients suitable.
  • surfactants foam inhibitors based on silicone and / or paraffin or textile softening compounds such as cationic surfactants. Particularly preferred are surfactants.
  • the amorphous silicate starting materials are not mixed with aqueous Solutions or dispersions of ingredients in washing or cleaning agents impregnated, since it is feared that the silicates in the Inside the grain by the water entered not only for gluing of the products and - without subsequent drying - to process engineering Difficulties in the manufacture of detergents or cleaning agents but also the secondary washing properties of the amorphous silicates negative could affect.
  • Particularly preferred impregnating agents are nonionic surfactants, for example alkoxylated, preferably ethoxylated and / or ethoxylated and propoxylated, aliphatic C 8 -C 22 alcohols.
  • nonionic surfactants for example alkoxylated, preferably ethoxylated and / or ethoxylated and propoxylated, aliphatic C 8 -C 22 alcohols.
  • These include in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (E0) per mole of alcohol, in which the alcohol radical can be methyl-branched linearly or preferably in the 2-position or contain linear and methyl-branched radicals in the mixture can, as is usually present in oxo alcohol residues.
  • 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 E0 per mole of alcohol are also preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 E0 or 4 E0, C 9 -C 11 alcohol with 7 E0, C 13 -C 15 alcohols with 3 E0, 5 E0, 7 E0 or 8 E0, C 12 -C 18 alcohols with 3 E0, 5 E0 or 7 E0 and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 E0 and C 12 -C 18 alcohol with 5 E0.
  • 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 E0 can also be used. Examples include tallow fatty alcohol with 14 E0, 25 E0, 30 E0 or 40 E0.
  • alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters
  • fatty acid alkyl esters preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters
  • the agent contains the alkoxylated fatty acid methyl ester in a weight ratio to the silicate (anhydrous active substance) or to a silicate-containing compound (likewise anhydrous active substance) of 1: 6 to 1:30.
  • the impregnated amorphous alkali silicates do not have satisfactory flow properties. Especially if nonionic surfactants are used as impregnating agents The impregnated alkali silicates have therefore proven to be advantageous to treat. For this become the impregnated Silicates with other ingredients of washing or cleaning agents, especially afterwards with builder substances or aqueous solutions treated according to usual methods.
  • impregnated amorphous alkali silicates or compounds which contain amorphous alkali silicates are provided, which were subsequently treated, that is to say in a second stage, with an aqueous solution which contains further detergent or cleaning agent ingredients.
  • an aqueous solution of water-soluble builder substances in particular polycarboxylates, polymeric polycarboxylates and / or amorphous alkali silicates with a molar ratio M 2 O: SiO 2 of 1: 5 to 1: 3.3 and in particular 1: 1 , 9 to 1: 2.5, this aqueous solution being sprayed onto the already impregnated amorphous silicates.
  • Examples of useful water-soluble organic builders are 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), if one such use is not objectionable for ecological reasons, and Mixtures of these.
  • Preferred salts are the salts of the 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 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 acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid have proven particularly suitable proven that 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid contain.
  • Their relative molecular mass, 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.
  • Terpolymers are also particularly preferred, for example those according to DE-A-43 00 772 as monomers 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 2-alkylallylsulfonic acid as well as sugar derivatives.
  • Other preferred copolymers are those described in German Patent application DE-A-4303320 and in EP-A-0684265 are described and the monomers preferably acrolein and acrylic acid / acrylic acid salts or Have acrolein and vinyl acetate.
  • Suitable builder systems are oxidation products from carboxyl-containing polyglucosans and / or their water-soluble Salts such as those used in the international patent application W0-A-93/08251 can be described or their production, for example, in of international patent application WO-A-93/16110.
  • polyacetals which by reaction of dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and have at least 3 hydroxyl groups, for example as in European Patent application EP-A-0 280 223 can be obtained.
  • Preferred polyacetals are derived from dialdehydes such as glyoxal, glutaraldehyde, Terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • Such amounts of ingredients are preferred in this aftertreatment of detergents or cleaning agents that these ingredients, expressed as a solid based on the non-impregnated Carrier, make up 0.5 to 10 wt .-%.
  • the impregnated silicates aftertreated with aqueous solutions can then dried and / or with finely divided ingredients, for example Silicas, silicates, zeolite or powdery polymeric polycarboxylates be powdered. It is expressly pointed out that also the impregnated silicates aftertreated with an aqueous solution preferably in granular form and a water content of 10 have up to 22 wt .-%, preferably from 12 to 20 wt .-%.
  • the powdering agents are preferably in amounts up to 3 wt .-%, based on the powdered silicate, included.
  • a wrapping is included aqueous solutions or dispersions without drying only possible if the overall water content is relatively low, i.e. highly concentrated Solutions / dispersions are used and / or the water content of the silicate carrier is correspondingly low.
  • wrapper although itself preferred water-soluble, delaying the hydrothermal attack.
  • the amorphous and impregnated alkali silicates with secondary washing ability can as an admixture component to powdery to granular washing or Detergent with bulk weights or as part of the manufacturing process the granular detergent or cleaning agent, preferably in the Granulation and / or compacting can be used.
  • the invention Detergents or cleaning agents can have a bulk density between 300 and 1200 g / l, preferably from 500 to 1000 g / l, and contain the impregnated silicates according to the invention preferably in amounts of 5 up to 50% by weight, in particular in amounts of 10 to 40% by weight. Your manufacture can be made by any of the known processes such as mixing, spray drying, Granulation, compacting such as roller compaction and extrusion take place.
  • Suitable surface modifiers are known from the prior art.
  • Particularly preferred embodiments of the invention are extruded Detergents or cleaning agents with a bulk density above 600 g / l, which anionic and optionally nonionic surfactants and a Amorphous and impregnated alkali silicate of the specified type in the extrudate contain.
  • anionic and optionally nonionic surfactants and a Amorphous and impregnated alkali silicate of the specified type in the extrudate contain are produced by these extruded detergents or cleaning agents.
  • the finished detergents or cleaning agents can also do the following Contain ingredients.
  • surfactants especially anionic surfactants and, if appropriate nonionic surfactants, but also cationic, amphoteric or zwitterionic surfactants.
  • Preferred anionic surfactants of the sulfonate type are C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates, and disulfonates such as are obtained, for example, from C 12 -C 18 monoolefins with an end or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.
  • alkanesulfonates obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfofatty acids are also suitable, for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • suitable anionic surfactants are the ⁇ -sulfofatty acids obtainable by ester cleavage of the ⁇ -sulfofatty acid alkyl esters or their di-salts.
  • the mono-salts of the ⁇ -sulfofatty acid alkyl esters are obtained in their industrial production as an aqueous mixture with limited amounts of di-salts.
  • the disalt content of such surfactants is usually below 50% by weight of the anionic surfactant mixture, for example up to about 30% by weight.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters, which represent mono-, di- and triesters and their mixtures as they do in the production by esterification by a monoglycerol with 1 to 3 Moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles Glycerin can be obtained.
  • 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 half-esters of the C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • C 16 -C 18 alk (en) yl sulfates are particularly preferred from the point of view 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.
  • the compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C 12 -C 14 fatty alkyl sulfates or C 12 -C 18 fatty alkyl sulfates with C 16 -C 18 fatty alkyl sulfates and in particular C 12 -C 16 -Fatty alkyl sulfates with C 16 -C 18 fatty alkyl sulfates.
  • saturated 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.
  • Mixtures of saturated sulfonated fatty alcohols predominantly consisting of C 16 and unsaturated sulfated fatty alcohols predominantly consisting of C 18 are particularly preferred, for example those derived from solid or liquid HD-Ocenol (R) fatty alcohol mixtures (commercial product of the applicant) .
  • Weight ratios of alkyl sulfates to alkenyl sulfates from 10: 1 to 1: 2 and in particular from about 5: 1 to 1: 1 are preferred.
  • the sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9 -C 11 alcohols with an average of 3.5 mol of ethylene oxide (E0) or C 12 - C 18 fatty alcohols with 1 to 4 E0 are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which represent monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 to C 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).
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • the agents can also contain soaps, preferably contained in amounts of 0.2 to 5 wt .-%.
  • Saturated ones are suitable Fatty acid soaps, such as the salts of lauric acid, myristic acid, Palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid as well especially from natural fatty acids, e.g. Coconut, palm kernel or Tallow fatty acids, derived soap mixtures.
  • the anionic surfactants and soaps can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, Di- or triethanolamine.
  • the anionic are preferably located Surfactants in the form of their sodium or potassium salts, especially in the form of Sodium salts.
  • detergents or cleaning agents especially preferred extruded washing or cleaning agents, which contain 10 to 30% by weight of anionic surfactants.
  • anionic surfactants preferably at least 3% by weight and in particular at least 5% % By weight of sulfate surfactants.
  • sulfate surfactants in the means - based on the total anionic surfactants - at least 15 wt .-%, in particular 20 to 100 wt .-% sulfate surfactants.
  • 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 (E0) per mole of alcohol, in which the alcohol radical 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.
  • 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 E0 per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 E0 or 4 E0, C 9 -C 11 alcohol with 7 E0, C 13 -C 15 alcohols with 3 E0, 5 E0, 7 E0 or 8 E0, C 12 -C 18 alcohols with 3 E0, 5 E0 or 7 E0 and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 E0 and C 12 -C 18 alcohol with 5 E0.
  • 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 E0 can also be used. Examples include tallow fatty alcohol with 14 E0, 25 E0, 30 E0 or 40 E0.
  • non-ionic surfactants that either as the sole nonionic surfactant or in combination with others nonionic surfactants, especially together with alkoxylated Fatty alcohols used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester, as for example in the Japanese patent application JP 58/217598 are described or which are preferably according to the in the international patent application WO-A-90/13533 getting produced.
  • 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.
  • 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 may be suitable.
  • the amount of this nonionic surfactants are preferably no more than that of the ethoxylated ones Fatty alcohols, especially not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I), in which R 2 is C0 for an aliphatic acyl radical with 6 to 22 carbon atoms, R 3 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 stands.
  • the polyhydroxy fatty acid amides are known substances that usually 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 can be obtained.
  • the polyhydroxy fatty acid amides are preferably derived from reducing agents Sugars with 5 or 6 carbon atoms, especially from that Glucose.
  • Nonionic surfactants are preferred in the agents according to the invention in amounts of 0.5 to 15% by weight, in particular in amounts of 2 to 10 % By weight.
  • the funds can also be used for further, additional Builders and cobuilders included.
  • additional Builders and cobuilders included.
  • the latter include in primarily the ingredients already mentioned above, for example Polycarboxylates and polymeric polycarboxylates.
  • These cobuilders are in the Agents preferably in amounts of 2 to 20% by weight and in particular 5 contain up to 15 wt .-%.
  • the synthetic zeolite used is preferably finely crystalline and contains bound water.
  • Zeolite A for example, but also zeolite X and zeolite P and mixtures of A, X and / or P are 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 may contain minor 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. It is also possible to use zeolite suspensions and zeolite powder. Suitable zeolite powders 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.
  • washing or Cleaning agent 10 to 16 wt .-% zeolite (based on anhydrous active substance) and 10 to 30% by weight of an impregnated alkali silicate.
  • the Washing or cleaning agents 0 to 5 wt .-% zeolite (based on anhydrous active substance) and 15 to 40 wt .-% of an impregnated alkali silicate. It is possible that the zeolite not only co-extrudes is, but that the zeolite partially or completely retrospectively, ie after introduced into the washing or cleaning agent during the extrusion step becomes. Washing or cleaning agents which are particularly preferred here contain an extrudate that is free from inside the extrudate grain Is zeolite.
  • Crystalline layered silicates can also be used as substitutes for the zeolite and / or conventional phosphates are used. However, it is preferred that phosphates only in small amounts, in particular up to a maximum 10% by weight, are contained in the washing or cleaning agents.
  • 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 disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • these crystalline layered silicates are preferably contained in the extrudates according to the invention only in amounts of not more than 10% by weight, in particular less than 8% by weight, advantageously not more than 5% by weight.
  • the agents can also contain components which and grease washability from textiles positively. This effect becomes particularly clear when a textile that is already soiled is soiled previously several times with a detergent according to the invention that this oil and contains fat-dissolving component, is washed.
  • nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion on methoxyl groups from 15 to 30% by weight and on hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic Cellulose ether, as well as the polymers known from the prior art Phthalic acid and / or terephthalic acid or their derivatives, in particular Polymers made from ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives of these.
  • the agents can also contain components which have solubility especially the heavy granules.
  • Such components and the introduction of such components for example in international patent application W0-A-93/02176 and in German patent application DE 42 03 031.
  • Ingredients include in particular fatty alcohols with 20 to 80 Moles of ethylene oxide per mole of fatty alcohol, for example tallow fatty alcohol with 30 E0 and tallow fatty alcohol with 40 E0, but also fatty alcohols with 14 E0 as well Polyethylene glycols with a molecular weight between 200 and 2000.
  • 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 or diperdodecanedioic acid.
  • the bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, with perborate monohydrate being advantageously used.
  • Percarbonate is also preferred as an ingredient. However, percarbonate is preferably not co-extruded, but optionally mixed in subsequently.
  • bleach activators can be incorporated into the preparations.
  • these are N-acyl or O-acyl compounds which form organic peracids with H 2 O 2 , preferably N, N'-tetraacylated diamines, p- (alkanoyloxy) benzenesulfonates, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate.
  • Other known bleach activators are acetylated mixtures of sorbitol and mannitol, as described, for example, in European patent application EP-A-0 525 239.
  • 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'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN).
  • TAED N, N, N ', N'-tetraacetylethylene diamine
  • DADHT 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine
  • SORMAN acetylated sorbitol-mannitol mixtures
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized 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 and / 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.
  • Enzymes come from the class of proteases, lipases, including in the context of this invention also lipolytic enzymes such as cutinases be understood, amylases, cellulases or mixtures thereof in question. Especially from bacterial strains or fungi such as Bacillus are well suited subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens obtained enzymatic active ingredients. Proteases are preferably from Subtilisin type and especially proteases derived from Bacillus lentus be used.
  • Enzyme mixtures are, for example, from Protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or Protease, lipase and cellulase, but especially protease and / or Mixtures of lipase of particular interest. Peroxidases or Oxidases have been found to be suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition.
  • the percentage of enzymes Enzyme mixtures or enzyme granules can for example be about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-%.
  • the stabilizers come in particular for per-compounds and enzymes Salts of polyphosphonic acids, especially 1-hydroxyethane-1,1-diphosphonic acid (HEDP), diethylenetriaminepentamethylenephosphonic acid (DETPMP) or Ethylenediaminetetramethylenephosphonic acid into consideration.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DETPMP diethylenetriaminepentamethylenephosphonic acid
  • Ethylenediaminetetramethylenephosphonic acid into consideration.
  • the agents can also contain further enzyme stabilizers.
  • enzyme stabilizers For example, 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.
  • boron compounds for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyrobic acid (tetraboric acid H 2 B 4 O 7 ), is particularly advantageous.
  • Graying inhibitors have the task of removing the fiber Keep dirt suspended in the fleet and prevent 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 Starch or the cellulose or salts of acidic sulfuric acid esters Cellulose or starch. Also water-soluble containing acidic groups Polyamides are suitable for this purpose.
  • soluble ones Use starch preparations and other starch products than those mentioned above, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful.
  • cellulose ethers such as carboxymethyl cellulose are preferred (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as Methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures, and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition.
  • the agents can, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed connections that instead the morpholino group is a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present be, e.g.
  • Example 2 Flow behavior of impregnated silicates
  • Example 1a To determine the pourability, 1 liter each of the non-impregnated amorphous sodium disilicate, which was used as the starting material in Example 1a), the impregnated silicates IS1 to IS3 and a heat-treated IS1 (called IS1 / 1) were placed in a powder funnel which was initially closed at its outlet opening filled and then measured the flow time of the silicates compared to dry sea sand. The run-out time of the dry sea sand after opening the outlet opening (13 seconds) was set to 100%. Flow behavior compared to dry sea sand (100%) silicate % non-impregnated silicate according to 1a) 92 IS1 12th IS1 / 1 35 IS2 59 IS3 68
  • Example 3 Production of extruded detergents E1 to E4 and comparison agents V1 to V4
  • the application test was carried out under practical conditions in household washing machines.
  • the machines with 3.0 kg clean laundry and 0.5 kg of test fabric loaded the test fabric from white stripes from standardized cotton fabric (laundry research institute Krefeld, WFK), nettle (BN), knitwear (cotton jersey; B) and terry toweling (FT).
  • standardized cotton fabric laundry research institute Krefeld, WFK
  • BN nettle
  • knitwear cotton jersey
  • B terry toweling
  • Washing conditions Tap water of 23 ° d (equivalent to 230 mg CaO / l), amount of detergent used per detergent and machine 80 g, wash temperature 90 ° C, liquor ratio (kg of laundry: liters of wash liquor in the main wash) 1: 5.7, rinse 3 times with tap water, spin off and drying, ashing.
  • Ash determination 25 washes Ash values Agent (not according to the invention) Wt% ash WFK BN FT B ⁇ Initial value 0.49 0.51 0.67 0.66 0.58 E1 5.04 3.44 2.84 3.19 3.63 V1 5.82 4.00 3.34 4.17 4.33 V2 4.81 3.22 2.29 2.60 3.23 E4 5.09 4.44 4.37 3.33 4.31 V3 5.37 4.90 4.57 3.55 4.60 V4 5.64 3.82 4.85 4.09 4.60
  • Extrudate E5 was produced, E5 containing 13.3% by weight of zeolite A (anhydrous active substance) and 20 parts by weight of a Britesil (R) impregnated with nonionic surfactants (module 2.0), C 12 fatty acid methyl ester with 12 EO was used and the weight ratio of nonionic surfactant to sodium disilicate (anhydrous active substance) was 1: 9. In addition, C 12 fatty acid methyl esters with 12 EO were used separately, so that the total content of E5 in this nonionic surfactant was 4.9% by weight.
  • the comparative extrudate V5 had a recipe similar to E5, but contained no impregnated silicate, but instead 28% by weight of zeolite (anhydrous active substance) and C 12 fatty acid methyl ester with 12 E0 as separate constituents.
  • the dissolving behavior showed only slightly better values for E5 compared to V5 (both values were good); on the other hand, it was observed that in a modified hand wash test, no gelling / clumping occurred when using E5, as was the case with V5.

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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)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Dental Preparations (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
EP95942157A 1994-12-23 1995-12-14 Amorphes alkalisilikat mit imprägnierung Expired - Lifetime EP0799302B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4446363 1994-12-23
DE4446363A DE4446363A1 (de) 1994-12-23 1994-12-23 Amorphes Alkalisilikat mit Imprägnierung
PCT/EP1995/004950 WO1996020269A1 (de) 1994-12-23 1995-12-14 Amorphes alkalisilikat mit imprägnierung

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EP0799302A1 EP0799302A1 (de) 1997-10-08
EP0799302B1 true EP0799302B1 (de) 1999-02-17

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DE19529908A1 (de) * 1995-08-15 1997-02-20 Henkel Kgaa Verfahren zur Herstellung eines amorphen Alkalisilikats mit Imprägnierung
DE19533790A1 (de) * 1995-09-13 1997-03-20 Henkel Kgaa Verfahren zur Herstellung eines amorphen Alkalisilikats mit Imprägnierung
DE19700775A1 (de) * 1997-01-13 1998-07-16 Henkel Kgaa Verfahren zur Herstellung aniontensidhaltiger wasch- und reinigungsaktiver Tensidgranulate
DE10064638A1 (de) * 2000-12-22 2002-07-04 Henkel Kgaa Silikatische Partikel
DE102007032670A1 (de) 2007-07-13 2009-01-15 Clariant International Ltd. Wässrige Zusammensetzungen enthaltend Alkylpolyethylenglykolethersulfate

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KR927003783A (ko) * 1989-08-09 1992-12-18 게오르그 차이트 세제용 압축과립의 제조방법
WO1993004153A1 (en) * 1991-08-13 1993-03-04 The Procter & Gamble Company Process for making granular automatic dishwashing detergent
DE4235646A1 (de) * 1992-10-22 1994-04-28 Henkel Kgaa Verfahren zur Herstellung wasch- und reinigungsaktiver Extrudate
DE4320358A1 (de) * 1993-06-21 1994-12-22 Henkel Kgaa Verfahren zur Herstellung wasch- oder reinigungsaktiver Extrudate

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CZ189097A3 (cs) 1998-06-17
ATE176802T1 (de) 1999-03-15
HU218141B (hu) 2000-06-28
SK79897A3 (en) 1998-02-04
DE59505132D1 (de) 1999-03-25
ES2129888T3 (es) 1999-06-16
DE4446363A1 (de) 1996-06-27
HUT77061A (hu) 1998-03-02
WO1996020269A1 (de) 1996-07-04

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