EP0839178B1 - Amorphes alkalisilicat-compound - Google Patents

Amorphes alkalisilicat-compound Download PDF

Info

Publication number
EP0839178B1
EP0839178B1 EP96924857A EP96924857A EP0839178B1 EP 0839178 B1 EP0839178 B1 EP 0839178B1 EP 96924857 A EP96924857 A EP 96924857A EP 96924857 A EP96924857 A EP 96924857A EP 0839178 B1 EP0839178 B1 EP 0839178B1
Authority
EP
European Patent Office
Prior art keywords
alkali metal
weight
metal silicate
compound
silicate
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.)
Expired - Lifetime
Application number
EP96924857A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0839178A1 (de
Inventor
Rene-Andrés Artiga Gonzalez
Volker Bauer
Katrin Burmeister
Stefan Hammelstein
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0839178A1 publication Critical patent/EP0839178A1/de
Application granted granted Critical
Publication of EP0839178B1 publication Critical patent/EP0839178B1/de
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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • 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
    • C11D17/06—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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates

Definitions

  • the invention relates to a method for producing a amorphous alkali silicate / alkali carbonate compounds containing surfactants Secondary washing ability, which as a water-soluble builder in Detergents or cleaning agents can be used, as well as the Use of such alkali silicate compounds in washing or cleaning agents, extruded detergents or cleaning agents and a Process for their production.
  • Modern, compacted detergents or cleaning agents generally have the disadvantage that they are due to their compact structure show poorer dissolving behavior in aqueous liquor than, for example lighter spray-dried washing or cleaning agents the state of the art.
  • Detergents or cleaning agents tend to do this generally at a slower dissolving rate in water, the higher their degree of compaction.
  • Zeolites in Washing or cleaning agents are usually used as builder substances may be included due to their water insolubility contribute to the deterioration in 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 can be obtained, using an alkali silicate solution with a Solids content between 30 and 53 wt .-% in a heated drum brings in the longitudinal axis of a shaft with a variety of arms rotating close to the inner surface of the drum, wherein the drum wall has a temperature between 150 and 200 ° C and the drying process by a gas fed into the drum is supported with a temperature between 175 and about 250 ° C. 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).
  • the older, unpublished application P 44 19 745.4 describes also a water-soluble, amorphous and granular Alkali silicate, which in a similar manner as in EP-A-0 526 978 described is produced, but is siliceous.
  • amorphous means "X-ray amorphous”. This means that the alkali silicates have no sharp reflections in X-ray diffraction deliver, but at most one or more broad maxima, the width of which is several degree units of the diffraction angle. However, this does not rule out the fact that in electron diffraction experiments Areas are found that have sharp electron diffraction reflections deliver. This is to be interpreted as the substance microcrystalline areas on the order of up to approx. 20 nm (max. 50 nm).
  • Granular amorphous sodium silicates which by spray drying aqueous Water glass solutions, subsequent grinding and subsequent Compacting and rounding with additional dehydration of the regrind are contained in the US patents 3,912,649, 3,956,467, 3,838,193 and 3,879,527.
  • the water content the products obtained are about 18 to 20% by weight with bulk weights significantly above 500 g / l.
  • EP-A-0 561 656 and EP-A-0 488 868 are compounds of alkali silicates with certain Q distributions and alkali carbonates.
  • the products are made by powdered anhydrous Sodium carbonate using a sodium silicate solution (water glass solution) granulated and the products dry so that they have a certain residual water content bound to the silicate. After attempts by the applicant, such products prove relatively low absorption capacity for nonionic surfactants in the area of ⁇ 30 g nonionic surfactants per 100 g compound. In the state of the art it is not known to use such compounds to produce anionic surfactant-containing aqueous preparations.
  • a method is known from international patent application WO-A-91/02047 known for producing high density extrudates, being a solid and free-flowing premix under pressure is pressed into a strand.
  • the solid and free-flowing premix contains a plasticizer and / or lubricant, which causes that the premix under the pressure or the entry more specific Work softens plastically and thus becomes extrudable. After this Leaving the hole shape has no shear forces on the system more and the viscosity of the system increases so much that the extruded strand to predeterminable Extrudate dimensions can be cut.
  • a common part of conventional laundry or detergent has dilatant properties; it are those used as builders and phosphate substitutes water-insoluble aluminosilicates such as zeolite.
  • W0-A-94/09111 are extruded washing or cleaning agents known, which 19 wt .-% zeolite (based on anhydrous active substance) and 12.5% by weight sodium carbonate and contain 2.2% by weight of amorphous sodium silicate; however it was not known that zeolite partially from a process engineering point of view or even entirely through water-soluble inorganic Builder substances such as amorphous alkali silicates can be replaced, if they are used in a certain form.
  • EP-A-651 050 describes a process for the production of granules, an amorphous silicate as essential components Anionic surfactant and another solid salt included, for example Can be sodium carbonate. This will add more salt submitted and with an aqueous "binder” Alkali metal silicate solution and anionic surfactant agglomerated.
  • Sodium carbonate is one of many selectable salt components
  • the alkali metal silicate and the anionic surfactant contains in weight ratios between 1: 3 and 3: 1 about the weight ratio between "binder" and salt component nothing said.
  • the manufactured in the embodiments Agglomerates have sodium carbonate contents of less than 10% by weight.
  • the preferred and in the exemplary embodiments in proportions of 35.5% by weight of the salt present is sodium sulfate.
  • An object of the invention was to provide more water-soluble Builder substances for the partial or complete replacement of To provide zeolite in detergents or cleaning agents, whereby the dissolving behavior, in particular of heavy washing or cleaning agents should be improved.
  • these should water-soluble builders also have a capacity for Liquid to waxy ingredients at processing temperature of detergents or cleaning agents.
  • Another The object of the invention was extruded washing or cleaning agents and to provide a process for their production, which the water-soluble builder substances to the extent contain that on zeolite not only from an application but also partially or entirely from a procedural point of view can be dispensed with.
  • 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 present as a compound with alkali carbonate, preferably sodium and / or potassium carbonate.
  • the water content of these preferred amorphous alkali silicate compounds is advantageously between 10 and 22% by weight, in particular between 12 and 20% by weight. Water contents of 14 to 19% by weight can be particularly preferred.
  • silicates can have been produced by spray drying, granulation and / or compacting, for example by roller compacting.
  • Compounds containing carbonate and silicate can also be produced by spray drying, granulation and / or compaction, for example by roller compaction.
  • Preferred carbonate-alkali 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.
  • These commercially available alkali silicates or compounds can be granulated, for example, with aqueous solutions of anionic surfactants or with anionic surfactant acids.
  • amorphous silicates which according to the above-mentioned US patents by spray drying or in granulators from the Type of turbo dryer, for example, manufactured by Vomm, Italy are suitable and quite preferred Starting materials with advantageous properties. It is at turbo granulation possible, the compounds directly on the to produce according to the invention.
  • Alkali metal silicate / alkali metal carbonate compounds can be used in general proceed in such a way that in a suitable mixing unit or in a fluidized bed at least one of the components Specifies alkali metal silicate or alkali metal carbonate in powder form and by spraying an aqueous solution of an anionic surfactant, the if necessary, an additional component of the to be manufactured Contains compounds in dissolved and / or dispersed form, sprayed on.
  • the anionic surfactant can be used as an alkali metal salt, for example as a sodium salt, as a surfactant acid or in partially neutralized Form are used.
  • a powdery mixture from alkali metal silicate and alkali metal carbonate and this using an aqueous anionic surfactant preparation agglomerate.
  • This aqueous preparation can be a real solution, an emulsion or a water-based one Trade surfactant paste.
  • the method according to the invention also be carried out in the form that one is pre-educated Compound of alkali metal silicate and alkali metal carbonate with a such aqueous anionic surfactant preparation agglomerated.
  • the preformed Compound of alkali metal silicate and alkali metal carbonate can for example by spray drying an aqueous solution or Suspension are obtained, which contains both components. It can however, a compound can also be used for this, which can be Agglomeration of one component in powder form with an aqueous Can get solution of the second components.
  • the preferred alkali metal carbonate is sodium and / or Potassium carbonate, with sodium carbonate for economic reasons is preferred.
  • the state of the art Use known mixing and agglomeration units.
  • the turbo dryer described in more detail above may be mentioned or also slower rotating and preferably with mixing Built-in drums, pelletizing plates that are around rotate an axis, preferably inclined to the vertical, and a fluidized bed fluidized by a gas stream.
  • Anionic surfactants that are used in the alkali silicate compounds are, above all, surfactants of the sulfonate and / or sulfate type.
  • Preferred 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 a terminal 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.
  • 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. show a low tendency to crystallize.
  • the compounds 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.
  • 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 -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 (EO) 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.
  • the Compounds 15 to 80% by weight alkali silicates, 1 to 20% by weight Anionic surfactants and 10 to 22 wt .-%, preferably 12 to 19 wt .-% and in particular 14 to 19 wt .-% water.
  • the compounds according to the invention 15 to 50 wt .-%, preferably 20 to 40% by weight alkali silicates, 30 to 70% by weight, preferably 40 to 65% by weight of alkali carbonates, 1.5 to 15% by weight and in particular 2 to 12% by weight of anionic surfactants, advantageously Alkylbenzenesulfonates and / or alk (en) ylsulfates, and 12 to 19 % By weight of water.
  • the alkali silicate compounds can also contain other ingredients of washing or cleaning agents, preferably in Amounts up to 10% by weight and especially in amounts not above 5 % By weight.
  • these include, for example, neutral salts such as Sodium or potassium sulfates, but also graying inhibitors or nonionic surfactants such as alkyl polyglycosides.
  • the alkali silicate compounds according to the invention have a significant one Capacity for at the usual processing temperatures liquid to waxy ingredients of washing or Detergents.
  • Alkali silicate compounds can also be used without Anionic surfactant add certain amounts of liquid components; However, it has been shown that the addition of anionic surfactants increases the absorption capacity of the alkali silicate compounds and that Trickle behavior is improved.
  • the anionic surfactant according to the invention have a capacity for liquid components that is at least 20% higher than that of the same quantity Alkali silicate compounds without anionic surfactants.
  • Alkali silicate compounds have a capacity for liquid components that is at least 20% higher than that of the same quantity Alkali silicate compounds without anionic surfactants.
  • their absorption capacity for liquid components even by at least 30% and advantageously even by at least 50%, each based on the absorption capacity of the same quantity corresponding alkali silicate compounds without anionic surfactants has been.
  • alkali silicate compounds produced according to the invention are therefore claimed, which have been aftertreated with liquid components, which in the context of this invention include liquid to waxy ingredients of washing or cleaning agents.
  • suitable liquid components which can be absorbed by the alkali silicate compounds according to the invention are, for example, nonionic surfactants, cationic surfactants and / or foam inhibitors such as silicone oils and paraffin oils.
  • nonionic surfactants are particularly preferred, for example alkoxylated, preferably ethoxylated and / or ethoxylated and propoxylated, aliphatic C 8 -C 22 alcohols.
  • alcohols with 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 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.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues from 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 also preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohol with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 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.
  • those produced according to the invention can Alkali silicate compounds with ingredients of washing or cleaning agents be treated. This can be done in a conventional manner be carried out, for example by mixing or spraying in a mixer / granulator, optionally with a subsequent one Heat treatment.
  • the amorphous alkali silicate compounds with secondary washing ability can be added as a component to powdery to granular Detergents or cleaning agents or as a component in the manufacture the granular washing or cleaning agents, preferably for granulation and / or compacting.
  • Each the bulk weights of the Alkali silicate compounds between approximately 300 and, for example, 950 g / l vary. With continuous production, bulk weights can up to 1150 g / l can be achieved.
  • the washing according to the invention or cleaning agents can have a bulk density between 300 and 1200 g / l, preferably from 500 to 1000 g / l, and preferably contain the alkali silicate compounds according to the invention in amounts of 5 to 50% by weight, in particular in amounts of 10 up to 40% by weight.
  • They can be produced by any of the known processes like mixing, granulating, compacting like Roll compacting and extrusion take place. Are particularly suitable processes in which several sub-components, for example spray-dried components and granulated and / or extruded components are mixed together.
  • Retrofitting components for example with nonionic surfactants, especially ethoxylated fatty alcohols, be applied according to the usual procedures.
  • nonionic surfactants especially ethoxylated fatty alcohols
  • further anionic surfactants in the form of a spray-dried, granulated or extruded compounds either as Additive component in the process or as an additive subsequently use other granules.
  • finely divided zeolites, Silicas, amorphous silicates, fatty acids or fatty acid salts for example calcium stearate, but especially mixtures of Zeolite and silica, especially in the zeolite weight ratio to silica of at least 1: 1, or zeolite and calcium stearate particularly preferred.
  • Particularly preferred embodiments of the invention are extruded washing or cleaning agents with a bulk weight above 600 g / l, which are anionic and optionally nonionic Surfactants and an amorphous alkali silicate compound Type according to the invention contained in the extrudate.
  • this extruded detergent or cleaning agent is on the known methods of extrusion, especially on the international Patent application WO-A-91/02047.
  • the finished detergents or cleaning agents can also be used now contain the following ingredients.
  • surfactants especially anionic surfactants as well optionally non-ionic surfactants, but also cationic, amphoteric or zwitterionic surfactants.
  • the anionic surfactants of the sulfonate type include those already mentioned above Alkyl benzene sulfonates, olefin sulfonates and alkane sulfonates into consideration.
  • the esters of ⁇ -sulfofatty acids are also suitable (Ester sulfonates), e.g. the ⁇ -sulfonated methyl esters hydrogenated coconut, palm kernel or tallow fatty acids.
  • Further suitable anionic surfactants are those by ester cleavage of the ⁇ -sulfofatty acid alkyl esters available ⁇ -sulfo fatty acids or their Di salts.
  • the mono-salts of the ⁇ -sulfofatty acid alkyl esters fall even in their industrial production as an aqueous mixture with limited amounts of di-salts.
  • the disalt content of such Surfactants is usually less than 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 in the manufacture by esterification through a Monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of Triglycerides with 0.3 to 2 moles of glycerin can be obtained.
  • Suitable surfactants of the sulfate type are the aforementioned sulfuric acid monoesters from primary alcohols of natural and synthetic origin and, if appropriate, their alkoxylated, preferably ethoxylated, derivatives.
  • 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 are nonionic surfactants in themselves. Again, sulfosuccinates whose fatty alcohol residues 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.
  • the agents can also contain soaps, preferably contained in amounts of 0.2 to 5 wt .-%.
  • soaps preferably contained in amounts of 0.2 to 5 wt .-%.
  • Suitable are saturated fatty acid soaps, like the salts of lauric acid, Myristic acid, palmitic acid, stearic acid, hydrogenated Erucic acid and behenic acid and in particular 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 as well as organic organic salts Bases, such as mono-, di- or triethanolamine, are present.
  • the anionic surfactants in the form of their sodium or potassium salts, especially in the form of the sodium salts.
  • detergents or cleaning agents in particular extruded washing or cleaning agents preferred, which contain 10 to 30 wt .-% anionic surfactants.
  • sulfate surfactants are in the means - based on the total anionic surfactants - at least 15% by weight, in particular Contain 20 to 100 wt .-% sulfate surfactants.
  • Preferred nonionic surfactants are those already described above alkoxylated, advantageously ethoxylated alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) used per mole of alcohol.
  • EO ethylene oxide
  • 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 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 them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I), in the R 2 CO for an aliphatic acyl radical having 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 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.
  • Nonionic surfactants are preferred in the agents according to the invention in quantities of 0.5 to 15% by weight, in particular in quantities contain from 2 to 10 wt .-%.
  • the compositions can also contain further, additional builder substances and cobuilders.
  • customary builder substances such as phosphates, zeolites and crystalline layered silicates can be contained in the agents.
  • 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. Zeolite can be contained in the washing or cleaning agents in amounts of up to about 40% by weight (based on anhydrous active substances).
  • Washing or cleaning agents 10 to 16 wt .-% zeolite (based on anhydrous active substance) and 10 to 30 wt .-% of one Alkali silicate compounds produced according to the invention.
  • the detergents or cleaning agents contain 0 to 5 % By weight of zeolite (based on anhydrous active substance) and 15 to 40% by weight of an alkali silicate compound produced according to the invention. It is possible that the zeolite not only is coextruded, but that the zeolite is partially or wholly subsequently, ie after the extrusion step into the washing or Detergent is introduced. Are particularly preferred here Detergents or cleaning agents that contain an extrudate that in the Inside of the extrudate grain is free of zeolite.
  • Crystalline can also be used as substitutes for the zeolite Layered silicates and / or conventional phosphates are used. However, it is preferred that phosphates only in small amounts, in particular up to a maximum of 10% by weight in the washing or cleaning agents are included.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline phyllosilicates of the formula given are those in which M is sodium and x is 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 .yH 2 O are preferred.
  • these crystalline layered silicates are preferably only contained in the extrudates according to the invention in amounts of not more than 10% by weight, in particular less than 8% by weight, advantageously not more than 5% by weight.
  • Polymeric polycarboxylates for example, can be used as cobuilders become.
  • Suitable polymeric polycarboxylates are, for example the sodium salts of polyacrylic acid or Polymethacrylic acid, for example those with a molecular weight from 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, which 50 to 90 wt .-% Contain acrylic acid and 50 to 10 wt .-% maleic acid. Your relative Molecular mass, based on free acids, is generally 5000 to 200000, preferably 10000 to 120000 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 acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomers Salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar Derivatives included.
  • organic cobuilders are preferably in the form their sodium salts used polycarboxylic acids, such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, Aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use cannot be objected to for ecological reasons is, 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 this.
  • Suitable builder systems are oxidation products from carboxyl-containing polyglucosans and / or their water-soluble salts, such as those found in international Patent application WO-A-93/08251 can be described or their Manufacturing, for example, in the international patent application WO-A-93/16110.
  • polyacetals which by Reaction of dialdehydes with polyol carboxylic acids, which 5 to 7 C atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0 280 223 can be obtained.
  • Preferred polyacetals are made from Dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde as well their mixtures and from polyol carboxylic acids such as gluconic acid and / or Obtain glucoheptonic acid.
  • cobuilders can be used in amounts of, for example, 0.5 to 20 % By weight, preferably from 2 to 15% by weight in the finished washing or cleaning agents.
  • the agents can also contain components which Oil and fat washability from textiles have a positive impact. This effect is particularly evident when a textile is dirty is that previously several times with an inventive Detergent containing this oil and fat-dissolving component is washed becomes.
  • 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 of 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 are, for example, in the international patent application WO-A-93/02176 and in German patent application DE-A-42 03 031.
  • the preferred ingredients include in particular fatty alcohols with 20 to 80 moles Ethylene oxide per mole of fatty alcohol, for example tallow fatty alcohol 30 E0 and tallow fatty alcohol with 40 E0, but also fatty alcohols with 14 E0 and polyethylene glycols with a molecular weight between 200 and 2000.
  • Sodium perborate monohydrate is of particular importance among the compounds which serve as bleaching agents and produce H 2 O 2 in water.
  • Further bleaching agents which can be used are, for example, sodium perborate tetrahydrate, 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, Amylases, cellulases or their mixtures in question. Particularly good are suitable from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola Insolens obtained enzymatic agents. Preferably be Subtilisin-type proteases, and in particular proteases derived from Bacillus lentus are used.
  • enzyme mixtures 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 lipase-containing Mixtures of special interest.
  • peroxidases or oxidases have proven 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.
  • enzyme mixtures or enzyme granules can, for example about 0.1 to 5% by weight, preferably 0.1 to about 2 % By weight.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DETPMP Diethylenetriaminepentamethylenephosphonic acid
  • Ethylenediaminetetramethylenephosphonic acid especially 1-hydroxyethane-1,1-diphosphonic acid (HEDP), Diethylenetriaminepentamethylenephosphonic acid (DETPMP) or 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 To keep dirt suspended in the fleet and so that To prevent graying.
  • Water-soluble colloids are usually used for this suitable for organic nature, for example the water-soluble salts of polymer Carboxylic acids, glue, gelatin, salts of ether carboxylic acids or Starch or cellulose or salts of ether sulfonic acids acidic sulfuric acid esters of cellulose or starch. Also water-soluble polyamides containing acid groups are for this Suitable purpose. Soluble starch preparations and use starch products other than the above, e.g. degraded Starch, aldehyde starches etc. Polyvinylpyrrolidone is also useful.
  • cellulose ethers such as Carboxymethyl cellulose (sodium salt), methyl cellulose, Hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, Methylcarboxymethylcellulose and their mixtures, as well Polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the funds used.
  • the agents can be used as optical brighteners Contain diaminostilbenedisulfonic acid or its 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 similar connections, which instead of the morpholino group is a diethanolamino group, a Methylamino group, an anilino group or a 2-methoxyethylamino group carry. Brighteners of the type of the substituted diphenyl styrenes, e.g.
  • the alkali salts 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 be used.
  • the agent can add other inorganic salts, too further amorphous alkali silicates of the type described above and Alkali carbonates and / or alkali hydrogen carbonates of those described above Kind included.
  • Other inorganic salts, which as Ingredients to be considered are neutral salts such as sulfates and optionally also chlorides in the form of their sodium and / or potassium salts.
  • Example 1 Preparation of alkali silicate / alkali carbonate compounds containing anionic surfactants
  • the alkali silicate compounds B1 to B4 according to the invention were obtained in different ways.
  • the composition of the compounds was as follows: B1 B2 B3 B4 amorphous sodium disilicate 28.1 28.1 28.1 28.1 sodium 53.4 53.4 53.4 53.4 C 12 -C 18 alkyl sulfate (sodium salt) 3.0 ---- ---- ----- C 12 alkyl benzene sulfonate (sodium salt) ---- 3.0 3.0 3.0 water 15.5 15.5 15.5 15.5 15.5 15.5 15.5
  • the sample to be examined is evenly distributed on an aluminum weighing pan and dried from above by infrared heating.
  • the drying temperature is controlled by a thermal sensor near the heating coil and is around 130 ° C.
  • the exact drying temperature and the required drying time must be determined by calibration. With this determination method, only the water that can be evaporated up to a temperature of about 130 ° C. is recorded, but not the water chemically bound to the amorphous silicate, for the elimination of which higher temperatures are required.
  • product B1 53.4 parts by weight were in the mixing unit calcined soda and 27.5 parts by weight of sodium silicate and mixed for a period of 2 minutes. Subsequently 5.5 parts by weight of an aqueous paste of Alkylbenzenesulfonate (solids content 55% by weight) and 13.6 Parts by weight of the water glass solution used for product B1 are metered in. The mixture was then mixed for 2 minutes.
  • the products had the following bulk densities (g / l): B1 809, B2 465, B3 704 and B4 719.
  • the absorption capacity of the alkali silicate compounds B1 to B4 according to the invention was compared to the reference compound Nabion R 15, surfactant-free soda / silicate compound from Rhône-Poulenc, which is believed to have been produced in accordance with EP-A-488 868, tested with the nonionic surfactant C 12 -C 18 fatty alcohol with 7 E0.
  • the nonionic surfactant absorption capacity was determined in accordance with DIN ISO 787, the above-mentioned nonionic surfactant being used instead of the linseed oil specified there. For this determination, a weighed amount of sample is placed on a plate. Slowly add 4 or 5 drops of nonionic surfactant from a burette.
  • the nonionic surfactant is rubbed into the powder with a spatula.
  • the addition of the nonionic surfactant continues accordingly until aggregations of nonionic surfactant and powder have formed. From this point on, a drop of nonionic surfactant is added and rubbed with the spatula.
  • the non-ionic surfactant addition is stopped when a soft paste has formed. This paste should just be able to spread without tearing or crumbling and just stick to the plate.
  • the amount of nonionic surfactant added is read off the burette and converted to ml nonionic surfactant per 100 g sample. The following results were obtained: ml nonionic surfactant per 100 g carrier B1 75 B2 80 B3 97 B4 70 Nabion R 15 ⁇ 30
  • extrudates E5 to E8 were produced in accordance with the teaching of international patent application WO-A-91/02047.
  • the extrusion mixtures of agents E5 to E8 could be extruded without any process problems.
  • the compositions of the extrudates were as listed in Table 1.
  • the bulk density of the extrudates was between 800 and 830 g / l.
  • the extrudates according to the invention showed good dissolving behavior: only small residues were obtained in the flushing-in behavior and in the solubility test.
  • compositions from E5 to E8 (in% by weight): E5 E6 E7 E8 C 9 -C 13 alkylbenzenesulfonate 11.5 11.5 11.5 11.5 C 12 -C 18 alkyl sulfate 10.5 10.5 10.5 10.5 C 12 -C 18 alcohol with 7 EO 4.0 4.0 4.0 C 12 -C 18 fatty acid soap 1.0 1.0 1.0 1.0 1.0 Polyethylene glycol with a molecular weight of 400 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Zeolite (anhydrous active substance) 19.0 19.0 19.0 19.0 Acrylic acid-maleic acid copolymer (sodium salt) 6.0 6.0 6.0 6.0 Alkali silicate compound B1 14.0 ---- ---- ---- Alkali silicate compound B2 --- 14.0 ---- ---- Alkali silicate compound B3 --- ---- 14.0 ---- Alkali silicate

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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Glass Compositions (AREA)
EP96924857A 1995-07-12 1996-07-03 Amorphes alkalisilicat-compound Expired - Lifetime EP0839178B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19525378 1995-07-12
DE19525378A DE19525378A1 (de) 1995-07-12 1995-07-12 Amorphes Alkalisilicat-Compound
PCT/EP1996/002902 WO1997003168A1 (de) 1995-07-12 1996-07-03 Amorphes alkalisilicat-compound

Publications (2)

Publication Number Publication Date
EP0839178A1 EP0839178A1 (de) 1998-05-06
EP0839178B1 true EP0839178B1 (de) 1999-12-08

Family

ID=7766637

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96924857A Expired - Lifetime EP0839178B1 (de) 1995-07-12 1996-07-03 Amorphes alkalisilicat-compound

Country Status (10)

Country Link
US (1) US6034050A (es)
EP (1) EP0839178B1 (es)
JP (1) JPH11509248A (es)
KR (1) KR19990028914A (es)
CN (1) CN1190430A (es)
AT (1) ATE187486T1 (es)
DE (2) DE19525378A1 (es)
ES (1) ES2142078T3 (es)
HU (1) HUP9802735A3 (es)
WO (1) WO1997003168A1 (es)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19501269A1 (de) * 1995-01-18 1996-07-25 Henkel Kgaa Amorphes Alkalisilikat-Compound
DE19611013A1 (de) * 1996-03-21 1997-09-25 Henkel Kgaa Festes Tensid- und Builder-haltiges Wasch- oder Reinigungsmittel mit hohem Schüttgewicht oder Compound hierfür
GB9825558D0 (en) * 1998-11-20 1999-01-13 Unilever Plc Granular detergent components and particulate detergent compositions containing them
GB0006443D0 (en) * 2000-03-18 2000-05-10 Pilkington Plc Fire resistant glazings
DE10027624A1 (de) * 2000-06-02 2001-12-06 Zschimmer & Schwarz Mohsdorf G Verfahren zur Nachreinigung von gefärbten oder bedruckten polyesterhaltigen textilen Produkten und Mischung zur Durchführung des Verfahrens
EP2152847A1 (en) * 2007-05-17 2010-02-17 The Procter & Gamble Detergent additive extrudates containing alkyl benzene sulphonate
EP3231770A1 (en) * 2016-04-13 2017-10-18 Solvay SA Extrusion process for the preparation of alkali metal carbonate, bicarbonate and sesquicarbonate formulation using a dissolved functionalizing agent
BR112019003035A2 (pt) * 2016-09-07 2019-05-14 Ecolab Usa Inc. bloco de detergente sólido, composição de bloco de detergente sólido, e, métodos para limpeza, sanitização e/ou branqueamento e para ajustar a taxa de dispensação de uma composição de detergente sólido existente

Family Cites Families (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3838193A (en) * 1971-03-13 1974-09-24 Kawasaki Heavy Ind Ltd Method of treating nitrogen oxide generating substances by combustion
US3879527A (en) * 1971-10-28 1975-04-22 Huber Corp J M Alkali metal polysilicates and their production
US3838192A (en) * 1971-10-28 1974-09-24 Huber Corp J M Production of alkali metal polysilicates
US3956467A (en) * 1974-06-07 1976-05-11 Bertorelli Orlando L Process for producing alkali metal polysilicates
US4265790A (en) * 1979-08-09 1981-05-05 Church & Dwight Co., Inc. Method of preparing a dry blended laundry detergent containing coarse granular silicate particles
DE3413571A1 (de) * 1984-04-11 1985-10-24 Hoechst Ag, 6230 Frankfurt Verwendung von kristallinen schichtfoermigen natriumsilikaten zur wasserenthaertung und verfahren zur wasserenthaertung
DE3706036A1 (de) * 1987-02-25 1988-09-08 Basf Ag Polyacetale, verfahren zu deren herstellung aus dialdehyden und polyolcarbonsaeuren und verwendung der polyacetale
DE3825858A1 (de) * 1988-07-29 1990-02-01 Henkel Kgaa Phosphatarme buildersalzkombination
WO1991002047A1 (de) * 1989-08-09 1991-02-21 Henkel Kommanditgesellschaft Auf Aktien Herstellung verdichteter granulate für waschmittel
DE488868T1 (de) * 1990-11-30 1994-02-03 Rhone Poulenc Chimie Gerüststoff auf Basis von Alkalimetallsilikaten für Reinigungsmittelzusammensetzungen.
DE69207990T2 (de) * 1991-07-02 1996-05-30 Crosfield Joseph & Sons Silicate
DE4124701A1 (de) * 1991-07-25 1993-01-28 Henkel Kgaa Verfahren zur herstellung fester wasch- und reinigungsmittel mit hohem schuettgewicht und verbesserter loesegeschwindigkeit
ATE155165T1 (de) * 1991-07-31 1997-07-15 Ausimont Spa Verfahren zur erhöhung der bleichwirksamkeit eines inorganischen persalzes
DE4134914A1 (de) * 1991-10-23 1993-04-29 Henkel Kgaa Wasch- und reinigungsmittel mit ausgewaehlten builder-systemen
IT1252682B (it) * 1991-11-13 1995-06-23 Vomm Impianti & Processi Srl Prodotto in granuli di elevato peso specifico, particolarmente quale additivo di detersivi in polvere e metodo per il suo ottenimento
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
DE4203923A1 (de) * 1992-02-11 1993-08-12 Henkel Kgaa Verfahren zur herstellung von polycarboxylaten auf polysaccharid-basis
FR2688798B1 (fr) * 1992-03-20 1994-10-14 Rhobb Poulenc Chimie Agent "builder" a base de silicate et d'un produit mineral.
DE4235646A1 (de) * 1992-10-22 1994-04-28 Henkel Kgaa Verfahren zur Herstellung wasch- und reinigungsaktiver Extrudate
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
EP0651050A1 (en) * 1993-11-03 1995-05-03 The Procter & Gamble Company Surfactant agglomerate particle
DE4435743C2 (de) * 1994-02-17 1998-11-26 Chemolux Sarl Verfahren zur Herstellung eines Mehrkomponenten-Granulates
DE4419745A1 (de) * 1994-06-06 1995-12-07 Henkel Kgaa Granuliertes wasserlösliches kieselsäurehaltiges Alkalisilicat
DE4442977A1 (de) * 1994-12-02 1996-06-05 Henkel Kgaa Wasch- oder Reinigungsmittel mit wasserlöslichen Buildersubstanzen
DE19501269A1 (de) * 1995-01-18 1996-07-25 Henkel Kgaa Amorphes Alkalisilikat-Compound

Also Published As

Publication number Publication date
ES2142078T3 (es) 2000-04-01
CN1190430A (zh) 1998-08-12
HUP9802735A2 (hu) 1999-03-29
US6034050A (en) 2000-03-07
HUP9802735A3 (en) 1999-08-30
DE59603874D1 (en) 2000-01-13
WO1997003168A1 (de) 1997-01-30
DE19525378A1 (de) 1997-01-16
ATE187486T1 (de) 1999-12-15
EP0839178A1 (de) 1998-05-06
KR19990028914A (ko) 1999-04-15
JPH11509248A (ja) 1999-08-17

Similar Documents

Publication Publication Date Title
EP0859827B1 (de) Verfahren zur herstellung eines amorphen alkalisilikats mit imprägnierung
EP0746599B1 (de) Waschmittel mit amorphen silikatischen buildersubstanzen
EP0804529B1 (de) Amorphes alkalisilikat-compound
EP0839178B1 (de) Amorphes alkalisilicat-compound
EP0828818B1 (de) Granulares wasch- oder reinigungsmittel mit hoher schüttdichte
WO1995029978A1 (de) Verfahren zur herstellung silikatischer buildergranulate mit erhöhtem schüttgewicht
EP0793708B1 (de) Verfahren zur herstellung extrudierter wasch- oder reinigungsmittel mit wasserlöslichen buildersubstanzen
EP0799302B1 (de) Amorphes alkalisilikat mit imprägnierung
EP0840780B1 (de) Granulares wasch- oder reinigungsmittel mit hoher schüttdichte
EP0845028B1 (de) Verfahren zur herstellung eines amorphen alkalisilikats mit imprägnierung
EP1012221B1 (de) Verfahren zur herstellung teilchenförmiger wasch- oder reinigungsmittel
EP0724620B1 (de) Verfahren zur herstellung wasch- oder reinigungsaktiver extrudate mit verbessertem redispergiervermögen
DE19622443A1 (de) Granulare Waschmittel, enthaltend optischen Aufheller
EP0874684B1 (de) Verfahren zur herstellung eines granularen additivs
EP0877789B1 (de) Waschmittel, enthaltend amorphe alkalisilikate und peroxybleichmittel
WO1997034977A1 (de) Verfahren zur herstellung von granularen silikaten mit hohem schüttgewicht
EP0705330A1 (de) Verfahren zur herstellung wasch- oder reinigungsaktiver extrudate
WO2000039261A1 (de) Niederdosierter, löslicher builder
WO1995004129A1 (de) Verfahren zur herstellung wasch- oder reinigungsaktiver extrudate
EP0936267A2 (de) Alkalimetallsilicat/Niotensid-Compound
WO1996001886A1 (de) Waschmittel mit cellulase

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: 19971219

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE DE ES FI FR IT NL

RIN1 Information on inventor provided before grant (corrected)

Inventor name: HAMMELSTEIN, STEFAN

Inventor name: BURMEISTER, KATRIN

Inventor name: BAUER, VOLKER

Inventor name: ARTIGA GONZALEZ, RENE-ANDRES

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

17Q First examination report despatched

Effective date: 19981104

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

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): AT BE DE ES FI FR IT NL

REF Corresponds to:

Ref document number: 187486

Country of ref document: AT

Date of ref document: 19991215

Kind code of ref document: T

REF Corresponds to:

Ref document number: 59603874

Country of ref document: DE

Date of ref document: 20000113

ET Fr: translation filed
ITF It: translation for a ep patent filed

Owner name: STUDIO JAUMANN P. & C. S.N.C.

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2142078

Country of ref document: ES

Kind code of ref document: T3

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

Ref country code: NL

Payment date: 20010730

Year of fee payment: 6

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

Ref country code: BE

Payment date: 20010817

Year of fee payment: 6

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

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020731

BERE Be: lapsed

Owner name: *HENKEL K.G.A.A.

Effective date: 20020731

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

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030201

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20030201

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

Ref country code: ES

Payment date: 20140611

Year of fee payment: 19

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

Ref country code: DE

Payment date: 20140625

Year of fee payment: 19

Ref country code: FI

Payment date: 20140710

Year of fee payment: 19

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

Ref country code: FR

Payment date: 20140708

Year of fee payment: 19

Ref country code: AT

Payment date: 20140626

Year of fee payment: 19

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

Ref country code: IT

Payment date: 20140718

Year of fee payment: 19

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 59603874

Country of ref document: DE

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 187486

Country of ref document: AT

Kind code of ref document: T

Effective date: 20150703

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

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150703

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160202

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20160331

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

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150731

Ref country code: FI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150703

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150703

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20160826

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 NON-PAYMENT OF DUE FEES

Effective date: 20150704