EP0839178A1 - Compose amorphe de silicate alcalin - Google Patents

Compose amorphe de silicate alcalin

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Publication number
EP0839178A1
EP0839178A1 EP96924857A EP96924857A EP0839178A1 EP 0839178 A1 EP0839178 A1 EP 0839178A1 EP 96924857 A EP96924857 A EP 96924857A EP 96924857 A EP96924857 A EP 96924857A EP 0839178 A1 EP0839178 A1 EP 0839178A1
Authority
EP
European Patent Office
Prior art keywords
alkali metal
silicate
weight
alkali
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP96924857A
Other languages
German (de)
English (en)
Other versions
EP0839178B1 (fr
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
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Henkel AG and Co KGaA
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Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0839178A1 publication Critical patent/EP0839178A1/fr
Application granted granted Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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 process for the production of a surfactant-containing amorphous alkali silicate / alkali carbonate compound with secondary washing ability, which can be used as a water-soluble builder in detergents or cleaning agents, and to the use of such alkali silicate compounds in washing or cleaning agents, extruded washing agents or Detergents and a process for their preparation.
  • Modern, compacted detergents or cleaning agents generally have the disadvantage that, owing to their compact structure, they show poorer dissolving behavior in aqueous liquors than, for example, lighter spray-dried detergents or cleaning agents of the prior art.
  • Detergents or cleaning agents generally tend to have a poorer dissolving rate in water, the higher their degree of compaction.
  • Zeolites which are usually contained in washing or cleaning agents as builder substances, can additionally contribute to the deteriorated dissolving behavior due to their insolubility in water.
  • a water-soluble alternative for the zeolite are amorphous alkali silicates with secondary washing power.
  • spray or roller drying of water glass solutions it is known to obtain hydrated water-soluble silicates in powder form which still contain about 20% by weight of water (cf. Ullmann's Encyclopedia of Industrial Chemistry, 4th edition 1982, volume 21, page 412).
  • Such products are commercially available for various purposes.
  • Such powders have a very loose structure due to spray drying; their bulk weights are generally well below 700 g / l.
  • Alkali silicates in granular form with higher bulk densities can be obtained according to the teaching of European patent application EP-A-0526978, an alkali silicate solution having a solids content of between 30 and 53% by weight being introduced into a heated drum along its longitudinal axis a shaft with a plurality of arms rotating close to the inner surface of the drum rotates, the drum wall having a temperature between 150 and 200 ° C and the drying process is assisted by a gas fed into the drum with a temperature between 175 and about 250 ° C . This process gives a product whose average particle size is in the range between 0.2 and 2 mm. A preferred 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 scoop-shaped blades rotates at such a speed that the silicate solution has a solids content of between 40 and 60% by weight .-% a 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 19745.4 also describes a water-soluble, amorphous and granular alkali silicate, which is prepared in a similar manner to that described in EP-A-0526978, but contains silicic acid.
  • amorphous means "X-ray amorphous”. This means that the alkali silicates do not provide sharp reflections in X-ray diffraction recordings, 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 possibility that areas are found in electron diffraction experiments which provide sharp electron diffraction reflections. This is to be interpreted in such a way that the substance has microcrystalline regions in a range of up to approximately 20 nm (max. 50 nm).
  • Granular amorphous sodium silicates which are obtained by spray drying aqueous water glass solutions, subsequent grinding and subsequent compression and rounding off 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 about 18 to 20% by weight with bulk weights significantly above 500 g / l.
  • a process for the production of extrudates with high density is known, a solid and free-flowing premix being extruded under pressure under pressure.
  • the solid and free-flowing premix contains a plasticizer and / or lubricant, which causes the premix to soften plastically under the pressure or the entry of specific work and thus to be extrudable. After exiting the hole shape, the system is no longer subjected to shear forces and the viscosity of the system increases in such a way that the extruded strand can be cut to predeterminable extrudate dimensions.
  • zeolite used as builders and phosphate substitutes.
  • Extruded washing or cleaning agents are known from international patent application WO-A-94/09111, which contain 19% by weight zeolite (based on anhydrous active substance) as well as 12.5% by weight sodium carbonate and 2.2 % By weight of amorphous sodium silicate;
  • zeolite can be partially or even completely replaced by water-soluble inorganic builder substances, such as amorphous alkali silicates, if these are used in a specific form.
  • EP-A-651 050 describes a process for producing granules which contain, as essential components, an amorphous silicate, an anionic surfactant and a further solid salt, which can be sodium carbonate, for example.
  • the further salt is initially introduced and agglomerated with an aqueous "binder" made from alkali metal silicate solution and anionic surfactant.
  • Sodium carbonate is one of many selectable salt components. While the binder contains the alkali metal silicate and the anionic surfactant in weight ratios between 1: 3 and 3: 1, the weight ratio between "binder" and salt component nothing said.
  • the agglomerates produced in the exemplary embodiments have sodium carbonate contents of less than 10% by weight.
  • the preferred salt, which is present in the exemplary embodiments in proportions of 35.5% by weight, is sodium sulfate.
  • An object of the invention was to provide further water-soluble builder substances for the partial or complete replacement of zeolite in detergents or cleaning agents, as a result of which the dissolving behavior, in particular of heavy detergents or cleaning agents, should be improved.
  • these water-soluble builder substances should also have an absorption capacity for ingredients of detergents or cleaning agents which are liquid to waxy at the processing temperature.
  • Another object of the invention was to provide extruded detergents or cleaning agents and a process for their preparation which contain the water-soluble builder substances to the extent that zeolite is partially or completely dispensed with, not only from an application point of view but also from a process point of view can be.
  • the invention accordingly relates to a process for the preparation of an anionic surfactant
  • the terms “powder form” or “powder form” mean that the substances are in solid, giant form and at least 90% by weight of the particles have a particle diameter of 1 mm or less.
  • Sodium and / or potassium silicate are particularly suitable here. Sodium silicates are preferred for economic reasons. However, if, for technical reasons, a particularly high dissolving rate in water is preferred, it is advisable to at least partially replace sodium with potassium.
  • the composition of the alkali silicate can be chosen so that the silicate has a potassium content, calculated as K2O, 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 can be produced according to the above-mentioned US patents by spray drying or in granulators of the turbo-dryer type, for example from Vornm, Italy, are suitable and entirely preferred starting materials with advantageous properties. In the case of turbo granulation, it is possible to produce the compounds directly in the manner according to the invention.
  • alkali metal silicate / alkali metal carbonate compounds containing anionic surfactants one can generally proceed in such a way that in a suitable mixing unit or in a fluidized bed at least one of the components alkali metal silicate or alkali metal carbonate is given in powder form and an aqueous solution is sprayed on Anionic surfactants, the if necessary, additionally contains a further component of the compound to be produced in dissolved and / or dispersed form.
  • 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.
  • powdered alkali metal arbonate can be initially charged and agglomerated using an aqueous alkali metal silicate solution containing anionic surfactants, which may optionally contain undissolved portions of alkali metal silicate.
  • powdered alkali metal silicate can be introduced and agglomerated using an alkali metal carbonate solution containing anionic surfactants.
  • a powdery mixture of alkali metal silicate and alkali metal arbonate can be initially charged and this agglomerated using an aqueous anionic surfactant preparation.
  • This aqueous preparation can be a real solution, an emulsion or a water-containing surfactant paste.
  • the process according to the invention can also be carried out in such a way that a preformed compound of alkali metal silicate and alkali metal arbonate is agglomerated with such an aqueous anionic surfactant preparation.
  • the preformed compound of alkali metal silicate and alkali metal arbonate can be obtained, for example, by spray drying an aqueous solution or suspension which contains both components.
  • a compound can also be used for this, which can be obtained by agglomeration of the one component in powder form with an aqueous solution of the second component.
  • the preferred alkali metal carbonate is sodium and / or potassium carbonate, sodium carbonate being preferred for economic reasons.
  • the mixing and agglomeration units known in the prior art can be used to produce the compounds. Examples include the turbo dryer described in more detail above, or slower rotating drums, preferably provided with mixing internals, pelletizing plates which rotate about an axis which is 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 C9-Ci3-alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates, and disulfonates such as are obtained, for example, from Ci2-Ci8 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 which are obtained from Ci2-Ci8-alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • Suitable surfactants of the sulphate 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 Ci2-Ci8 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ⁇ o-C2 ⁇ - 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, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on fatty chemical raw materials.
  • Ciö-Cj ⁇ - Alk (en) yl sulfates are particularly preferred. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use Ci6-Ci8 ⁇ alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants that have a lower Krafft point and at relatively low washing temperatures of for example, room temperature up 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 C12-Cj4-fatty alkyl sulfates or with Cis-Cjg-fatty alkyl sulfates and in particular Ci2-Ci6-fatty alkyl sulfates with Cjö-Cis-fatty alkyl sulfates.
  • fatty alkyl sulfates preferably mixtures of C12-Cj4-fatty alkyl sulfates or with Cis-Cjg-fatty alkyl sulfates and in particular Ci2-Ci6-fatty alkyl sulfates with Cjö-Cis-fatty alkyl sulfates.
  • not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably CIOE to C22 are used.
  • the sulfuric acid monoesters of the straight-chain or branched C7-C2i alcohols ethoxylated with 1 to 6 mol ethylene oxide such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 mol ethylene oxide (EO) or Ci2-Ci8 fatty alcohols with 1 up to 4 EO are suitable. Because of their high foam behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight. In a preferred embodiment of the invention, the compounds contain 15 to 80% by weight alkali silicates, 1 to 20% by weight anionic surfactants and 10 to 22% by weight, preferably 12 to 19% by weight and in particular 14 to 19% by weight. % Water.
  • the compounds according to the invention contain 15 to 50% by weight, preferably 20 to 40% by weight alkali silicates, 30 to 70% by weight, preferably 40 to 65% by weight.
  • Alkali carbonates 1.5 to 15% by weight and in particular 2 to 12% by weight anionic surfactants, advantageously alkylbenzenesulfonates and / or alk (en) yl sulfates, and 12 to 19% by weight water.
  • the alkali silicate compounds can additionally contain further ingredients of detergents or cleaning agents, preferably in amounts of up to 10% by weight and in particular in amounts not above 5% by weight.
  • detergents or cleaning agents 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 absorption capacity for liquid to wax-like ingredients of washing or cleaning agents at the usual processing temperatures.
  • Alkali silicate compounds can also absorb certain quantities of liquid components without the addition of anionic surfactants; However, it has been shown that the addition capacity of anionic surfactants increases the absorption capacity of the alkali silicate compounds and improves the flow behavior.
  • the alkali silicate compounds containing anionic surfactants according to the invention have an absorption capacity for liquid components which is at least 20% higher than that of the equal-quantity alkali silicate compounds without anionic surfactants.
  • Compounds are preferred whose absorption capacity for liquid components has been increased by at least 30% and advantageously even by at least 50%, in each case based on the absorption capacity of the equivalent alkali silicate compounds without anionic surfactants.
  • alkali silicate compounds produced according to the invention are therefore claimed, which have been post-treated with liquid components, which include liquid to waxy ingredients of detergents or cleaning agents at processing temperature in the context of this invention.
  • 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
  • the alcohol radical can be methyl-branched linearly or preferably in the 2-position or linear and methyl-branched May contain residues in the mixture, such as are usually present in oxo alcohol residues.
  • 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, Ci2-Ci4 alcohols with 3 EO or 4 EO, Cg-C ⁇ alcohol with 7 EO, Ci3-C ⁇ s alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci2- Ci8 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of Ci2-Ci4 alcohol with 3 EO and Ci2-Ci8 alcohol with 5 EO.
  • the specified degrees of ethoxylation represent statistical mean values, which can be an integer or a fraction for a special 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 of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • the alkali silicate compounds produced according to the invention can subsequently be treated with ingredients of washing or cleaning agents. This can be carried out in a conventional manner, for example by mixing or by spraying in a mixer / granulator, if appropriate with subsequent heat treatment.
  • the amorphous alkali silicate compounds with secondary washing ability can be used as an additive component to powdery to granular washing or cleaning agents or as a component in the production of the granular washing or cleaning agents, preferably in the granulation and / or compacting.
  • the bulk densities of the alkali silicate compounds can vary between approximately 300 and, for example, 950 g / l. Bulk weights of up to 1150 g / l can be achieved with continuous production.
  • the washing or cleaning agents according to the invention can have a bulk density between 300 and 1200 g / 1, preferably from 500 to 1000 g / 1, 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 to 40% by weight.
  • They can be produced by any of the known methods such as mixing, granulating, compacting such as roller compaction and extrusion. Processes in which several subcomponents, for example spray-dried components and granulated and / or extruded components are mixed together. It is also possible for spray-dried or granulated components to be subsequently treated, for example with nonionic surfactants, in particular ethoxylated fatty alcohols, by the customary processes.
  • the additional anionic surfactants which may be present in the form of a spray-dried, granulated or extruded compound, either as an additive component in the process or as an additive to other granules.
  • Suitable surface modifiers are known from the prior art.
  • suitable, finely divided zeolites, silicas, amorphous silicates, fatty acids or fatty acid salts, for example calcium stearate but especially mixtures of zeolite and silica, in particular in a weight ratio of zeolite to silica of at least 1: 1, or zeolite and calcium stearate are particularly preferred.
  • Particularly preferred embodiments of the invention are extruded washing or cleaning agents with a bulk density above 600 g / l, which contain anionic and optionally nonionic surfactants and an amorphous alkali silicate compound of the type produced according to the invention in the extrudate.
  • the alkali silicate compounds containing anionic surfactants surprisingly also have advantages over the alternative alkali silicate compound alternatives free of anionic surfactants from a process engineering point of view. It has been shown that extrusion processes in which in particular anionic surfactant-free alkali silicate-carbonate compounds were used should not be interrupted, since the extrusion mixture lost its plasticity and lubricity so quickly in the rest phase that restarting the system brought about safety-related problems . This problem was solved by replacing the anionic surfactant-free alkali silicate compounds containing anionic surfactant, in particular alkali silicate compounds containing anionic surfactant and carbonate.
  • the finished washing or cleaning agents can additionally contain the following ingredients.
  • surfactants especially anionic surfactants and, if appropriate, nonionic surfactants, but also cationic, amphoteric or zwitterionic surfactants.
  • Suitable anionic surfactants of the sulfonate type are the alkylbenzenesulfonates, olefin sulfonates and alkanesulfonates already mentioned above.
  • the esters of oc-sulfo fatty acids are also suitable, e.g. the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • Further suitable anionic surfactants are the ⁇ -sulfofatty acids obtainable by ester cleavage of the oc-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, such as those produced by esterification by a monoglycerol with 1 to 3 mol fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol can be obtained.
  • Suitable surfactants of the sulfate type are the sulfuric acid monoesters mentioned 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 the Monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain CQ to Ci8 ⁇ fatty alcohol residues or mixtures thereof.
  • preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which are nonionic surfactants in themselves.
  • sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred.
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • compositions can also contain beefs, preferably in amounts of 0.2 to 5% by weight.
  • Saturated fatty acid soaps such as 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 and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • detergents or cleaning agents in particular extruded detergents or cleaning agents, which contain 10 to 30% by weight of anionic surfactants are preferred.
  • at least 3% by weight and in particular at least 5% by weight of sulfate surfactants are preferred.
  • the compositions — based on the total anionic surfactants — contain at least 15% by weight, in particular 20 to 100% by weight, of sulfate surfactants.
  • alkoxylated, advantageously ethoxylated alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol are preferably used as nonionic surfactants.
  • alkyl glycosides of the general formula R0 (G) x can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched, in particular in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms means 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-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (D,
  • R 2 is C0 for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R3 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 is up to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • Nonionic surfactants are contained in the agents according to the invention preferably in amounts of 0.5 to 15% by weight, in particular in amounts of 2 to 10% by weight.
  • the compositions can also contain further, additional builder substances and cobuilders.
  • additional 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. Suitable are, for example, zeolite A, but also zeolite X and zeolite P and mixtures of A, X and / or P.
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production Come into play.
  • the zeolite in the event that the zeolite is used as a suspension, it can contain small amounts of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated Ci2-Ci8 fatty alcohols with 2 to 5 ethylene oxide groups , Ci2-Ci4 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. It is also possible 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 detergents or cleaning agents in amounts of up to about 40% by weight (based on anhydrous active substances).
  • detergents or cleaning agents contain 10 to 16% by weight of zeolite (based on anhydrous active substance) and 10 to 30% by weight of an alkali silicate compound produced according to the invention.
  • the washing 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 prepared in accordance with the invention. It is possible for the zeolite not only to be coextruded, but for the zeolite to be introduced into the washing or cleaning agent partially or completely subsequently, that is to say after the extrusion step. Washing or cleaning agents which contain an extrudate which is free of zeolite in the interior of the extrudate grain are particularly preferred.
  • Crystalline phyllosilicates and / or conventional phosphates can also be used as substitutes for the zeolite. However, it is preferred that phosphates are contained in the washing or cleaning agents only in small amounts, in particular up to a maximum of 10% by weight.
  • Crystalline layered silicates are, in particular, crystalline, layered sodium silicates of the general formula NaMSi x ⁇ 2 ⁇ + ryH2 ⁇ , where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are suitable.
  • 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 fr-sodium disilicate Na2S ⁇ ' 2 ⁇ 5 * yH2 ⁇ 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 can be used as cobuilders.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
  • Terpolymers are also particularly preferred, for example those which, according to DE-A-43 00 772, are salts of monomers Acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
  • Other useful organic cobuilders 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), provided that such use is not objectionable 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 these.
  • Suitable builder systems are oxidation products of carboxyl-containing polyglucosans and / or their water-soluble salts, as are described, for example, in international patent application WO-A-93/08251 or the production of which is described, for example, in international patent application WO-A-93/16110 .
  • polyaspartic acids or their salts and derivatives are also to be mentioned as further preferred builder substances.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0 280 223.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • cobuilders can be present in the finished washing or cleaning agents in amounts of, for example, 0.5 to 20% by weight, preferably 2 to 15% by weight.
  • the agents can also contain components which have a positive influence on the oil and fat washability from textiles. This effect is particularly evident when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil- and fat-dissolving component.
  • the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methylhydroxypropyl cellulose with a proportion of methoxy1 groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, based in each case on the nonionic Cellulose ethers, and the polymers of phthalic acid and / or terephthalic acid or of their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof.
  • nonionic cellulose ethers such as methyl cellulose and methylhydroxypropyl cellulose with a proportion of methoxy1 groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, based in each case on the nonionic Cellulose ethers
  • the agents can also contain constituents which further improve the solubility, in particular of the heavy granules.
  • constituents and the introduction of such constituents are described, for example, in international patent application WO-A-93/02176 and in German patent application DE-A-4203031.
  • the components preferably used 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 alcohol with 40 E0 r, but also fatty alcohols with 14 E0 and polyethylene glycols with a relative molecular weight between 200 and 2000.
  • Sodium perborate monohydrate is of particular importance among the compounds which provide H2O2 in water and which serve as bleaching agents.
  • Other bleaches that can be used are, for example, sodium perborate tetrahydrate, sodium percarbonate,
  • Peroxypyrophosphates citrate perhydrates and H2O2-providing peracid 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 advantageously being 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 H2O2, 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.
  • bleach activators in the bleach-containing agents is in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.
  • Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylenediamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,5,5-triazine (DADHT) and acetylated sorbitoi-mannitol mixtures (S0RMAN).
  • foam inhibitors are suitable as foam inhibitors, for example of natural or synthetic origin, which have a high proportion of Ci8 ⁇ C24 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.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures are here, for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures of protease and / or lipase of special interest.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in Hü11 substances to protect them against premature decomposition.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • DETPMP Diethylenetriaminepentamethylenephosphonic acid
  • ethylenediaminetetramethylenephosphonic acid Diethylenetriaminepentamethylenephosphonic acid (DETPMP) or ethylenediaminetetramethylenephosphonic acid.
  • 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 (H3BO3), metaboric acid (HBO2) and pyroboric acid (tetraboric acid H2B4O7), is particularly advantageous.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing graying.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc.
  • Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethy1ce11u1ose, methylhydroxypropy1ce11ulose, Methylcarboxymethylcellulose and mixtures thereof, and also polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition.
  • the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similar compounds, instead of the morpholino group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyryl type may be present, e.g.
  • the agents can contain further inorganic salts, also further amorphous alkali silicates of the type described above, and alkali carbonates and / or alkali hydrogen carbonates of the type described above.
  • Other inorganic salts which can be considered as ingredients are neutral salts such as sulfates and possibly also chlorides in the form of their sodium and / or potassium salts.
  • dyes and fragrances usually contained in washing or cleaning agents can also be contained.
  • 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 (in% by weight) was as follows:
  • 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 of calcined soda and 27.5 parts by weight of sodium silicate were placed in the mixing unit and mixed for a period of 2 minutes. Then 5.5 parts by weight of an aqueous paste of alkylbenzenesulfonate (solids content 55% by weight) and 13.6 97/03168 31 PC ⁇ 7EP96 / 02902
  • Parts by weight of the water glass solution used for product B1 are metered. The mixture was then mixed for 2 minutes.
  • the products had the following bulk weights (g / 1): Bl 809, B2 465, B3704 and B4719.
  • Example 2 Nonionic surfactant absorption capacity of the alkali silicate compounds
  • the absorption capacity of the alkali silicate compounds B1 to B4 according to the invention was compared to the reference compound Nabion R 15, tenside-free soda / silicate compound from Rh ⁇ ne-Poulenc, which is assumed to be used was produced according to EP-A-488 868, tested with the nonionic surfactant Ci2 ⁇ Ci8 fatty alcohol with 7 E0.
  • the nonionic surfactant absorption capacity was determined in accordance with DIN ISO 787, where the above-mentioned nonionic surfactant was used instead of the linseed oil specified there. For this determination, a weighed sample amount is placed on a plate.
  • nonionic surfactant Slowly add 4 or 5 drops of nonionic surfactant from a burette. After each addition, the nonionic surfactant is rubbed into the powder with a spatula. The addition of the nonionic surfactant is continued 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 nonionic surfactant addition is ended 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 of nonionic surfactant per 100 g of sample. The following results were obtained:
  • extrudates E5 to E8 according to the invention were produced.
  • the extrusion mixtures of agents E5 to E8 could be extruded without any process problems.
  • the together Extrudate ratios were as listed in Table 1.
  • the bulk density of the extrudates was between 800 and 830 g / 1.
  • the extrudates according to the invention showed good dissolving behavior: only slight residues were obtained in the flushing-in behavior and in the solubility test.
  • compositions from E5 to E8 (in% by weight):

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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)
  • Glass Compositions (AREA)

Abstract

Le procédé décrit permet de produire un composé de silicate de métal alcalin ou de carbonate de métal alcalin qui contient des agents tensioactifs anioniques et qui a un pouvoir détergent secondaire. A cet effet, on agglomère un composant pulvérulent sélectionné parmi les carbonates de métaux alcalins, les silicates de métaux alcalins amorphes ou un mélange de ceux-ci, en utilisant une composition aqueuse qui contient des agents tensioactifs et le cas échéant les composants non pulvérulents du composé que l'on veut produire. L'invention concerne également des produits de lavage et de nettoyage, notamment sous forme d'extrudats, qui contiennent un composé ainsi produit.
EP96924857A 1995-07-12 1996-07-03 Compose amorphe de silicate alcalin Expired - Lifetime EP0839178B1 (fr)

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 (fr) 1995-07-12 1996-07-03 Compose amorphe de silicate alcalin

Publications (2)

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

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US (1) US6034050A (fr)
EP (1) EP0839178B1 (fr)
JP (1) JPH11509248A (fr)
KR (1) KR19990028914A (fr)
CN (1) CN1190430A (fr)
AT (1) ATE187486T1 (fr)
DE (2) DE19525378A1 (fr)
ES (1) ES2142078T3 (fr)
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WO (1) WO1997003168A1 (fr)

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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
CN101679927B (zh) * 2007-05-17 2012-06-27 宝洁公司 包含烷基苯磺酸盐的去污添加剂挤出物
EP3231770A1 (fr) * 2016-04-13 2017-10-18 Solvay SA Procédé d'extrusion destiné à la préparation de formulation de carbonate de métal alcalin, bicarbonate et sesquicarbonate à l'aide d'un agent de fonctionnalisation dissous
AU2017324520B2 (en) * 2016-09-07 2020-01-23 Ecolab Usa Inc. Solid detergent compositions and methods of adjusting the dispense rate of solid detergents using solid anionic surfactants

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HUP9802735A2 (hu) 1999-03-29
ATE187486T1 (de) 1999-12-15
US6034050A (en) 2000-03-07
KR19990028914A (ko) 1999-04-15
DE19525378A1 (de) 1997-01-16
EP0839178B1 (fr) 1999-12-08
ES2142078T3 (es) 2000-04-01
WO1997003168A1 (fr) 1997-01-30
HUP9802735A3 (en) 1999-08-30
CN1190430A (zh) 1998-08-12
JPH11509248A (ja) 1999-08-17
DE59603874D1 (en) 2000-01-13

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