EP0888428A1 - Procede de production de silicates granulaires a masse volumique apparente elevee - Google Patents

Procede de production de silicates granulaires a masse volumique apparente elevee

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Publication number
EP0888428A1
EP0888428A1 EP97914226A EP97914226A EP0888428A1 EP 0888428 A1 EP0888428 A1 EP 0888428A1 EP 97914226 A EP97914226 A EP 97914226A EP 97914226 A EP97914226 A EP 97914226A EP 0888428 A1 EP0888428 A1 EP 0888428A1
Authority
EP
European Patent Office
Prior art keywords
spray
weight
dried
acid
bulk density
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.)
Ceased
Application number
EP97914226A
Other languages
German (de)
English (en)
Inventor
Rene-Andres Artiga Gonzalez
Claus Peter Thiessies
Wieland Schulze
Hubert Freese
Bernd Larson
Volker Bauer
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 EP0888428A1 publication Critical patent/EP0888428A1/fr
Ceased legal-status Critical Current

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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
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/32—Alkali metal silicates
    • C01B33/325—After-treatment, e.g. purification or stabilisation of solutions, granulation; Dissolution; Obtaining solid silicate, e.g. from a solution by spray-drying, flashing off water or adding a coagulant
    • 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

Definitions

  • the invention relates to the production of granular silicates with high bulk density, which are also free-flowing.
  • hydrated water-soluble silicates can be obtained in a table shape by spray drying waterglass solutions and contain about 15 to 22% by weight of water.
  • Such products are commercially available for various purposes. However, they have a very loose structure and have a bulk density which is generally well below 500 g / l, for example 300 g / l or even less.
  • the object of the invention was to produce, starting from spray-dried amorphous alkali silicates, granular amorphous alkali silicates with a high bulk density, which have a high absorbency, i.e. even after impregnation with ingredients of detergents or cleaning agents which are liquid or flowable at the processing temperature, still have sufficient free-flowing properties.
  • the invention accordingly relates to a process for the production of granular amorphous alkali silicates by spray drying and subsequent compression of the spray-dried bead, the spray-dried bead being ground and granulated at the same time or subsequently with the addition of a liquid granulating aid, a bulk density of at least 700 g / l is set.
  • the preferred amorphous sodium silicates include those with a module Na2Ü: SiÜ2 of 1: 2 to 1: 3.3, preferably of 1: 2 to 1: 2.8 and in particular of 1: 2 to 1: 2.6, which delays dissolution are and have secondary washing properties.
  • the release delay compared to conventional amorphous sodium silicates takes place within the scope of the present invention on the one hand through the compaction / compression, but on the other hand can also be caused by overdrying, for example drying water contents below 15% by weight.
  • X-ray amorphous silicates which do not provide any sharp X-ray reflections in the X-ray diffraction spectrum, as are typical for crystalline substances, but at most one or more maxima of the scattered X-ray radiation, which have a width of several degree units of the diffraction angle, but on the other hand are washed out in electron diffraction experiments or even deliver sharp diffraction maxima show properties that are delayed in dissolution.
  • X-ray amorphous silicates of this type have microcrystalline regions of the size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • aqueous silicate solutions which preferably have a silicate content of 25 to 60% by weight, are first spray-dried, water contents generally being set to from 5 to 23% by weight and preferably from 10 to 19% by weight and grind before further granulation.
  • Various types of mills can be used here, particle sizes preferably being less than 0.2 mm. For example, pin mills, friction mills, fan wheel mills or fine praline mills can be used here.
  • the solutions to be spray-dried can also have other ingredients.
  • Their amorphous silicate content, based on the spray-dried bead, is preferably more than 50% by weight.
  • the amorphous silicates are regarded as water-containing ingredients. In this case, the water content of the beads has been included in the specified amount.
  • ingredients of the solutions to be spray-dried are, for example, alkali metal (bi) carbonates, alkali metal sulfates, hydrogen sulfates, anionic surfactants such as alkylbenzenesulfonates and / or alkyl sulfates, polycarboxylic acids or polycarboxylates and / or (co-) polymeric polycarboxylates, preferably citric acid or citrate, and citrate / or complexing agents.
  • Sodium carbonate and / or alkylbenzenesulfonate are particularly preferred.
  • the spray-dried silicates or compounds containing amorphous silicates generally have a very low bulk density of, for example, well below 300 g / l and can advantageously be compacted to bulk densities of 450 to 700 g / l already in the grinding stage. If a bulk density of 700 g / l is already reached in this stage, the bulk density after the subsequent granulation is above 700 g / l.
  • the spray-dried bead is moistened before or during the grinding.
  • moistening is generally understood to mean wetting with liquids, ie not only treatment with water, aqueous solutions or aqueous dispersions, but also with non-aqueous liquids, for example nonionic surfactants. All known nonionic surfactants which have a melting point below 45 ° C. are particularly suitable.
  • the moistening is preferably carried out with water or aqueous solutions, in particular aqueous solutions of ingredients of washing or cleaning agents.
  • an advantageous solution is an aqueous silicate solution, for example a 30 to 50% by weight silicate solution. It is it is particularly preferred that 1 to 5 parts by weight of liquid (s) are used per 100 parts by weight of the spray-dried beads.
  • aqueous alkali silicate solution is also used as the granulation aid. It is particularly advantageous that a separate moistening can be omitted in this case because An ⁇ moist and Granulationsunterstützung simultaneously through the same medium insbeson ⁇ particular by 30 to 60 wt .-% aqueous silicate solution can take place.
  • a friction compactor has rollers similar to a roller compactor or roller mill, in contrast to the roller compactor, the rollers of a friction compactor rotate at different speeds. Apparatus from Alexanderwerke or Bepex, for example, can be mentioned as suitable friction compactors.
  • grinding is carried out first and then granulation of the milled and, if appropriate, moistened spray-dried beads before or during the milling, a further compaction being effected compared to the milling stage.
  • the bulk density in the granulation stage preferably increases again by 50 to 200 g / l.
  • the granulation can be carried out by any of the known processes for producing detergent or cleaning agent granules.
  • the granulation in a slow-running mixer / compressor or in two consecutive mixers / granulators / compressors, which preferably have different stirring speeds, is used here as an example exhibit, called.
  • the granulation it is possible, for example, for the granulation to be carried out first in a so-called high-speed mixer and then in a slower-running mixer or else first in a slower-running mixer and then in a high-speed mixer, in which case it must be ensured that the resulting granules not be smashed again.
  • Particularly preferred is the so-called roll granulation, in which the agglomerates are built up and compacted under rolling conditions. Almost spherical end products are obtained as finished granules.
  • Such roll granulation is possible, for example, in high-quality fillets (Marumerizers).
  • Another roll granulation process is described in international patent application WO-A-94/13779.
  • aqueous solutions and / or aqueous dispersions are used as the liquid granulating aid.
  • the salts are preferably alkali silicates, alkali carbonates, alkali bicarbonates and / or alkali sulfates, with silicates and (bi-) carbonates being particularly preferred.
  • an aqueous solution of an organic cobuide is used as the granulating aid.
  • organic cobuilders are, for example, the polycarboxylic acids optionally used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures from 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.
  • polymeric polycarboxylates for example the sodium salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular weight of 800 to 150,000 (based on acid) are particularly preferred.
  • 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 contained 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.
  • polymers of more than two different monomer units for example those described in DE-A-43 00 772 as monomeric salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomeric salts of acrylic acid and 2-alkylallyisulfonic acid and sugar derivatives.
  • Further preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • aqueous dispersions and in particular aqueous emulsions are used as granulation aids.
  • Liquid to flowable ingredients of detergents or cleaning agents are used in particular at the processing temperature.
  • Mixtures of nonionic surfactants and water and / or mixtures of nonionic surfactants and the above-mentioned aqueous solutions, in particular aqueous silicate solutions, are to be mentioned in particular.
  • alkoxylated, preferably ethoxylated and / or ethoxylated and propoxylated aliphatic which includes in particular primary 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 can contain linear and methyl-branched radicals in the mixture, as they are usually 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 alcohol with 3 EO or 4 EO, Cg-Cn alcohol with 7 EO, Ci3-C ⁇ s alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci2-C ⁇ 8 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-C-14 alcohol with 3 EO and Ci2-C ⁇ alcohol with 7 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 of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.
  • alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms can also be used as further nonionic surfactants means and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for giucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10.
  • granulation and drying take place in a so-called fluidized bed granulator.
  • fluidized bed granulator not only apparatus from Aeromatic, Federal Republic of Germany, but also turbo dryers, such as are available from Vomm, Italy, are counted in the context of this invention.
  • Further apparatuses in which the granules can also be dried indirectly are, for example, plate dryers from Krauss-Maffei, disc dryers from Babcock or Nara paddle dryers from Gouda.
  • the granular amorphous alkali silicates obtained preferably have a bulk density of between 750 and 1100 g / l at nonionic surfactant contents of 1 to 15% by weight and are still free-flowing under these conditions (even after storage for several weeks).
  • the amorphous alkali silicate granules produced according to the invention thus differ in their high absorbency compared to liquid to flowable ingredients of detergents or cleaning agents from conventional known amorphous alkali silicate granules in the processing temperature.
  • the use of the compounds produced according to the invention in compacted washing or cleaning agents with bulk densities above 700 g / l and surfactant contents above 15% by weight, preferably above 17% by weight, has proven to be particularly advantageous.
  • the amorphous alkali silicate granules produced according to the invention can, as an admixture component in powdery to granular washing or cleaning agents or as a component in the production of granular washing or cleaning agents with bulk densities, advantageously above 600 g / l, preferably during granulation and / or compacting, be used.
  • Such agents can have the granular amorphous alkali silicates produced according to the invention preferably 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 processes such as mixing, granulating, compacting such as roller compaction and extrusion.
  • nonionic surfactants in particular ethoxylated fatty alcohols
  • Suitable surface modifiers are known from the prior art.
  • finely divided zeolites, hydrophilic or hydrophobized silicas, amorphous silicates, fatty acids or fatty acid salts, for example calcium stearate, but in particular hydrophilic silicas or mixtures of zeolite and silicic acid, 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 of at least 750 g / l, which contain the granular amorphous alkali silicates produced according to the invention with secondary washing power.
  • the granular amorphous alkali silicates produced according to the invention can serve once as an admixture component, as in other manufacturing processes, but it is particularly preferred to incorporate these alkali silicates into the premix to be extruded and to carry out a coextrusion of these silicates.
  • the building properties of the granular amorphous silicates are retained even after extrusion.
  • the finished washing or cleaning agents can contain the following ingredients in addition to the impregnated alkali silicates produced according to the invention.
  • the following list also contains more detailed descriptions for some of the ingredients found in the silicate additives produced according to the invention.
  • surfactants especially anionic surfactants and, if appropriate, nonionic surfactants, but also cationic, amphoteric or zwitterionic surfactants.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • Preferred surfactants of the sulfonate type are Co, -Ci3-alkylbenzenesulfonates, olefin sulfonates, i.e. Mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained, for example, from Ci2-C-
  • alkanesulfonates which are obtained from C 1 -C 8 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids e.g. the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters and their mixtures, such as those produced by esterification with a monogtycerol containing 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol can be obtained.
  • the sulfonation products are a complex mixture which contains mono-, di- and triglyceride sulfonates with a sulfonic acid group in the a and / or in the interior.
  • sulfonated fat acid salts As by-products, sulfonated fat acid salts, glyceride sulfates, glycerine sulfates, glycerin and soaps. If one starts from the sulfonation of saturated fatty acids or hardened fatty acid glycerol ester mixtures, the proportion of the ⁇ -sulfonated fatty acid disalts can, depending on the procedure, be up to about 60% by weight.
  • Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C ⁇ to cis fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • the alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half-esters of the C 12 -C 18 -fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the CIO-C2o Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • Ci6-C ⁇ -alk (en) yl sulfates are particularly preferred for washing technology reasons. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use Ci6-C ⁇ -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 compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C12-Ci4-fatty alkyl sulfates or Ci2-C ⁇ -fatty alkyl sulfates with Ci6-C-i8-fatty alkyl sulfates and in particular C-i2-Ci 6 - Fatty alkyl sulfates with C-i ⁇ -Ci ⁇ fatty alkyl sulfates.
  • not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C16 to C22 are used.
  • 2,3-Alkyl sulfates which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN, are also suitable anionic surfactants.
  • the sulfuric acid monoesters of the straight-chain or branched C7-C2i alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched Cg-Ci --- alcohols with an average of 3.5 mol of ethylene oxide (EO) or C-
  • a preferred use is found in mixtures in which the proportion of the alkyl radicals is 15 to 40% by weight on C12, 5 to 15% by weight on C14, 15 to 25% by weight on C16, 30 to 60% by weight .-% on Ci ⁇ , and less than 1 wt .-% distributed on C10.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated fatty acid soaps are particularly suitable, 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 beef mixtures.
  • the anionic surfactants 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.
  • non-ionic surfactants such as alkoxylated fatty alcohols, alkyl glycosides and ethoxylated fatty acid methyl esters
  • suitable non-ionic surfactants are, in particular, amine oxides, polyhydroxy fatty acid amides and so-called mini-surfactants.
  • 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 alkanol amides 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 (I),
  • R- ⁇ CO for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R 3 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [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 preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
  • R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R represents a linear, branched or cyclic alkyl radical or is an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C 1 -C 4 -alkyl or phenyl radicals being preferred
  • [Z] is also preferably obtained here by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international patent application WO-A-95/07331, be converted into the desired polyhydroxyfatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • So-called gemini surfactants can be considered as further surfactants. These are generally understood to mean those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated from one another by a so-called “spacer”.
  • This spacer is generally a carbon chain which should be long enough that the hydrophilic groups are sufficiently far apart that they can act independently of one another.
  • Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, however, the term gemini surfactants means not only dimeric but also trimeric surfactants.
  • Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to German patent application DE-A-43 21 022 or dimer alcohol bis and trimeral alcohol tris sulfates and ether sulfates according to older German patent application P 195 03 061.3.
  • End group-capped dimeric and trimeric mixed ethers according to the older German patent application P 195 13 391.9 are distinguished in particular by their bi- and multifunctionality.
  • the end-capped surfactants mentioned have good wetting properties and are low-foaming, so that they are particularly suitable for use in machine washing or cleaning processes.
  • gemini-polyhydroxyfatty acid amides or poly-polyhydroxyfatty acid amides already mentioned, as described in the international patent applications WO-A-95/19953, WO-A-95/19954 and W095-A- / 19955, can also be used .
  • the agents can contain known additives commonly used in washing or cleaning agents, for example builders, bleaching agents and bleach activators, graying inhibitors, foam inhibitors, salts of citric acid, salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, small amounts contain neutral to weakly acidic filling salts as well as colorants and fragrances, opacifiers or pearlescent agents.
  • the builders which can be used in addition to the granular amorphous alkali silicates produced according to the invention include, in particular, zeolites, crystalline layered (di) silicates, carbonates and, if appropriate, phosphates, provided that such use is not objectionable for ecological reasons.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP *** (commercial product from Crosfield) is particularly preferred.
  • zeolite X and Mi ⁇ are mixtures of A, X and / or P.
  • the zeolite may be used as spray dried powder or even as an undried still moist from their preparation, stabilized suspension ⁇ A kit come.
  • the zeolite in the event that the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 1 -C 8 -fatty alcohols with 2 to 5 ethylene oxide groups, C. -i2-C-i4 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x ⁇ 2 ⁇ + ⁇ yH2 ⁇ , 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 are 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline sheet silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si2 ⁇ s yH2 ⁇ are preferred.
  • organic cobuilders can also be used; this includes in particular the polycarbonate already mentioned above, such as citric acid or its salts, such as citrate, but also the (co) polymeric polycarboxylates.
  • suitable organic cobuilders are known dextrins, starch derivatives, polyaspartic acid and certain polyacetals.
  • Dextrins for example oligomers or polymers of carbohydrates, can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000.
  • DE dextrose equivalent
  • Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0427 349, EP-A-0472 042 and EP-A-0 542 496 and international patent applications WO-A- 92/18542, WO-A-93/08251, WO-A-94/28030, WO-A-95/07303, WO-A-95/12619 and WO-A-95/20608.
  • a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
  • the starch derivatives include, in particular, oxidation products of carboxyl group-containing polyglucosans and / or their water-soluble salts, as are described, for example, in international patent application WO-A-93/08251 or their preparation, for example, in international patent application WO-A -93/16110 is described.
  • Oxidized oligosaccharides according to the older German patent application P 196 00 018.1 are also suitable.
  • polymeric aminodicarboxylic acids their salts or their precursor substances.
  • Particularly preferred are polyaspartic acids or their salts and derivatives, of which German Patent Application P 195 40 086.0 discloses that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.
  • 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.
  • Suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate. Also particularly preferred in this context are glycerol disuccinates and glycerol trisuccinates, as described, for example, in US Pat. Nos. 4,524,009, 4,639,325, in European patent application EP-A-0 150 930 and in Japanese patent application JP 93/339896 to be discribed. Suitable amounts are 3 to 15% by weight in formulations containing zeolite and / or silicate.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • Such cobuilders are described, for example, in international patent application WO-A-95/20029.
  • bleaching agents are, for example, sodium percarbonate, peroxypyrophosphate, citrate perhydrates and H2O2-providing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • bleach activators can be incorporated into the preparations.
  • these are N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably multiply acylated alkylenediamines such as N, N'-tetraacylated diamines, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, Triazoles, triazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, also carboxylic acid esters such as p- (alkanoyl-oxy) benzenesulfonates, in particular sodium isononanoyl-oxybenzenesulfonate, furthermore caprolactam derivatives, carboxylic acid anhydrides such as phthalic acid pentane anhydride and esters of polye
  • 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-di-acetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol -Mannitol blends (SORMAN).
  • TAED N, N, N ', N'-tetraacetylethylene diamine
  • DADHT 1,5-di-acetyl-2,4-dioxo-hexahydro-1,3,5-triazine
  • SORMAN acetylated sorbito
  • the bleach activator can be coated with coating substances in a known manner or, if appropriate using auxiliaries, in particular methyl celluloses and / or carboxymethyl celluloses, can have been granulated or extruded / pelletized and, if desired, contain further additives, for example dye. Such a granules over 70 wt .-%, in particular from 90 to 99 wt .-% bleach activator.
  • a bleach activator is preferably used which forms peracetic acid under washing conditions.
  • the agents can also contain components which have a positive effect on the oil and fat washability from textiles. This effect becomes particularly clear when a textile is contaminated which 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, non-ionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and hydroxypropoxyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or 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.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin which have a high proportion of C- (8-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, for example those made of silicones, paraffins or waxes, are also advantageously used.
  • foam inhibitors in particular silicone and / or paraffin-containing foam inhibitors, are preferred gates, bound to a granular, water-soluble or water-dispersible carrier substance, in particular mixtures of paraffins and bistearylethylene diamides are preferred.
  • Enzymes in particular include those from the class of hydrolases, such as proteases, lipases or enzymes having a tipolytic action, amylases, cellulases or mixtures thereof. Oxireductases are also suitable.
  • Enzymatic active substances 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 are preferred Proteases obtained from Bacillus lentus are used.
  • Enzyme mixtures are, for example, from protease and amylase or protease and lipase or lipolytically acting enzymes or protease and cellulase or from cellulase and lipase or lipolytically acting enzymes or from protease, amylase and lipase or lipolytically acting enzymes or protease, lipase or lipolytically active enzymes and cellulase, but in particular, however, mixtures containing protease and / or lipase or mixtures with lipolytically active enzymes of particular interest.
  • Known cutinases are examples of such lipolytic enzymes.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • Cellobiohydrolases, endoglucanases and ⁇ -giucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since the different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order 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.
  • the salts of polyphosphonic acids in particular 1-hydroxyethane-1,1-diphosphonic acid (HEDP), diethylenetriaminepentamethylenephosphonic acid (DETPMP) or ethylenediaminetetramethylenephosphonic acid are suitable as stabilizers, in particular for per compounds and enzymes which are sensitive to heavy metal ions.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DETPMP diethylenetriaminepentamethylenephosphonic acid
  • ethylenediaminetetramethylenephosphonic acid are suitable as stabilizers, in particular for per compounds and enzymes which are sensitive to heavy metal ions.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed.
  • 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 methylhydroxyethyl cellulose, methylhydroxypro- pylcellulose, 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, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which instead of the Morphoiino group, wear a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenyl styrene type can also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.
  • Example B1 and B2 70 parts by weight of the spray-dried compound were mixed with 7 parts by weight of 10 parts by weight of C.sub.2 -C.sub.4 fatty alcohol before granulation
  • a spray-dried compound V3 (comparative example, composition see table 1) was ground using a pin mill. The bulk density rose from 110 g / l to 650 g / l. The product was then granulated in an Eirich mixer (B4 and B5) or in a continuous pelletizer from a ploughshare mixer from Lödige and a high-speed mixer from Schugi with the addition of nonionic surfactant and polymeric polycarboxylate.
  • Table 1 Composition of products B4 to B6 in% by weight
  • V3 B4 B5 B6 amorphous sodium disilicate 74, 3 63.1 65.5 65.5
  • the bulk weights of these 6 extrudates were all above 800 g / l. None of the extrudates tended in the test (bowl test, description see below) for gelation (grades in both subtests between 1 and 2).
  • test agent 25 g were sprinkled into 5 l of tap water (30 ° C.) in a wash bowl made of dark plastic (for example dark red). After 15 seconds, the agent was distributed in the bowl by hand. After a further 15 seconds, a blue terry towel was added to the wash liquor and moved as in a typical hand wash. After 30 seconds the wall of the bowl was wiped with the towel. Finally, after another 30 seconds, the towel was wrung out and visually graded.
  • dark plastic for example dark red
  • Grade 1 flawless, no recognizable residues
  • Grade 2 tolerable, isolated, not yet disturbing residues
  • Grade 3 recognizable residues from grade 4, which are already disturbing in the event of a critical assessment: clearly recognizable and disturbing residues in increasing numbers and quantities
  • Grade 2 tolerable, isolated, not yet disturbing residues, very finely divided, not gelling when water is added
  • Grade 3 recognizable residues that are already annoying when critically assessed, from grade 4: clearly recognizable and disturbing residues in increasing numbers and

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
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Abstract

L'invention concerne des silicates alcalins amorphes granulaires à masse volumique apparente d'au moins 700 g/l, à pouvoir d'absorption élevé, qui demeurent suffisamment coulants, même après imprégnation de constituants de détergents ou de nettoyants qui sont liquides à coulants à la température de traitement. Ces silicates alcalins s'obtiennent grâce à un procédé fondé sur le séchage par pulvérisation et comprend le compactage de billes séchées par pulvérisation. La bille séchée par pulvérisation est moulue et granulée simultanément ou à la suite, sous apport d'un adjuvant de granulation liquide, les masses volumiques apparentes étant ajustées pour être comprises entre au moins 700 g/l et jusqu'à 1 000 g/l et plus. Les granulats de ce type se prêtent particulièrement bien à être utilisés dans des détergents ou des nettoyants compacts, à forte teneur en tensioactifs et à masse volumique apparente supérieure à 700 g/l, car ils évitent le risque de gélification lorsque l'agent se dissout dans l'eau ou le réduise du moins sensiblement.
EP97914226A 1996-03-21 1997-03-12 Procede de production de silicates granulaires a masse volumique apparente elevee Ceased EP0888428A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19611012 1996-03-21
DE1996111012 DE19611012A1 (de) 1996-03-21 1996-03-21 Verfahren zur Herstellung von granularen Silikaten mit hohem Schüttgewicht
PCT/EP1997/001243 WO1997034977A1 (fr) 1996-03-21 1997-03-12 Procede de production de silicates granulaires a masse volumique apparente elevee

Publications (1)

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EP0888428A1 true EP0888428A1 (fr) 1999-01-07

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EP97914226A Ceased EP0888428A1 (fr) 1996-03-21 1997-03-12 Procede de production de silicates granulaires a masse volumique apparente elevee

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WO (1) WO1997034977A1 (fr)

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Publication number Priority date Publication date Assignee Title
DE19858887A1 (de) * 1998-12-19 2000-06-21 Henkel Kgaa Kompaktat mit silicatischem Builder
DE19936613B4 (de) 1999-08-04 2010-09-02 Henkel Ag & Co. Kgaa Verfahren zur Herstellung eines Waschmittels mit löslichem Buildersystem
DE19939804A1 (de) * 1999-08-21 2001-02-22 Cognis Deutschland Gmbh Schaumkontrollierte feste Waschmittel
DE19939805A1 (de) * 1999-08-21 2001-02-22 Cognis Deutschland Gmbh Schaumkontrollierte feste Waschmittel
DE102015205799A1 (de) 2015-03-31 2016-10-06 Henkel Ag & Co. Kgaa Waschmittelzusammensetzung mit verbesserter Fleckentfernung

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Publication number Priority date Publication date Assignee Title
US4022704A (en) * 1971-06-21 1977-05-10 Stauffer Chemical Company Production of spray dried, high bulk density hydrous sodium silicate mixtures
US3868227A (en) * 1972-04-05 1975-02-25 Philadelphia Quartz Co Agglomerating fine alkali metal silicate particles to form hydrated, amorphous, granules
GB1417475A (en) * 1972-10-12 1975-12-10 Stauffer Chemical Co Process for agglomerating hydrous sodium silicate
JPS5830247B2 (ja) * 1977-07-27 1983-06-28 日本化学工業株式会社 高かさ密度の珪酸ソ−ダ水和物の製造法
DE3620010A1 (de) * 1986-06-13 1987-12-17 Henkel Kgaa Verfahren zur herstellung von natriummetasilikat-agglomeraten
GB9004562D0 (en) * 1990-03-01 1990-04-25 Unilever Plc Silicate

Non-Patent Citations (1)

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Title
See references of WO9734977A1 *

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WO1997034977A1 (fr) 1997-09-25

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