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WO1995000629A1 - Procede de fabrication de produits d'extrusion ayant un effet nettoyant et detergent - Google Patents

Procede de fabrication de produits d'extrusion ayant un effet nettoyant et detergent Download PDF

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Publication number
WO1995000629A1
WO1995000629A1 PCT/EP1994/001918 EP9401918W WO9500629A1 WO 1995000629 A1 WO1995000629 A1 WO 1995000629A1 EP 9401918 W EP9401918 W EP 9401918W WO 9500629 A1 WO9500629 A1 WO 9500629A1
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WO
WIPO (PCT)
Prior art keywords
weight
silicates
solid
amorphous silicates
premix
Prior art date
Application number
PCT/EP1994/001918
Other languages
German (de)
English (en)
Inventor
Kathrin Schnepp
Wolfgang Seiter
Bernd Larson
Manfred Greger
Hubert Pawelczyk
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to EP94920447A priority Critical patent/EP0705330A1/fr
Publication of WO1995000629A1 publication Critical patent/WO1995000629A1/fr

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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
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • 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 a method for producing washable or cleaning-active extrudates with high density.
  • a process for the production of extrudates wherein a solid premix is extruded under pressure and the strand is cut to the predetermined granule size after exiting the hole shape by means of a cutting device.
  • the solid and free-flowing premix contains a plasticizer and / or lubricant, which causes the premix to become plastically softened and extrudable under pressure or under the entry of specific work.
  • Preferred plasticizers and / or lubricants are surfactants and / or polymers, which are preferably used in liquid, paste-like or gel-like preparation form.
  • the premix can also contain powders and / or granules, the granules being obtained, inter alia, by granulation processes or also by conventional spray drying processes. After exiting the hole shape, the system no longer has any shear forces and the viscosity of the system is reduced in such a way that the extruded strand can be cut to predeterminable extrudate dimensions.
  • an extruder is known from international patent application WO-A-91/13678 which can be used to carry out this method.
  • the object of the invention was to provide a process for the production of extrudates which are active in washing or cleaning and which have improved redispersibility and which additionally allows zeolite and amorphous silicon to process likate.
  • the extrudates should have improved redispersion behavior even when a premix is used which contains at least one spray-dried component.
  • the invention accordingly relates to a method for producing washable or cleaning-active extrudates with high density, wherein a solid premix, which contains a plasticizer and / or lubricant, is extruded under pressure, the strand after exiting the hole shape by means of a cutting device onto the predetermined granule dimension cut and amorphous silicates are used in the solid premix, either
  • amorphous silicates at least partially as a solid component and as a plasticizer and / or lubricant, water or aqueous solutions or
  • the amorphous silicates are used at least partially in the form of an aqueous solution as plasticizers and / or lubricants.
  • the premix is preferably continuously fed to a 2-screw extruder with a co-rotating or counter-rotating screw guide, the housing and the extruder granulating head of which can be heated to the predetermined extrusion temperature.
  • the premix is compressed, plasticized, and extruded in the form of fine strands through the perforated die plate in the extruder head under pressure, which is preferably at least 25 bar, but can also be below this at extremely high throughputs depending on the apparatus used and finally the extrudate is preferably reduced to approximately spherical to cylindrical granules by means of a rotating cutting knife.
  • the hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granule dimension.
  • the production of granules of an essentially uniformly predeterminable particle size succeeds, the absolute particle size large can be adapted to the intended purpose.
  • particle diameters of up to at most 0.8 cm are preferred.
  • Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from approximately 0.8 to 3 mm.
  • the length / diameter ratio of the chipped primary granules is in the range from about 1: 1 to about 3: 1.
  • zeolite powder such as zeolite NaA powder
  • the extrudates are then preferably fed to a drying step, for example a fluidized bed dryer.
  • the extruded granules which contain peroxy bleaching agents, for example perborate monohydrate, can be dried at supply air temperatures between 80 and 150 ° C. without loss of active oxygen.
  • peroxy bleaching agents for example perborate monohydrate
  • the amorphous silicates used in accordance with the invention are preferably amorphous alkali silicates such as sodium silicates and potassium silicates, especially sodium silicates, with a molar ratio of metal oxide to silicon dioxide of 1: 1 to 1: 4.5, preferably of 1: 1.9 to 1: 4.0 and especially from 1: 2 to 1: 3.5.
  • the content of the extrudates in amorphous alkali likates, in particular in sodium silicates is generally up to 10% by weight and preferably between 2 and 8% by weight.
  • the amorphous silicates are preferably introduced into the extrusion process at least in part in the form of an aqueous solution. In the process, these solutions serve as plasticizers and / or lubricants.
  • the concentration of the aqueous solutions of amorphous silicates can vary over a wide range. In the course of the extrusion process, however, it is preferred to use aqueous solutions use which have an amorphous silicate content of between 10 and 45% by weight, in particular between 20 and 40% by weight.
  • amorphous silicates can also be used in addition or even exclusively in solid form as an admixture component to at least one further solid.
  • granular or powdery, in particular spray-dried, water glasses come into consideration.
  • they can also be part of a granular component which contains various, preferably customary, ingredients of washing or cleaning agents.
  • This granular component - if it contains silicates in amounts above 3% by weight - is essentially free of zeolite, ie it contains not more than 5% by weight, preferably not more than 3% by weight, of zeolite (based on anhydrous Active substance) and in particular contains no zeolite at all.
  • water is a preferred plasticizer and / or lubricant.
  • amorphous silicates are used in the form of an aqueous solution and additionally as a solid powdery or granular admixture component in the solid premix.
  • amorphous silicates are also taken to mean those X-ray amorphous silicates as are described in the older German patent application P 4400024.3. These silicates are particularly suitable as powdery or granular admixture components. In a particularly preferred embodiment of the invention, however, amorphous silicates are only introduced into the extrusion process in the form of an aqueous solution as plasticizers and / or lubricants. The silicates not only improve the redispersion behavior of the extrudates, they also contribute to the stability of the extrudate.
  • the solids contained in the premix can be introduced into the process as powdered raw materials. However, it is preferred that at least one granular component, which was produced by granulation, extrusion or conventional spray drying, is used for the production of the premix. It can be particularly advantageous if the premix contains at least one spray-dried component, which zeolite, preferably in substantial amounts, ie in amounts above 10% by weight (calculated as anhydrous active Substance), based on the component contains.
  • zeolite and amorphous silicates are preferred which do not contain amorphous silicates in amounts above 3% by weight, preferably in amounts up to 1% by weight and in particular no amorphous ones Contain silicates.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quality.
  • zeolite NaX and mixtures of NaA and NaX are also suitable.
  • the zeolite can be used as a spray-dried powder as a solid admixture. However, it is preferred that it is used in the spray-dried component mentioned which also contains other ingredients.
  • the zeolite is used in particular as a suspension which contains small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated with 2 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, in particular 20 to 22,% by weight of bound water.
  • the zeolite is preferably introduced into the process in the form of this finely divided powder or in the form of a granular component which can be granulated or spray-dried.
  • ingredients of the granular component (s) and in particular of the spray-dried component (s) mentioned are, for example, anionic sides, further builders such as phosphates, crystalline layer silicates, polycarboxylates and (co) polymeric polycarboxylates, alkali metal carbonates, in particular sodium carbonate, optical brighteners and / or other inorganic salts.
  • a spray-dried component is preferred which contains polymeric polycarboxylates in amounts of 1 to 5% by weight and in particular in amounts of 2 to 4% by weight, based in each case on the spray-dried component.
  • At least one further plasticizer and / or lubricant is used in the solid premix in addition to the aqueous silicate solutions.
  • plasticizing and / or lubricants can be considered here, is already known from international applications W0-A-91/02047 and W0-A-93/02176.
  • liquid surfactants or liquid surfactant mixtures and / or aqueous polymeric polycarboxylate solutions are used as further plasticizers and / or lubricants in the context of this invention.
  • no polymeric polycarboxylates in the form of an aqueous solution are introduced into the process as plasticizers and / or lubricants if the premix has zeolite and / or amorphous silicates as solid admixing components.
  • the components used in the premix in addition to zeolite and amorphous silicates are for the most part the usual ingredients of detergents or cleaning agents. These include, in particular, anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and zwitterionic surfactants, as well as other builder substances, alkaline salts, bleaching agents, graying inhibitors, foam inhibitors, optical brighteners and enzymes.
  • premixes which contain 30 to 60% by weight, preferably 35 to 50% by weight, in each case based on anhydrous active substance, zeolite in detergent quality, 0.5 to 10% by weight and above ⁇ preferably 1 to 5 wt .-% amorphous silicates and 5 to 40 wt .-%, preferably 10 to 30 wt .-% surfactants.
  • Weight ratios of anionic surfactants to nonionic surfactants of 10: 1 to 1: 5 are preferred. Amounts of 5 to 15% by weight of anionic surfactants and 5 to 15% by weight of nonionic surfactants are particularly preferred.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • Preferred surfactants of the sulfonate type are Cg-Ci3-alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates as well as disulfonates, such as are obtained, for example, from Ci2-Ci8 * monoolefins with a terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates which are obtained from C 1 -C 8 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the esters of ⁇ -sulfofatty acids are also suitable, for example the ⁇ -sulfonated methyl esters of the hydrogenated ten coconut, palm kernel or tallow fatty acids and their salts.
  • Other suitable anionic surfactants are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 mol of fatty acid or by the esterification of triglycerides with 0.3 to 2 moles of glycerol can be obtained.
  • Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • the salts of alkylsulfosuccinic acid can also be used.
  • Suitable sulfate-type surfactants are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin.
  • the alk (en) yl sulfates are the sulfuric acid half-esters of the Ci2-Ci8 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C ⁇ o-C2 ⁇ "0 ⁇ oa crude oils, and those sekun ⁇ Preferred alcohols of this chain length are further preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic straight-chain alkyl radical which is produced on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials Ci6-Ci8-Alk (en) yl sulfates are particularly preferred, but it can also be particularly advantageous and particularly advantageous for machine washing agents to use Ci6-Ci8-alk (
  • the agents therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C8-Cis-alkyl sulfates, in particular C ⁇ -alkyl sulfate, Ci2-alkyl sulfate or C 2 ⁇ Ci ⁇ -alkyl sulfate mixtures with high proportions of Ci2 Alkyl sulfate in combination with Ci6-Ci8-fatty alkyl sulfates. It is particularly advantageous that these alkyl sulfates are again in the form of a spray-dried, spray-neutralized, granulated or granulated and, at the same time, dried. Compounds are used.
  • Compounds are preferred which contain C 1 -C 2 -alkyl sulfate and alkali carbonate, in particular sodium carbonate, and optionally alkoxylated alcohols having 10 to 40 ethylene oxide groups (EO) as the carrier material for the alkyl sulfate.
  • EO ethylene oxide groups
  • saturated alkyl sulfates not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C ⁇ to C22 are used.
  • Mixtures of saturated, predominantly C 6 -sulfonated fatty alcohols and unsaturated, predominantly C 18 -sulfonated fatty alcohols are particularly preferred, for example those which are derived from solid or liquid HD-Ocenol ( R ) fatty alcohol mixtures (commercial product of the applicant) deduce.
  • Weight ratios of alkyl sulfates to alkenyl sulfates of 10: 1 to 1: 2 and in particular of about 5: 1 to 1: 1 are preferred.
  • the sulfuric acid monoesters of the straight-chain or branched C7 ⁇ C2i alcohols ethoxylated with 1 to 6 moles of ethylene oxide such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 moles of ethylene oxide (E0) or Ci2-Ci8 -Fatty alcohols with 2 to 4 E0 are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Suitable anionic surfactants are, in particular, soaps, preferably in amounts of up to 4% by weight.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated Ci2-C24 fatty acid soaps and 0 to 50% by weight of oleic acid soap.
  • the anionic surfactants can be present 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 Form their sodium or potassium salts, especially in the form of the sodium salts before.
  • the nonionic surfactants used are preferably alkoxylated, advantageously liquid ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 40 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear or preferably in 2 Position can be methyl-branched, or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 C atoms are preferred, e.g. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred.
  • the preferred ethoxylated alcohols include, for example, Ci2-Ci4 alcohols with 3 EO or 4 EO, Cg-Cn alcohol with 7 EO, Ci3-Ci5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci2-Ci8- Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci2-Ci4 alcohol with 3 EO and Ci2-Ci8 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical mean values which can be an integer or a fractional number for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • nonionic surfactants are, in particular, tallow fatty alcohols with 11 EO, 14 EO or 25 EO. It has been shown that these nonionic surfactants can also be granulated or spray-dried together with anionic surfactants and thus lead to improved application properties of the finished extrudates. According to the teaching of international application WO-A-93/02176, in addition to the alkoxylated alcohols mentioned, alkoxylated alcohols with up to 80 EO, preferably tallow fatty alcohol with 40 E0, or polyethylene glycols, preferably with a relative molecular weight between 200 and 600, can also be used in mi ⁇ be used with other nonionic surfactants. In the context of this invention, however, it is preferred to introduce alkoxylated alcohols with 10 to 40 E0 in the form of a solid preparation into the premix, particularly preferably if the premix contains alk (en) yl sulfates.
  • alkyl glycosides of the general formula R0 (G) x in which R is a primary non-ionic surfactant can also be used. Radkettigen or methyl branched, in particular in the 2-position methyl branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose .
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • the alkyl glycosides can be present in the premix in amounts of, for example, 1 to 5% by weight.
  • 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-A-58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.
  • 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 non-ionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Other suitable surfactants which can replace alkyl glycosides or can be used in combination with them are polyhydroxy fatty acid amides of the formula (I),
  • 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 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid iden 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. With regard to the processes for their preparation, reference is made to US Pat. Nos. 1,985,424, 2,016,962 and 2,703,798, as well as international patent application WO 92/06984.
  • the builders may include phosphates, preferably in amounts not exceeding 15% by weight, and in particular crystalline, layered sodium silicates of the general formula (II) NaMS x ⁇ 2 ⁇ + ⁇ , yH2 ⁇ , where M is sodium or hydrogen means 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.
  • M sodium or hydrogen means 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 layered silicates of the formula (II) are those in which M is sodium and x is 2 or 3.
  • Layered silicates which are known, for example, from patent applications DE-B-23 34 899, EP-A-0 026 529 and DE-A-35 26 405 are also suitable. Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonite, are preferred here.
  • Usable organic builders are, for example, 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. 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 thereof, preferably in amounts of 2 to 10% by weight and in particular in amounts of 3 to 8% by weight. .
  • 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.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution, 20 to 55% by weight. % aqueous solutions are preferred. Also particularly preferred are biodegradable terpolymers, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers.
  • 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-0280 223 .
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • Suitable ingredients of the premix are water-soluble inorganic, in particular alkaline, salts such as bicarbonates and carbonates.
  • the sodium carbonate content of the agents is preferably up to 20% by weight, advantageously between 5 and 15% by weight.
  • Alkali carbonates can also be replaced by sulfur-free, 2 to 11 carbon atoms and, if appropriate, a further carboxyl and / or amino group having amino acids and / or their salts.
  • the alkali metal carbonates it is entirely possible for the alkali metal carbonates to be partially or completely replaced by glycine or glycinate.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H2O2-providing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
  • the bleaching agent content of the premix is preferably 5 to 25% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate.
  • bleach activators can be incorporated into the preparations.
  • these are N-acyl or 0-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose sepentaacetate.
  • 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'-tetraacetylethylenediamine and 1,5-diacety1-2,4-dioxo-hexahydro-1,3,5-triazine.
  • Suitable foam inhibitors are, for example, soaps 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 different foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
  • the foam inhibitors in particular silicone 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. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • enzyme mixtures for example of protease and aylase 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 containing cellulase .
  • (Per) 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.
  • the salts of polyphosphonic acids are suitable as stabilizers, in particular for per-compounds and enzymes.
  • 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) "" d, pyrobic acid (tetraboric acid H2B4O7), is particularly advantageous.
  • the agents can also contain components which have a positive effect on the ability to wash off fat and fat 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 hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, based in each case the nonionic cellulose ether, and the Polymers of phthalic acid and / or terephthalic acid or, respectively, known from the prior art. of their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates.
  • 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, e.g. degraded starch, aldehyde starches, etc.
  • Polyvinylpyrrolidone can also be used.
  • Cellulose ethers such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl ethyl 11, methyl hydroxypropyl ethyl 11, methyl carboxymethyl cellulose and mixtures thereof, and polyvinyl pyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the extrudates, are preferred. used.
  • 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-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which contain an replace the morpholino group with a diethanola ino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenylstyryl type may 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. It has been found that uniform white granules are obtained if, apart from the customary brighteners, the agents are used in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight.
  • % also small amounts, for example 10 ⁇ 6 to 10 -3 wt .-%, preferably around 10 ⁇ 5 wt .-%, of a blue dye.
  • a particularly preferred dye is Tinolu ⁇ ( R ) (commercial product from Ciba-Geigy).
  • the finished washing or cleaning agents can be built up uniformly from extrudates which have the above-mentioned ingredients.
  • the extrudates are prepared with further ingredients of washing or cleaning agents. This can be such that the washing or cleaning agents are obtained from a mixture of several different granules, of which the extrudates according to the invention form the main component.
  • Bleach activators for example N, N'-tetraacylated diamines such as N, N, N ', N'-tetraacetylethylenediamine, enzyme granules containing enzymes, in particular protease and / or lipase and / or cellulase and / or amylase, with mixtures of 2 or 3 enzymes can be particularly beneficial, and perfume added afterwards.
  • the extrudates can also be prepared with further finely divided dry powders before the enzymes and the other constituents are mixed. Examples of these are zeolite, silicas and salts of fatty acids, for example calcium stearate, bleach activator or mixtures of zeolite with one of the other powders mentioned.
  • the foam behavior for detergents can be influenced positively if the foam inhibitor, for example organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized Silica or bistearylethylenediamide, at least partially not extruded, but is subsequently mixed with the extrudate.
  • the surface of the extrudate according to the invention is first coated, for example, with zeolite or a mixture containing zeolite and then with a foam inhibitor. Such measures make it possible to further improve the flushing behavior of the extrudates.
  • the bulk density of the extrudates produced according to the invention is preferably between 600 and 1200 g / 1, bulk densities between 700 and 1000 g / 1 and in particular between 750 and 950 g / 1 being particularly preferred. Examples
  • the spray-dried product (“tower powder”, abbreviated TP) contained 10.3 parts by weight of Cg-Cis-alkylbenzenesulfonate, 2.9 parts by weight of Ci2-Ci8 * sodium fatty acid soap, 1.5 parts by weight of tallow fatty alcohol 5 E0, 56.4 parts by weight of zeolite (calculated as anhydrous active substance), 3.4 parts by weight of sodium carbonate, 2.3 parts by weight of polyvinylpyrrolidone, 1 part by weight of other salts from solutions and raw materials, 16, 8 parts by weight of water and 5.4 parts by weight of Sokalan CP ⁇ ( R ) (commercial product from BASF, copolymers based on the sodium salts of acrylic acid and maleic acid), which is 3.6 parts by weight , based on the premix.
  • the finished extrudate was dried, but not worked up any further.
  • the bulk density was 750 g / 1.
  • Example 1 was repeated with a premix, now containing 7 parts by weight of the 30% by weight waterglass solution and 3.6 parts by weight of Sokalan CP ⁇ ( R ), which in turn was introduced into the premix via the spray drying product .
  • the bulk density was 780 g / 1.
  • Example 1 was repeated, but now 2.2 parts by weight became amorphous
  • Comparative example 1 was repeated, but the spray drying product contained no copolymer of acrylic and maleic acid. Instead, 7 parts by weight of the 30% by weight aqueous Sokalan CP 5 ( R ) solution were introduced into the premix. The bulk density was 825 g / 1.
  • Comparative Example 1 was repeated. However, now only 5.1 parts by weight of the aqueous Sokalan CP ⁇ ( R ) solution and 2 parts by weight of amorphous water glass (1: 2.0) were used, the water glass being incorporated as a powder in the premix. This premix was not capable of extrusion (disturbances until the conveying elements failed in the extruder; sticking in the knife area).
  • grade 1 perfect, no discernible 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 number and quantity
  • Example 1 3.0 2.1 19.2 135
  • Example 2 2.6 2.1 21.5 149

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  • Detergent Compositions (AREA)

Abstract

L'invention concerne des produits d'extrusion ayant un meilleur pouvoir redispersant, obtenus à l'aide d'un procédé selon lequel un mélange initial solide contenant un plastifiant et/ou un lubrifiant est comprimé sous pression pour former un extrudat qui, à sa sortie de la filière, est découpé à la dimension de granulation prédéterminée au moyen d'un dispositif de coupe, lorsque des silicates amorphes sont incorporés dans le mélange initial solide. Ces silicates amorphes sont utilisés (a) au moins en partie sous forme de constituants solides, de l'eau ou des solutions aqueuses étant alors utilisées comme plastifiants et/ou comme lubrifiants, ou (b) au moins en partie sous forme de solution aqueuse comme plastifiants et/ou comme lubrifiants. On utilise de préférence (b) pour le procédé. Les silicates contribuent également à la stabilité granulaire des produits d'extrusion.
PCT/EP1994/001918 1993-06-21 1994-06-13 Procede de fabrication de produits d'extrusion ayant un effet nettoyant et detergent WO1995000629A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP94920447A EP0705330A1 (fr) 1993-06-21 1994-06-13 Procede de fabrication de produits d'extrusion ayant un effet nettoyant et detergent

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4320358.2 1993-06-21
DE19934320358 DE4320358A1 (de) 1993-06-21 1993-06-21 Verfahren zur Herstellung wasch- oder reinigungsaktiver Extrudate

Publications (1)

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WO1995000629A1 true WO1995000629A1 (fr) 1995-01-05

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EP (1) EP0705330A1 (fr)
DE (1) DE4320358A1 (fr)
WO (1) WO1995000629A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5755992A (en) * 1994-04-13 1998-05-26 The Procter & Gamble Company Detergents containing a surfactant and a delayed release peroxyacid bleach system

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4442977A1 (de) * 1994-12-02 1996-06-05 Henkel Kgaa Wasch- oder Reinigungsmittel mit wasserlöslichen Buildersubstanzen
DE4446363A1 (de) * 1994-12-23 1996-06-27 Henkel Kgaa Amorphes Alkalisilikat mit Imprägnierung
GB9520024D0 (en) * 1995-09-30 1995-12-06 Procter & Gamble Detergent composition
DE19858887A1 (de) * 1998-12-19 2000-06-21 Henkel Kgaa Kompaktat mit silicatischem Builder

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1963275A1 (de) * 1968-12-17 1970-09-17 Raion Yushi Kabushiki Kaisha Verfahren und Vorrichtung zum Granulieren von Detergentien
US4265790A (en) * 1979-08-09 1981-05-05 Church & Dwight Co., Inc. Method of preparing a dry blended laundry detergent containing coarse granular silicate particles
JPS6169899A (ja) * 1984-09-14 1986-04-10 花王株式会社 流動性の改良された高密度の粒状洗剤の製法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1963275A1 (de) * 1968-12-17 1970-09-17 Raion Yushi Kabushiki Kaisha Verfahren und Vorrichtung zum Granulieren von Detergentien
US4265790A (en) * 1979-08-09 1981-05-05 Church & Dwight Co., Inc. Method of preparing a dry blended laundry detergent containing coarse granular silicate particles
JPS6169899A (ja) * 1984-09-14 1986-04-10 花王株式会社 流動性の改良された高密度の粒状洗剤の製法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 8621, Derwent World Patents Index; Class A81, AN 86-133906 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5755992A (en) * 1994-04-13 1998-05-26 The Procter & Gamble Company Detergents containing a surfactant and a delayed release peroxyacid bleach system

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EP0705330A1 (fr) 1996-04-10
DE4320358A1 (de) 1994-12-22

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