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WO1994009111A1 - Procede de preparation d'extrudats a action lavante et nettoyante - Google Patents

Procede de preparation d'extrudats a action lavante et nettoyante Download PDF

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Publication number
WO1994009111A1
WO1994009111A1 PCT/EP1993/002836 EP9302836W WO9409111A1 WO 1994009111 A1 WO1994009111 A1 WO 1994009111A1 EP 9302836 W EP9302836 W EP 9302836W WO 9409111 A1 WO9409111 A1 WO 9409111A1
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WO
WIPO (PCT)
Prior art keywords
weight
throughput
specific work
zeolite
premix
Prior art date
Application number
PCT/EP1993/002836
Other languages
German (de)
English (en)
Inventor
Jochen Jacobs
Bernd Larson
Hubert Pawelczyk
Norbert Kühne
Kathrin Schnepp
Wolfgang Seiter
Rene-Andres Artiga Gonzalez
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 DE59305176T priority Critical patent/DE59305176D1/de
Priority to KR1019950701549A priority patent/KR950704471A/ko
Priority to JP6509634A priority patent/JPH08502312A/ja
Priority to EP93923465A priority patent/EP0665879B1/fr
Publication of WO1994009111A1 publication Critical patent/WO1994009111A1/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
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • 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

Definitions

  • the invention relates to a process for the production of washable or cleaning-active extrudates with a high density, which permits high throughput, the granules obtained by using the process and storage-stable and free-flowing detergent or cleaning agent concentrates containing them.
  • a process for the production of extrudates with high density whereby a homogeneous solid and free-flowing premix is extruded under pressure and the strand is cut to the predetermined granule size by means of a cutting device after exiting the hole shape becomes.
  • the homogeneous solid and free-flowing premix contains a plasticizer and / or lubricant, which has the effect that the solid and free-flowing premix is plastically softened and extrudable under the pressure or under the entry of specific work.
  • Preferred plasticizers and / or lubricants are surfactants and / or polymers, which are preferably used in liquid, pasty or gel-like preparation form.
  • an extruder is known from international patent application WO-A-91/13678 which can be used to carry out this method.
  • the extruded detergent or cleaning agent granules which can be produced by this process can contain high proportions of surfactants, for example up to 35% by weight, and have very good properties in terms of both use and consumption.
  • Structurally viscous behavior affects the lowering of plasticity with increasing shear rate.
  • the opposite behavior is called dilatancy. If there are only structurally viscous constituents in a premix, then it can happen that the premix softens so much under a strong shear gradient that it becomes almost liquid so that it is no longer capable of being cut after exiting the hole shapes. This also applies in particular to mixtures which contain high amounts of surfactants, for example nonionic surfactants or anionic surfactant pastes.
  • the extrudates produced according to WO-A-91/02047 therefore preferably contain not only constituents with a pseudoplastic viscosity, but also constituents with a dilatant action, which have increasing plasticity with increasing shear rate.
  • An increase in the throughput through the extruder initially results in an increase in pressure. Premixes which only contain constituents having a viscous structure soften under these conditions. At the same time, however, an increased throughput also means an increased energy input into the system (the Tool performance must be increased).
  • An increase in the throughput of a given formulation in a given extruder system also means an increase in the shear gradient and thus brings about the described decrease in plasticity in the case of structurally viscous components and an increase in the plasticity in the case of dilatant components.
  • the value of the specific work should be as low as possible for reasons of energy saving, the size of the system and drive of the systems, and the material stress. In view of this, a limited reduction in plasticity with increasing shear rate is even desirable for a given system.
  • the object of the invention was to develop a method for producing extrudates, the pressure (as a measurable parameter) and thus the specific work does not increase significantly when increasing the throughput.
  • another object of the invention was that the pressure and thus the specific work in a given system should not only not increase significantly when increasing the throughput, but should not decrease significantly either. This should ensure a constant cutting behavior of the plasticized strand even with different throughputs.
  • the extrudates obtained by the process should also meet the formulation requirements of modern washing or cleaning agents. It should therefore be possible to produce extrudates with a content of up to about 45% by weight of anionic and nonionic surfactants. It should also be possible to incorporate peroxy bleaching agents, for example perborate, into the extrudates using the process according to the invention.
  • the invention relates in a first embodiment to a process for producing washable or cleaning-active extrudates with high density, a homogeneous, solid and free-flowing premix being extruded under pressure and the strand after exiting the perforated shape by means of a cutting device onto the predetermined extrudate - Dimension is cut and in the premix to be extruded, a self-regulating system of recipe constituents having a structure-viscous effect under the process conditions and dilatant-acting recipe constituents is used, with the result that the value of the specific work does not significantly increase when the throughput is increased increases.
  • the specific work required for the extrusion should be as small as possible.
  • a value of max. 120 kJ / kg therefore represents a preferred upper limit for the specific work.
  • the value of the specific work should not increase significantly as the throughput increases; this means that the value of the specific work in a given system should preferably not increase by more than 10% of the initial value when the throughput is increased by at least 10%. It is preferred that the pressure and thus the value of the specific work should remain almost constant when the throughput is increased or should not decrease so much that the plastic decorated strand softened too much to be able to cut.
  • the deviation of the specific work when increasing the throughput in a given system by at least 10%, preferably by 10 to 50% and in particular up to 40%, not more than ⁇ 10% , preferably not more than ⁇ 5% and in particular not more than ⁇ 3%, in each case based on the initial value.
  • the throughput is increased, a transition to another extruder system, which, for example, has tools that work differently, is required. Regardless of the recipe, this can cause either an increase or a decrease in the specific work, whereby the size of the change cannot be stated as a percentage.
  • the specific work should preferably not increase above a value of 120 kJ / kg, in particular above 100 kJ / kg.
  • the lower limit of the specific work is again determined by the cutting ability of the strand.
  • Preferred throughput quantities are quantities in the range from 400 to 10,000 kg / h. Quantities below are unrenta ⁇ bel for large-scale production. Throughput rates of 600 to 7000 kg / h are particularly preferred.
  • the extrusion process according to WO-A-91/02047 is designed in such a way that widely variable formulations of solid and liquid constituents can be extruded under certain process conditions. Under the influence of the high pressure, the formulations should soften to such an extent that they spontaneously harden again after exiting the hole shapes so that they can be cut.
  • the plasticizers and / or lubricants as well as the selection and the amount of the plasticizers and / or lubricants used, which ensure the extrudability, are therefore a particularly important feature. What is new compared to WO-A-91/02047 is the feature that components which have a dilatant effect are present in the premixes.
  • zeolite and / or sand in particular for the production of detergents zeolite, are preferably used as dilatant active ingredients, whereas particularly preferred structurally viscous components are surfactants and / or polymeric polycarboxylates .
  • the zeolite used with preference is a finely crystalline, synthetic and bound water-containing zeolite, in particular 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 or as an undried stabilized suspension which is still moist from its production.
  • Suitable solid zeolites have an average particle size of less than 10 ⁇ (volume distribution; measurement method: Coulter Counter) and preferably contain 20 to 22% by weight of bound water.
  • the zeolite can contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 2 -C 6 fatty alcohols with 2 to 5 ethylene oxide groups or ethoxylated sotridecanols.
  • the extrusion process is preferably carried out at pressures of up to 260 bar, in particular between 25 and 200 bar.
  • the lower pressure of at least 25 bar disclosed in international applications WO-A-91/02047 and WO-A-93/02176 does not represent an absolutely fixed limit, but instead depends on the The type of extruder and the throughput of, for example, about 7000 kg / h or more can also be undercut. at Such high throughputs obviously play an important role in technical apparatus parameters, which were not foreseeable at lower throughputs, for example between 600 and 2000 kg / h.
  • zeolite preferably zeolite NaA, optionally in combination with zeolite NaX, in particular zeolite NaA in detergent quality in amounts of 10 to 60% by weight, advantageously in amounts of 15 to 55% by weight. % and in particular from 18 to 50% by weight, calculated in each case as an anhydrous active substance and based on the finished granules.
  • the proportion of the components with a pseudoplastic effect is then adjusted so that the difference between the microscopically occurring pressure increase (caused by the increase in throughput and the behavior of the dilating components) and the microscopically occurring pressure reduction (caused by the softening) of the components with a pseudoplastic effect) is so low or almost zero that macroscopically no change in the pressure occurs to the extent that a substantial change in the specific work would be effected.
  • the self-regulating system not only brings about an approximate pressure constant for a given formulation system in a given extruder system, but also enables approximate temperature constancy in a further aspect of the invention due to the approximately constant specific work, since extruders have only a low level Have heat exchange surface and the residence time of the plasticized premix in the extruder is relatively short.
  • the extrusion is carried out in a temperature range between 30 and 70 ° C., in particular between 35 and 65 ° C., which ensures that temperature-sensitive components, for example peroxy bleaching agents such as perborate, can also be processed.
  • temperature-sensitive components for example peroxy bleaching agents such as perborate
  • Lubricant is referred to the disclosure of WO-A-91/02047.
  • the premix is preferably fed continuously to a 2-screw extruder with a co-rotating or counter-rotating screw guide, the housing and the extruder pelletizing head of which can be heated to the predetermined extruded temperature.
  • the premix is compressed, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally the extrudate is preferably reduced to spherical to cylindrical granules by means of a rotating knives.
  • the hole diameter in the perforated nozzle plate and the strand cut length are matched to the selected granule dimension.
  • granules of a substantially uniformly predeterminable particle size can be produced, the absolute particle sizes in particular being able to be adapted to the intended use.
  • particle diameters up to at most 0.8 cm are preferred.
  • Important embodiments provide for the production of uniform granules with diameters 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 chopped-off primary granules is in the range from about 1: 1 to about 3: 1.
  • edges present on the raw granulate are rounded off so that ultimately spherical or at least approximately spherical granules can be obtained.
  • small amounts of dry powder for example zeolite powder such as zeolite NaA powder, fatty acid salts such as calcium stearate, finely divided silicas and mixtures of these, can also be used in this stage.
  • This shaping can be carried out in standard rounding machines, for example in rounders with a rotating base plate.
  • the granules are then preferably fed to a drying step, for example a fluidized bed dryer.
  • extruded Granules which contain peroxy compounds as bleaching agents, for example perborate monohydrate, are dried at supply air temperatures between 80 and 150 ° C. without loss of active oxygen.
  • the free water content of the dried granules is preferably up to about 3% by weight, in particular between 0.1 to 1% by weight.
  • dry powders are again zeolite-NaA powder, but also precipitated or pyrogenic silica, such as are commercially available, for example, as Aerosil (R) or Sipernat (O (products from Degussa), and fatty acid salts such as calcium stearate.
  • zeolite-NaA powder but also precipitated or pyrogenic silica, such as are commercially available, for example, as Aerosil (R) or Sipernat (O (products from Degussa), and fatty acid salts such as calcium stearate.
  • fatty alcohol sulfate powder which consists essentially, that is to say at least 90%, of particles with a particle size of less than 100 ⁇ m.
  • mixtures of zeolite and fatty alcohol sulfate powder, zeolite and silica or zeolite and calcium stearate are preferred.
  • solid washing or cleaning agents are claimed, which are produced by the process according to the invention and have a bulk density of preferably 600 to 1200 g / 1 and in particular 750 to 1000 g / 1.
  • detergents which contain 10 to 45% by weight, preferably 15 to 40% by weight, of surfactants produced by the process according to the invention are preferred.
  • Suitable anionic surfactants are, for example, those of the sulfonate and sulfate type.
  • Suitable surfactants of the sulfonate type come alkyl benzene sulfonates (Cg-Ci5 alkyl), olefin sulfonates, ie mixtures of alkene and hybrid droxyalkansulfonaten and the disulfonates obtained, for example, 'f' from Ci2-CI8 ° M ° no l e 'nen with a double and internal double bond obtained by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • dialkane sulfonates which are derived from C ⁇ -Cig-Al anen by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and in particular the esters of ⁇ -sulfofatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids. Salts of alkylsulfosuccinic acid can also be used.
  • Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, that is to say from fatty alcohols, for example coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the CIQ-C20 -0 ⁇ oa l alcohols, and those of secondary alcohols of this chain length.
  • the sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched Cg-Cu alcohols with an average of 3.5 mol of ethylene oxide, are also suitable.
  • Sulfated fatty acid monoglycerides are also suitable.
  • Soaps from natural or synthetic, preferably saturated, fatty acids can also be used.
  • Soap mixtures derived from natural fatty acids for example coconut, palm kernel or tallow fatty acids, are particularly suitable.
  • Preferred are those which are composed of 50 to 100% of saturated C 1 -C 6 fatty acid soaps and 0 to 50% of oleic acid soaps.
  • the anionic surfactants can be in the form of their sodium, potassium and ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the content of anionic surfactants or anionic surfactant mixtures in detergents according to the invention is preferably 5 to 40% by weight, in particular 8 to 35% by weight. It is particularly advantageous if the sulfonate and / or sulfate content of the agents is 10 to 35% by weight, in particular 15 to 30% by weight, and the soap content is up to 8% by weight, in particular 0%. 5 to 5% by weight.
  • the anionic surfactants can be used in solid form, for example in spray-dried or granulated form, or in liquid to pasty form. It is preferred to use the anionic surfactants as plasticizers. and / or lubricants and / or as a solid premix component in the form of a spray-dried, granulated or extruded compound in the
  • the nonionic surfactants used are preferably liquid ethoxylated, in particular primary, alcohols having preferably 9 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear or methyl-branched in the 2-position may, or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • linear residues from alcohols of native origin with 12 to 18 carbon atoms e.g. from coconut, tallow or oleyl alcohol, which have an average of 2 to 8 EO, preferred.
  • the content of the agents in ethoxylated alcohols used according to the invention as nonionic surfactants is preferably 1 to 15% by weight and in particular 2 to 10% by weight.
  • the weight ratio of anionic surfactant to ethoxylated fatty alcohols is preferably 1: 2 to 6: 1 and in particular 1: 1.2 to 6: 1.
  • Polyhydroxy fatty acid amides are suitable as further nonionic surfactants. These are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkyl in 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 production, reference is made to US Pat. Nos. 1,985,424, 2,016,962 and 2,703,798, as well as international patent application WO-A-92/06984.
  • nonionic surfactants can also be alkyl glycosides of the general formula R-0- (G) x , in which R is a primary straight-chain or aliphatic radical with 8 to 22, preferably 12 to 18, C-atoms, methyl-branched, G is a symbol which stands for a glycose unit with 5 or 6 carbon atoms and the degree of oligomerization x is between 1 and 10, preferably between 1 and 2 and is particularly clear is less than 1.4, for example in amounts of 1 to 10% by weight.
  • R is a primary straight-chain or aliphatic radical with 8 to 22, preferably 12 to 18, C-atoms, methyl-branched
  • G is a symbol which stands for a glycose unit with 5 or 6 carbon atoms and the degree of oligomerization x is between 1 and 10, preferably between 1 and 2 and is particularly clear is less than 1.4, for example in amounts of 1 to 10% by weight.
  • Further builder constituents are crystalline, layered sodium silicates of the general formula Na Si 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 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-164514.
  • Preferred crystalline layered silicates are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and fr-sodium disilicate Na2Si2 ⁇ 5 * yH2 ⁇ are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171.
  • the crystalline layered silicates are preferably introduced into the process in amounts of 1 to 10% by weight and in particular in amounts of 2 to 8% by weight.
  • bu lder components which can be used in particular as plasticizers and / or lubricants are (co) polymeric polycarboxylates, such as polyacrylates, polyethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those from 50 % to 10% maleic acid.
  • the relative molecular weight of the homopolymers is generally between 1,000 and 100,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, based on free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000. Suitable, albeit less preferred, compounds of this class are copolymers de.
  • Acrylic acid or methacrylic acid with vinyl ethers such as vinyl methyl ethers, in which the proportion of acid is at least 50%.
  • biodegradable terpolymers are preferred.
  • polyacetal carboxylic acids as described for example in the patents US-A-4,144,226 and US-A-4,146,495, and polymeric acids which are obtained by polymerizing acrolein and subsequent disproportionation by means of alkalis and from acrylic acid units and vinyl alcohol units or acrolein units are built up.
  • the (co) polymeric polycarboxylates are in solid form or in liquid form Form, ie in the form of an aqueous solution, preferably in the form of a 30 to 55 wt .-% aqueous solution, introduced into the process.
  • the content of the agents in (co) polymeric polycarboxylates is preferably up to 10% by weight and in particular 2 to 8% by weight.
  • 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 and mixtures of these and nitrilotriacetate (NTA), provided that such use is not objectionable for ecological reasons is.
  • 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 and mixtures of these and nitrilotriacetate (NTA), provided that such use is not objectionable for ecological reasons is.
  • Suitable ingredients of the agents are water-soluble inorganic alkalizing agents such as bicarbonates or carbonates, in particular alkali carbonate, especially sodium carbonate, and amorphous silicates are used.
  • the alkalizing agents are preferably introduced into the process in solid form. However, it is also possible to use the alkalizing agents at least partially in the form of an aqueous solution, e.g. in the form of a mixture of solid alkali carbonate and an alkali silicate solution.
  • the sodium carbonate content of the agents is preferably up to 20% by weight, advantageously between 5 and 15% by weight.
  • Preferred alkali silicates have a molar M2 ⁇ : Si ⁇ 2 ratio of 1: 1.9 to 1: 4.5 and in particular of 1: 2 to 1: 3.3, where M is sodium or potassium, and are in amounts of 0 , 5 to 15% by weight, preferably in amounts of 1 to 12% by weight and in particular in amounts of 1 to 10% by weight, in each case based on the finished granules.
  • the other detergent components include graying inhibitors (dirt carriers), foam inhibitors, bleaching agents and bleach activators, optical brighteners, enzymes, fabric softening agents, colorants and fragrances as well as neutral salts.
  • bleaching agents which can be used are, for example, peroxycarbonate, peroxypyophosphates, citrate perhydrates and peracid salts or peracids which provide H2O2, such as perbenzoates, peroxo- phthalates, 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 onohydrate advantageously being used.
  • 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, such as N, N, N ', N'-tetraacetylethylene diamine, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate.
  • the bleach activator content of 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.
  • 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, such as, 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.
  • Carboxymethyl cellulose sodium salt
  • methyl cellulose methyl cellulose
  • hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose and mixtures thereof
  • polyvinylpyrrolidone in particular in amounts of 0.5 to 5% by weight, based on the composition, are preferably used.
  • the foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants; a reduction can also be achieved by adding non-surfactant-like organic substances.
  • a reduced foaming power, which is desirable when working in machines, is often achieved by combining different types of surfactants, for Example of sulfates and / or sulfonates with nonionic surfactants and / or with soaps.
  • soaps the foam-suppressing effect increases with the degree of saturation and the C number of the fatty acid ester. Soaps of natural and synthetic origin are suitable as foam-inhibiting soaps which have a high proportion of C 1 -C 24 -fatty acids.
  • Suitable non-surfactant-like foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally silanized silica, paraffin, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also advantageously used, for example those composed of silicones and paraffins or waxes.
  • the foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance or are admixed with the plasticizer and / or lubricant.
  • the detergents can contain, as optical brighteners, 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-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure which carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group instead of the morpholino group.
  • Brighteners of the substituted 4,4'-distyryl-di-phenyl type may also be present; for example the compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.
  • uniformly white granules are obtained if, apart from the customary optical brighteners, the agents are present in customary amounts, for example between 0.1 and 0.5, preferably around 0.1 to 0.3, by weight. %, even small amounts, for example 10 ⁇ 6 to 10 "3 wt .-%, preferably around 10" 5 wt .-%, of a blue dye.
  • a particularly preferred dye is Tinolux ( R ) (product name of Ciba-Geigy).
  • Enzymes from the class of proteases, lipases, cellulases and amylases or mixtures thereof are possible. Particularly well suited net are enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Strepto yces griseus. Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentus are preferably used.
  • the enzymes can be adsorbed on carriers and / or embedded in shell substances in order to protect them against premature decomposition.
  • the salts of polyphosphonic acids are suitable as stabilizers, in particular for per-compounds and enzymes.
  • the agents can also contain constituents which improve the solubility of the compacted granules. Such constituents and the introduction of these constituents into the premix to be extruded are described, for example, in the international patent application WO-A-93/02176 and the older German patent application P 4203031.5.
  • the preferred ingredients used to improve the solubility of the granules include, in particular, fatty alcohols with 20 to 80 moles of ethylene oxide per mole of fatty alcohol, for example tallow fatty alcohol with 30 E0 and tallow fatty alcohol with 40 E0, and polyethylene glycols with a relative molecular weight. cooling mass between 200 and 2000.
  • the detergents and cleaning agents can be produced uniformly from extrudates which have the above-mentioned ingredients.
  • the agents can also be obtained from a mixture of several different granules, of which the extrudates according to the invention form the main component.
  • the bleach activator, the enzymes, and colorants and fragrances can be subsequently added to the extrudates. It is preferred to use the bleach activator and the enzymes in each case in compacted granular form, for example as extrudates produced separately in each case, which are obtained by means of a kneader of the configuration described above or via a pellet press. Examples
  • a homogeneous solid and free-flowing premix containing anionic surfactants (Cg-Ci3-alkylbenzenesulfonate and Ci6-Ci8-F etta alcohol sulfate with a weight ratio of 2: 1), with 5 EO, zeolite, perborate monohydrate, sodium carbonate, Sokalan ( R ) CP5 (copoly eres of acrylic acid and maleic acid, commercial product from BASF), amorphous sodium silicate (Na2 ⁇ : SiÜ2 1: 3.0) and polyethylene glycol with a relative molecular weight of 400 was extruded in a Werner & Pfleiderer twin-screw extruder (type C120, with co-rotating screws) at throughputs of 600 kg / h, 700 kg, h and 800 kg / h and a pressure of 170 bar.
  • anionic surfactants Cg-Ci3-alkylbenzenesulfonate and Ci6-C
  • the same premix was then extruded in a twin-screw extruder from Lihotzky (type 2000, with counter-rotating screws) at a throughput of 2000 kg / h and a pressure of 32 bar.
  • the temperature of the mixture to be extruded was 60 to 62 ° C. in each case before the hole emerged. The corresponding values of the specific work can be found in the table.
  • the extrudates were then dried in a fluidized bed.
  • Extrudates were obtained with a content of 23% by weight of anionic surfactants, 2.7% by weight of nonionic surfactant, 19% by weight of zeolite (calculated as an anhydrous active substance), 18% by weight of perborate monohydrate, 5% by weight sodium carbonate, 6.0% by weight Sokalan ( R ) cP5, 2.2% by weight amorphous sodium silicate, 2.2% by weight polyethylene glycol and 11.0% by weight Water.
  • the rest consisted of salts derived from the raw materials.
  • the differences in the values of the specific work for throughputs between 600 and 800 kg / h in the same extruder system were less than 1.5%, based on the initial value at 600 kg / h.
  • the relatively large difference to the value of the specific work at a throughput of 2000 kg / h arises from the transition to another extrusion system.
  • the bulk weights of the products were between 840 and 880 g / 1.

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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)
  • Detergent Compositions (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention vise à produire des extrudats à haute densité, sous pression. Un prémélange solide homogène est comprimé à ces pressions pour former une barre qui, à sa sortie du trou de la filière, est découpée au moyen d'un dispositif coupant à une dimension prédéfinie de granulat, sans à avoir pour autant à augmenter sensiblement la pression et par conséquent le travail spécifique lorsque le débit augmente. C'est possible du fait qu'on introduit dans le prémélange à extruder un système autorégulateur constitué de composants de formulation aux effets de viscosité de structure dans les conditions opératoires, et de composants aux effets dilatants. Comme du point de vue macroscopique la pression ne change pas de manière suffisante pour induire une modification sensible du travail spécifique, l'extrusion peut également s'effectuer dans un système donné, lorsque le débit augmente, approximativement à la même température ou dans la même plage de températures qu'avant l'augmentation du débit (constance approchée de températures). Ce procédé permet d'extruder des composants sensibles aux températures, par exemple des décolorants péroxy, en dépit de l'augmentation du débit.
PCT/EP1993/002836 1992-10-22 1993-10-14 Procede de preparation d'extrudats a action lavante et nettoyante WO1994009111A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
DE59305176T DE59305176D1 (de) 1992-10-22 1993-10-14 Verfahren zur herstellung wasch- oder reinigungsaktiver extrudate
KR1019950701549A KR950704471A (ko) 1992-10-22 1993-10-14 세제 또는 세정제로서 사용되는 압출물의 제조방법[process for producing extrudates used as detergents or cleaning agents]
JP6509634A JPH08502312A (ja) 1992-10-22 1993-10-14 洗浄または清浄活性な押出物の製造方法
EP93923465A EP0665879B1 (fr) 1992-10-22 1993-10-14 Procede de preparation d'extrudats a action lavante et nettoyante

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4235646.6 1992-10-22
DE4235646A DE4235646A1 (de) 1992-10-22 1992-10-22 Verfahren zur Herstellung wasch- und reinigungsaktiver Extrudate

Publications (1)

Publication Number Publication Date
WO1994009111A1 true WO1994009111A1 (fr) 1994-04-28

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PCT/EP1993/002836 WO1994009111A1 (fr) 1992-10-22 1993-10-14 Procede de preparation d'extrudats a action lavante et nettoyante

Country Status (8)

Country Link
EP (1) EP0665879B1 (fr)
JP (1) JPH08502312A (fr)
KR (1) KR950704471A (fr)
AT (1) ATE147777T1 (fr)
CA (1) CA2147744A1 (fr)
DE (2) DE4235646A1 (fr)
ES (1) ES2096336T3 (fr)
WO (1) WO1994009111A1 (fr)

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996020269A1 (fr) * 1994-12-23 1996-07-04 Henkel Kommanditgesellschaft Auf Aktien Silicate alcalin amorphe contenant des substances impregnees
WO1996038530A1 (fr) * 1995-05-30 1996-12-05 Henkel Kommanditgesellschaft Auf Aktien Produit de lavage ou detergent en granules a densite en vrac elevee
US5668100A (en) * 1993-09-23 1997-09-16 Henkel Kommanditgesellschaft Auf Aktien Detergent mixtures and detergents or cleaning formulations with improved dissolving properties
US5683377A (en) * 1995-06-30 1997-11-04 Uni-Charm Corporation Individually wrapped sanitary napkin
WO1999021955A1 (fr) * 1997-10-23 1999-05-06 Henkel Kommanditgesellschaft Auf Aktien Procede servant a preparer un produit lavant ou detergent au parfum renforce
US6034050A (en) * 1995-07-12 2000-03-07 Henkel Kommanditgesellschaft Auf Aktien Amorphous alkali metal silicate compound
US6191096B1 (en) 1995-01-18 2001-02-20 Henkel Kommanditgesellschaft Auf Aktien Spray-dried amorphous alkali metal silicate compound and its use in detergent compositions
US6479452B2 (en) 2000-06-29 2002-11-12 Cognis Deutschland Gmbh & Co. Kg Surfactant granules with an improved dissolving rate comprising alky and alkenyl sulfates
US6616705B2 (en) 2000-09-08 2003-09-09 Cognis Deutschland Gmbh & Co. Kg Laundry detergent compositions
US6620209B2 (en) 2000-09-08 2003-09-16 Cognis Deutschland Gmbh & Co. Kg Laundry detergent compositions
US6797687B2 (en) 2001-08-07 2004-09-28 Cognis Deutschland Gmbh & Co. Kg Gemini surfactant compositions
US6881359B2 (en) 2000-01-26 2005-04-19 Cognis Deutschland Gmbh & Co. Kg Processes for the preparation of low dust, limited particle size distribution, surfactant granules
US6897193B2 (en) 2001-12-22 2005-05-24 Cognis Deutschland Gmbh & Co., Kg Hydroxy mixed ethers and polymers in the form of solid preparations as a starting compound for laundry detergents, dishwashing detergents and cleaning compositions
US6977239B1 (en) 1999-11-25 2005-12-20 Cognis Deutschland Gmbh & Co. Kg Detergent tablets
US7049279B1 (en) 1999-11-25 2006-05-23 Cognis Deutschland Gmbh & Co. Kg Process for preparing detergent granules with an improved dissolution rate
US7087570B2 (en) 1999-12-24 2006-08-08 Cognis Deutschland Gmbh & Co. Kg Detergent tablets
US7098178B2 (en) 2000-03-16 2006-08-29 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Silicic acid ester mixtures
US7186678B2 (en) 1999-12-24 2007-03-06 Cognis Deutschland Gmbh & Co. Kg Tenside granules with improved disintegration rate
US7199096B1 (en) 1999-11-09 2007-04-03 Cognis Deutschland Gmbh & Co. Kg Detergent tablets
DE102015002877A1 (de) 2015-03-09 2016-09-15 Henkel Ag & Co. Kgaa Granulares Wasch- oder Reinigungsmittel mit verbesserter Lösegeschwindigkeit

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4434500A1 (de) * 1994-09-27 1996-03-28 Henkel Kgaa Verbessertes Extrusionsverfahren zur Herstellung von Waschmitteln
DE4435742A1 (de) * 1994-10-06 1996-04-11 Henkel Kgaa Verfahren zur Herstellung wasch- oder reinigungsaktiver Extrudate
DE4442977A1 (de) * 1994-12-02 1996-06-05 Henkel Kgaa Wasch- oder Reinigungsmittel mit wasserlöslichen Buildersubstanzen
DE10009819A1 (de) 2000-03-01 2001-09-06 Trw Airbag Sys Gmbh & Co Kg Verfahren zur Herstellung von Treibstoff-Formlingen
DE102015206547A1 (de) 2015-04-13 2016-10-13 Henkel Ag & Co. Kgaa Flüssiges Wasch- oder Reinigungsmittel mit suspendierten Partikeln

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3824189A (en) * 1972-05-11 1974-07-16 G Borello Detergent compositions and methods for making same
EP0328880A1 (fr) * 1988-01-19 1989-08-23 Colgate-Palmolive Company Produit d'extrusion d'une composition détergente organique synthétique renforcée en forme particulaire et en forme de "petit pâté", et procédés de préparation et d'utilisation de ce dernier
WO1991002047A1 (fr) * 1989-08-09 1991-02-21 Henkel Kommanditgesellschaft Auf Aktien Fabrication de granules comprimes pour produits de lavage

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3824189A (en) * 1972-05-11 1974-07-16 G Borello Detergent compositions and methods for making same
EP0328880A1 (fr) * 1988-01-19 1989-08-23 Colgate-Palmolive Company Produit d'extrusion d'une composition détergente organique synthétique renforcée en forme particulaire et en forme de "petit pâté", et procédés de préparation et d'utilisation de ce dernier
WO1991002047A1 (fr) * 1989-08-09 1991-02-21 Henkel Kommanditgesellschaft Auf Aktien Fabrication de granules comprimes pour produits de lavage

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5668100A (en) * 1993-09-23 1997-09-16 Henkel Kommanditgesellschaft Auf Aktien Detergent mixtures and detergents or cleaning formulations with improved dissolving properties
WO1996020269A1 (fr) * 1994-12-23 1996-07-04 Henkel Kommanditgesellschaft Auf Aktien Silicate alcalin amorphe contenant des substances impregnees
US6191096B1 (en) 1995-01-18 2001-02-20 Henkel Kommanditgesellschaft Auf Aktien Spray-dried amorphous alkali metal silicate compound and its use in detergent compositions
US6458755B2 (en) 1995-01-18 2002-10-01 Henkel Kommanditgesellschaft Auf Aktien Amorphous alkali metal silicate compound
WO1996038530A1 (fr) * 1995-05-30 1996-12-05 Henkel Kommanditgesellschaft Auf Aktien Produit de lavage ou detergent en granules a densite en vrac elevee
US5683377A (en) * 1995-06-30 1997-11-04 Uni-Charm Corporation Individually wrapped sanitary napkin
US6034050A (en) * 1995-07-12 2000-03-07 Henkel Kommanditgesellschaft Auf Aktien Amorphous alkali metal silicate compound
WO1999021955A1 (fr) * 1997-10-23 1999-05-06 Henkel Kommanditgesellschaft Auf Aktien Procede servant a preparer un produit lavant ou detergent au parfum renforce
US6228833B1 (en) * 1997-10-23 2001-05-08 Henkel Kommanditgesellschaft Auf Aktien Method for producing scent intensifying washing and cleaning detergents
US7199096B1 (en) 1999-11-09 2007-04-03 Cognis Deutschland Gmbh & Co. Kg Detergent tablets
US6977239B1 (en) 1999-11-25 2005-12-20 Cognis Deutschland Gmbh & Co. Kg Detergent tablets
US7049279B1 (en) 1999-11-25 2006-05-23 Cognis Deutschland Gmbh & Co. Kg Process for preparing detergent granules with an improved dissolution rate
US7087570B2 (en) 1999-12-24 2006-08-08 Cognis Deutschland Gmbh & Co. Kg Detergent tablets
US7186678B2 (en) 1999-12-24 2007-03-06 Cognis Deutschland Gmbh & Co. Kg Tenside granules with improved disintegration rate
US6881359B2 (en) 2000-01-26 2005-04-19 Cognis Deutschland Gmbh & Co. Kg Processes for the preparation of low dust, limited particle size distribution, surfactant granules
US7098178B2 (en) 2000-03-16 2006-08-29 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Silicic acid ester mixtures
US6479452B2 (en) 2000-06-29 2002-11-12 Cognis Deutschland Gmbh & Co. Kg Surfactant granules with an improved dissolving rate comprising alky and alkenyl sulfates
US6620209B2 (en) 2000-09-08 2003-09-16 Cognis Deutschland Gmbh & Co. Kg Laundry detergent compositions
US6616705B2 (en) 2000-09-08 2003-09-09 Cognis Deutschland Gmbh & Co. Kg Laundry detergent compositions
US6797687B2 (en) 2001-08-07 2004-09-28 Cognis Deutschland Gmbh & Co. Kg Gemini surfactant compositions
US6897193B2 (en) 2001-12-22 2005-05-24 Cognis Deutschland Gmbh & Co., Kg Hydroxy mixed ethers and polymers in the form of solid preparations as a starting compound for laundry detergents, dishwashing detergents and cleaning compositions
DE102015002877A1 (de) 2015-03-09 2016-09-15 Henkel Ag & Co. Kgaa Granulares Wasch- oder Reinigungsmittel mit verbesserter Lösegeschwindigkeit
DE102015002877B4 (de) 2015-03-09 2024-09-12 Henkel Ag & Co. Kgaa Wasch- oder reinigungsaktive Extrudate, deren Herstellung und Verwendung in granularen Wasch- oder Reinigungsmitteln

Also Published As

Publication number Publication date
DE4235646A1 (de) 1994-04-28
JPH08502312A (ja) 1996-03-12
ATE147777T1 (de) 1997-02-15
EP0665879B1 (fr) 1997-01-15
DE59305176D1 (de) 1997-02-27
CA2147744A1 (fr) 1994-04-28
KR950704471A (ko) 1995-11-20
ES2096336T3 (es) 1997-03-01
EP0665879A1 (fr) 1995-08-09

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