EP0711338A1 - Procede de fabrication d'un produit extrude a activite detergente ou nettoyante - Google Patents

Procede de fabrication d'un produit extrude a activite detergente ou nettoyante

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Publication number
EP0711338A1
EP0711338A1 EP94924270A EP94924270A EP0711338A1 EP 0711338 A1 EP0711338 A1 EP 0711338A1 EP 94924270 A EP94924270 A EP 94924270A EP 94924270 A EP94924270 A EP 94924270A EP 0711338 A1 EP0711338 A1 EP 0711338A1
Authority
EP
European Patent Office
Prior art keywords
weight
premix
anionic surfactants
acid
alk
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.)
Withdrawn
Application number
EP94924270A
Other languages
German (de)
English (en)
Inventor
Hubert Pawelczyk
Jochen Jacobs
Bernd Larson
Norbert Kühne
Kathrin Schnepp
Wolfgang Seiter
Monika Böcker
Eduard Smulders
Günther VOGT
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 EP0711338A1 publication Critical patent/EP0711338A1/fr
Withdrawn legal-status Critical Current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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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 process for the production of solid detergents or cleaning agents or components of solid detergents or cleaning agents, a premix being used which contains anionic surfactants in a solid preparation form and preferably highly concentrated anionic sides. At the same time, the winding and / or dissolving behavior of the extrudates is improved.
  • Solid detergent or cleaning agent with a high bulk density i.e. Agents with a bulk density above 500 g / l have, owing to their compact shape and the resulting smaller surface area, a lower dissolving rate, especially at low temperatures around 15 to 60 ° C., than agents with a comparable composition, but which have a bulk density of, for example, only 300 g / 1. Analogous problems occur when washing in detergents with a high bulk density in washing machines.
  • a process for the production of extrudates with high density wherein a solid premix is extruded under pressure and the strand is cut to the predeterminable granulate size after exiting the hole shape by means of a cutting device.
  • the homogeneous and solid premix contains a plasticizer and / or lubricant, which causes the premix to become 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.
  • nonionic surfactants and aqueous anionic surfactant pastes which are liquid at the processing temperature are preferred. After exiting the hole shape, the system is no longer subjected to shear forces and the viscosity changes in such a way that the extruded strand can be cut to predetermined extrudate dimensions.
  • the invention accordingly relates to a process for the production of high density, washable or cleaning-active extrudates, a solid premix being extruded under pressure and the strand being cut out of the hole shape by means of a cutting device to the predetermined granule dimension, the premixed anionic and nonionic surfactants contains and the anionic surfactants are introduced into the premix only via a solid, powdery or granular preparation form.
  • the anionic surfactants are introduced at least in part via a formulation with an anionic surfactant content of at least 50% by weight, based on the formulation.
  • 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 extrusion temperature.
  • the premix is pressed under pressure, which is preferably at least 25 bar, at Extremely high throughputs, depending on the apparatus used, but can also be lower, compressed, plasticized, extruded in the form of fine strands through the perforated nozzle plate in the extruder head and finally the extrudate preferably reduced to approximately spherical to cylindrical granules by means of a rotating knives.
  • the hole diameter of the perforated nozzle plate and the length of the strand cut are matched to the selected granule dimension.
  • granules of an essentially 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 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 anionic surfactants used are only introduced into the premix via a solid preparation.
  • These solid preparation forms can be in powder form, but can also be made of neten and / or granulated compounds with more or less high proportions of anionic surfactants.
  • the anionic surfactants are preferably at least 30% by weight and in particular at least 50% by weight, in each case based on the total amount of anionic surfactant, as a solid, powdery or granular formulation an anionic surfactant content of at least 50% by weight, preferably from 60 to 100% by weight and in particular from 70 to 95% by weight, in each case based on the solid preparation, introduced into the process.
  • anionic surfactants are contained in a solid preparation form or are distributed over several solid preparation forms.
  • a spray-dried granulate which contains one or more anionic surfactants in amounts of, for example, up to 45% by weight, and a granulate obtained by granulation or a powder with preferably at least 75% by weight of anionic surfactant in the Premix can be used.
  • only preparation forms are used which each contain at least 75% by weight and preferably at least 80% by weight of one or more anionic surfactants.
  • the content of the anionic surfactants in the premix is preferably 5 to 30% by weight, but can also go well beyond this. Lower proportions of anionic surfactants are less preferred for technical reasons.
  • 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, i.e. Mixtures of alkene and hydroxyalkane sulfonates and disulfonates, such as those obtained, for example, from Ci2-Ci8 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates which are obtained from Ci2-Ci8-alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfofatty acids esters of ⁇ -sulfofatty acids (ester sulfonates), for example the -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, or the disalts of the corresponding ⁇ -sulfofatty acids.
  • Other suitable anionic surfactants are sul- gated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures as obtained in the production by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become.
  • the sulfonation products are a complex mixture which contains mono-, di- and triglyceride sulfonates with oc and / or sulfonic acid groups in the interior.
  • sulfonated fatty acid salts, glyceride sulfates, glycerine sulfates, glycerin and soaps are formed. If one starts from the sulfonation of saturated fatty acids or hardened fatty acid glycerol esters, the proportion of the ⁇ -sulfonated fatty acid disalts can, depending on the procedure, be up to about 60% by weight.
  • 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 ⁇ -oxo alcohols, and those secondary alcohols this chain length preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • Ci6-Ci8-alk (en) yl sulfates are particularly preferred from the point of view of washing technology. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use Ci6-Ci8-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 with relatively low detergents temperatures of, for example, room temperature to 40 ° C.
  • the compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of (2-Ci4-fatty alkyl sulfates or Ci2-Ci8-fatty alkyl sulfates with Ci6-Ci8-fatty alkyl sulfates and in particular Ci2-Ci6-
  • alk (en) yl sulfates are used in the premix for reasons of washing technology used, the proportion of short-chain alkyl sulfates such as C ⁇ 2-alkyl sulfate or even shorter-chain alkyl sulfates, based on the sum of the total alk (en) yl sulfates used, not more than 30% by weight.
  • 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 consisting of (45 existing sulfated fatty alcohols and unsaturated, predominantly consisting of Ci8 sulfated fatty alcohols are preferred, for example those derived from solid or liquid fatty alcohol mixtures of the HD-Ocenol ( R ) type (commercial product of the applicant) 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 mol of ethylene oxide such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 mol 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 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 in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain CQ to Ci ⁇ fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols which, viewed in isolation, are nonionic surfactants (for a 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.
  • preferred anionic surfactants are alkylbenzenesulfonates and / or alk (en) - ylsulfates, especially fatty alkyl sulfates. In a further preferred embodiment of the invention, 8 to 25% by weight of alkylbenzenesulfonates and / or alk (en) ylsulfates are used in the premix.
  • alkylbenzenesulfonates are used as the sole anionic surfactants in the form of a highly concentrated powder, for example as a powder with an active substance content of above 85% by weight, for example around 90% by weight.
  • alkylbenzenesulfonate and alk (en) ylsulfonate, in particular fatty alkyl sulfate in a weight ratio of 0.5: 1 to 1.5: 1, preferably up to 1.2: 1 and used in particular by 1: 1 in the premix.
  • premixes free from alkylbenzenesulfonate are also preferred.
  • alk (en) yl sulfates are introduced into the premix as the sole anionic surfactant or as one anionic surfactant, there are solid preparation forms with alk (en) yl sulfate contents of at least 75% by weight and in total particularly preferred of at least 80% by weight, which can be produced, for example, by means of a process according to international patent application WO-A-93/04162 or the older German patent application DE 4232874 by granulation with, if appropriate, simultaneous drying, in particular in a fluidized bed .
  • 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 triethanola in.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • ingredients of the premix include soaps, preferably in amounts of 0.5 to 4% by weight.
  • Saturated fatty acid soaps are particularly suitable, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • soap mixtures are preferred which are 50 to 100% by weight saturated C12-C24- Fatty acid soaps and 0 to 50 wt .-% are composed of oleic acid soap.
  • 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 30 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, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are 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 fraction for a special 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 30 or 40 E0, or polyethylene glycols, preferably with a relative molecular weight between 200 and 600, can be used in a mixture with other nonionic surfactants.
  • alkoxylated alcohols with a maximum of 40 E0 in the form of a solid preparation into the premix is preferred and particularly preferred if the premix is granular preparation forms with high contents contains alk (en) yl sulfates.
  • alkyl glycosides of the general formula R0 (G) x can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18, C. -Atoms means and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; 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 that can be used, 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),
  • R2C0 for an aliphatic acyl residue with 6 to 22 carbon atoms
  • R-3 for hydrogen, an alkyl or hydroxyalkyl residue with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydro xyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • Non-ionic surfactants are preferably used in the premix in amounts of 0.5 to 25% by weight. Amounts of 2 to 20% by weight and preferably 5 to 15% by weight of nonionic surfactants are advantageous, with 50 to 100% by weight, based on the nonionic surfactants, of ethoxylated alcohols.
  • premixes which contain 15 to 25% by weight alkylbenzenesulfonates as sole anionic surfactants, preferably in the form of an 85 to 95% by weight powder, and 0.5 to 5 %
  • nonionic surfactants preferably ethoxylated fatty alcohols and / or alkyl glycosides, in particular ethoxylated fatty alcohols or mixtures of ethoxylated fatty alcohols and alkyl glycosides.
  • premixes which contain 10 to 20% by weight of anionic surfactants, preferably alkylbenzenesulfonates and alk (en) yl sulfates in a weight ratio of 0.8: 1 to 1.2: 1, and Contain 0.5 to 5 wt .-% nonionic surfactants as above.
  • anionic surfactants preferably alkylbenzenesulfonates and alk (en) yl sulfates in a weight ratio of 0.8: 1 to 1.2: 1, and Contain 0.5 to 5 wt .-% nonionic surfactants as above.
  • premixes which contain 5 to 15% by weight of anionic surfactants, preferably mixtures of alkylbenzenesulfonates and alk (en) ylsulfates in a weight ratio of 0.5: 1.2, in particular of 0.5: 1 to a maximum of 1: 1, and 10 to 20% by weight nonionic surfactants, preferably ethoxylated fatty alcohols or mixtures of ethoxylated fatty alcohols and other nonionic surfactants, the content of ethoxylated fatty alcohols based on the total amount of nonionic surfactants, is at least 50% by weight, in particular is at least 60% by weight, or premixes are used which, as the sole anionic surfactant, are 5 to 15% by weight, preferably contain at least 8% by weight alk (en) yl sulfates and 5 to 15% by weight, preferably at least 8% by weight nonionic surfactants as stated above.
  • anionic surfactants preferably mixtures of alkylbenzen
  • the alk (en) yl sulfates are preferably always used in the form of highly concentrated granules with contents between 80 and 95% by weight alk (en) yl sulfate, while the alkylbenzenesulfonates in cases in which they are not the sole anionic surfactant can also be used in the form of, for example, spray-dried granules with contents below 45% by weight of alkylbenzenesulfonate, based on these spray-dried granules.
  • ingredients of the premix are, for example, inorganic and organic builder substances, alkali carbonates and alkali silicates, optical brighteners, bleaching agents, optical brighteners, graying inhibitors and, if appropriate, foam inhibitors, bleach activators, enzymes, textile-softening substances, colorants and fragrances and neutral salts such as sulfate salts Chlorides in the form of their sodium or potassium salts.
  • Suitable inorganic buder substances are, for example, zeolites, phosphates and layered silicates.
  • the fine 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 or as an undried stabilized suspension which is still moist from its production.
  • the zeolite can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups 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.
  • Suitable substitutes or partial substitutes for the zeolite are layer silicates of natural and synthetic origin.
  • layer sil kate are known for example from the patent applications DE-B-23 34899, EP-A-0 026 529 and DE-A-35 26 405.
  • Their usability is not limited to a special composition or structural formula.
  • smectites, in particular bentonites, are preferred here.
  • the layered silicates can contain hydrogen, alkali, alkaline earth ions, in particular Na + and Ca ++ .
  • the amount of water of hydration is usually in the range of 8 to 20% by weight and depends on the swelling condition or the type of processing.
  • Layered silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.
  • 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 2, 3 or 4 are.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0164514.
  • Preferred crystalline layered silicates are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ft-sodium disilicate Na2Si2 ⁇ 5 * H2 ⁇ are preferred.
  • the content of these inorganic builder substances in the premixes is preferably between 15 to 60% by weight, phosphate contents preferably being less than 15% by weight and particularly preferred premixes being free of phosphate-containing builder substances.
  • 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, nitric 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 Ci tronic acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • 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.
  • Biodegradable terpolymers are also particularly preferred, for example those which, as monomers, contain salts of acrylic acid and maleic acid and vinyl alcohol or Contain vinyl alcohol derivatives or the salts of acrylic acid and 2-alkylallylsulfonic acid as monomers and sugar derivatives.
  • the (co) polymeric or terpolymeric polycarboxylates can be used either as a powder, as a spray-dried or granulated compound or as an aqueous solution, with 20 to 55% by weight aqueous solutions being preferred.
  • the content of the premixes of (co) polymeric or terpoly eren polycarboxylates is preferably up to a maximum of 8 wt .-% and in particular between 0 and 5 wt .-%.
  • 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 ingredients of the premixes are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures thereof; in particular, alkali carbonate and amorphous alkali silicate, especially sodium silicate with a molar ratio Na2 ⁇ : Si ⁇ 2 from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5.
  • the content of sodium carbonate in the premixes is preferably up to 20% by weight, advantageously between 2 and 15% by weight.
  • the sodium silicate content of the premixes is generally up to 10% by weight and preferably between 2 and 8% by weight.
  • alkali metal carbonates can also be replaced by sulfur-free amino acids and / or salts thereof having 2 to 11 carbon atoms and optionally a further carboxyl and / or amino group.
  • the alkali metal carbonates be partially or completely replaced by glycine or glycinate.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and peracid salts or peracids providing H2O2, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
  • the bleaching agent content of the premixes 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 pentaacetate.
  • the content of bleach activators in the pre-primers or in the finished agents of bleach activators is in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.
  • Particularly preferred bleach activators are NNN'.N'-tetraacetyl-ethylenediamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.
  • the agents can also contain components which have a positive influence on the oil and fat washability from textiles. This effect is particularly evident when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component.
  • the preferred oil- and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl 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 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 cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, are preferably used.
  • 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, eg those made of silicone, 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. Enzymes 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 amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest.
  • (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 stabilizers particularly for per-compounds and enzymes are the salts of polyphosphonic acids, preferably the neutral-reacting sodium salts of, for example, l-hydroxyethane-II-diphosphonate and diethylenetriaminepentamethylenephosphonate in amounts of 0.1 to 1.5% by weight and in particular of l-hydroxyethane-l, l-diphosphonic acid.
  • Sodium formate for example, can also be used as stabilizers. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • boron compounds for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H3BO3), metaboric acid (HBO2) and pyroboric acid (tetraboric acid H2B4O7), is particularly advantageous for stabilizing enzymes ).
  • Derivatives of diaminosilbenesulfonic acid or their alkali metal salts can be used as optical brighteners.
  • 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 instead of the morpholino- Group carry a diethanolamino group, a methylamino group, 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) diphenyls. Mixtures of the aforementioned brighteners can also be used.
  • Uniform white extrudates are obtained when, in addition to the usual brighteners, in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, even small amounts, for example 10 ⁇ 6 to 10 "3 wt .-%, preferably by 10" 5 wt .-%, a blue dye can be used.
  • 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 other finely divided dry powders before the enzymes and the other components 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 foaming behavior for detergents can be positively influenced if the foam inhibitor, for example organopolysiloxanes and their mixtures with microfine, given if necessary, silanized silica and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide, at least partially not extruded, but mixed subsequently 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 enable a further improvement in the flushing-in 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.
  • premixes M1 to M5 according to the invention and corresponding premixes VI to V2 were extruded according to the teaching of international application W0-A-91/02047.
  • the finished extrudates were dried, but not worked up further.
  • the compositions of the finished extrudates can be found in Tables 1 and 3, their bulk weights and their dissolving behavior can be found in Tables 2 and 4.
  • alk (en) yl sulfate cuts with up to a maximum of 30% by weight of C8-Ci2-alkyl sulfates, the redispersion behavior could be further improved.
  • tallow fatty alcohol sulfate to replace PEG 400 with tallow fatty alcohol with 40 E0.
  • ABS Cg-Ci3-alkylbenzenesulfonate sodium salt calculated as 100% active substance, used as 90% by weight powder (Maranil
  • TAS91 tallow fatty alcohol sulfate calculated as 100% active substance, used as 91% by weight granules, which contained sodium carbonate and less than 1% by weight of non-chemically bound water as a carrier, produced according to the teaching of the international patent application message WO-A-93/04162
  • TAS84 tallow fatty alcohol sulfate, calculated as 100% active substance, used as 84% by weight granules, which contained sodium carbonate and less than 1% by weight of non-chemically bound water as a carrier, produced according to the teaching of the international patent application message W0-A-93/04162
  • TAS47 tallow fatty alcohol sulfate calculated as 100% active substance, used as 47% by weight granules which contained sodium carbonate and less than 1% by weight of non-chemically bound water as a carrier, produced according to the teaching of the international patent application message WO-A-93/04162
  • SIK foam inhibitor granules based on soda and sulfate with 15% by weight
  • Maleic acid PEG 400 polyethylene glycol with a molecular weight of 400 HEDP 1-hydroxyethane-l, 1-diphosphonic acid tetrasodium salt
  • Table 1 Compositions from Ml to M3 and VI (in% by weight)

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

Abstract

Le comportement à la solubilisation de produits détergents ou nettoyants extrudés dépend, dans une large mesure, de la forme sous laquelle les agents tensioactifs anioniques sont introduits dans le prémélange à extruder. Le comportement à la solubilisation du produit extrudé est amélioré par l'introduction des agents tensioactifs dans le prémélange, uniquement sous une forme de préparation solide pulvérulente ou granulaire, lesdites formes de préparation présentant au moins partiellement une teneur en agents tensioactifs anioniques d'au moins 50 % en poids.
EP94924270A 1993-07-29 1994-07-21 Procede de fabrication d'un produit extrude a activite detergente ou nettoyante Withdrawn EP0711338A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4325500 1993-07-29
DE19934325500 DE4325500A1 (de) 1993-07-29 1993-07-29 Verfahren zur Herstellung wasch- oder reinigungsaktiver Extrudate
PCT/EP1994/002403 WO1995004129A1 (fr) 1993-07-29 1994-07-21 Procede de fabrication d'un produit extrude a activite detergente ou nettoyante

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EP0711338A1 true EP0711338A1 (fr) 1996-05-15

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CN (1) CN1127525A (fr)
DE (1) DE4325500A1 (fr)
HU (1) HUT73038A (fr)
WO (1) WO1995004129A1 (fr)

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DE19524722A1 (de) * 1995-07-12 1997-01-16 Henkel Kgaa Granulares Wasch- oder Reinigungsmittel mit hoher Schüttdichte
CN101240227B (zh) * 2007-02-09 2012-02-22 宝洁公司 较慢溶解的、改进型、符合人机工程学的衣物洗涤剂条棒
CN101670251B (zh) * 2009-06-09 2012-01-04 中轻化工股份有限公司 一种圆球形阴离子表面活性剂的制造方法

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US3824189A (en) * 1972-05-11 1974-07-16 G Borello Detergent compositions and methods for making same
ATE107352T1 (de) * 1989-08-09 1994-07-15 Henkel Kgaa Herstellung verdichteter granulate für waschmittel.
DE4124701A1 (de) * 1991-07-25 1993-01-28 Henkel Kgaa Verfahren zur herstellung fester wasch- und reinigungsmittel mit hohem schuettgewicht und verbesserter loesegeschwindigkeit
DE4203031A1 (de) * 1992-02-04 1993-08-05 Henkel Kgaa Verfahren zur herstellung fester wasch- und reinigungsmittel mit hohem schuettgewicht und verbesserter loesegeschwindigkeit

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CN1127525A (zh) 1996-07-24
DE4325500A1 (de) 1995-02-02
HUT73038A (en) 1996-06-28
HU9503968D0 (en) 1996-03-28

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