EP0815196B1 - Procede de fabrication d'un detergent ou nettoyant en poudre - Google Patents

Procede de fabrication d'un detergent ou nettoyant en poudre Download PDF

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Publication number
EP0815196B1
EP0815196B1 EP96906756A EP96906756A EP0815196B1 EP 0815196 B1 EP0815196 B1 EP 0815196B1 EP 96906756 A EP96906756 A EP 96906756A EP 96906756 A EP96906756 A EP 96906756A EP 0815196 B1 EP0815196 B1 EP 0815196B1
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EP
European Patent Office
Prior art keywords
fatty acid
weight
washing
carbon atoms
branched
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.)
Expired - Lifetime
Application number
EP96906756A
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German (de)
English (en)
Other versions
EP0815196A1 (fr
Inventor
Ansgar Behler
Monika Böcker
Thomas Förster
Manfred Greger
Peter Krings
Amerigo Pastura
Renate Pfennig-Dahmen
Peter Sandkühler
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication date
Priority claimed from PCT/EP1995/004950 external-priority patent/WO1996020269A1/fr
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0815196A1 publication Critical patent/EP0815196A1/fr
Application granted granted Critical
Publication of EP0815196B1 publication Critical patent/EP0815196B1/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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0086—Laundry tablets
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the invention relates to a method for producing solid washing or Detergents.
  • Granular washing or cleaning agents with high bulk densities and high Surfactant levels are known and are used, for example, in European countries Patent applications EP 340 013, EP 352 892 and EP 460 925 are described. The one in these Agents described are obtained by granulation.
  • Washing or cleaning agents contain anionic and nonionic surfactants as well optionally soap and other common ingredients such as builder substances and optionally alkalizing agents.
  • alkylbenzenesulfonates have the disadvantage that they are made from petrochemicals Basic materials can be obtained.
  • Alkyl sulfates, especially the Fatty alkyl sulfates are based on renewable fat chemical raw materials, however on the other hand, is known to be in higher amounts, and especially in combination with nonionic surfactants, can lead to unacceptable dissolving and flushing behavior.
  • Japanese patent application Heisei 6-116599 describes granular detergents with a bulk density of 0.5 to 1.2 g / cm 3 .
  • the detergents contain fatty acid alkyl ester alkoxylates as nonionic surfactants.
  • Another goal in the manufacture of detergents or cleaners is to use detergents high levels of active detergent. Especially when washing or It is intended to produce cleaning agents with lower foaming power possible to add foam inhibitors, but this increases the cost, or lower the surfactant content of the products, but this leads to a significant loss of Washing performance leads
  • the present invention was based on the object of a method for producing solid detergents or cleaning agents with a high bulk density to develop the good solubility and good washing-in behavior in conventional household washing machines show, with an at least equally good detergency compared to that of the prior art Technology known washing or cleaning agents is obtained, and that the solid Detergents or cleaning agents as extrudates or tablets with an increased non-ionic surfactant content can be produced without these sticking.
  • a premix is first is made from detergent ingredients.
  • This solid, preferably free-flowing Premix is with the addition of a plasticizer and / or lubricant over hole forms with opening widths of the predetermined granule dimension at high pressures between 25 and 200 bar extruded.
  • the strand is immediately after leaving the Hole shape by means of a cutting device to the predetermined granule dimension tailored.
  • the application of the high working pressure causes the plasticization of the Premix in the formation of granules and provides the cutting ability of the freshly extruded Strands sure.
  • the premix consists at least partly of solid, preferably fine-particle usual ingredients of washing and cleaning agents, which optionally liquid components are mixed.
  • the solid ingredients can Tower powder obtained by spray drying, but also agglomerates, each selected mixture components as pure substances, which are in the finely divided state with one another be mixed, as well as mixtures of these.
  • the liquid ingredients are added and then the invention selected plasticizers and / or lubricants mixed.
  • a plasticizer and / or Lubricants are aqueous solutions of polymeric polycarboxylates as well highly concentrated anionic surfactant pastes and nonionic surfactants preferred.
  • the liquid nonionic surfactants also as a liquid component or as a plasticizer and / or lubricant be added to the solid premix or they are part of a solid Mixing component of the premix, this solid mixing component consisting of may consist of a carrier bead which is mixed with the nonionic surfactant or an aqueous dispersion of the non-ionic surfactant was applied.
  • this solid mixing component consisting of may consist of a carrier bead which is mixed with the nonionic surfactant or an aqueous dispersion of the non-ionic surfactant was applied.
  • the addition of the liquid component in liquid Form can be made at any point in the process, for example during manufacture of the premix, but also when processing the plasticized premix, however, before passing through the perforated shape (perforated nozzle plate).
  • a homogenizer can preferably kneaders of any configuration, for example 2-screw kneaders to get voted.
  • the intensive mixing process can already lead to a desired increase in temperature. In doing so moderately elevated temperatures of, for example, 60 to 70 ° C usually not exceeded.
  • the premix is preferred continuously fed to a 2-screw kneader (extruder), its housing and whose extruder pelletizing head is tempered to the predetermined extrusion temperature, for example, are heated to 40 to 60 ° C.
  • the premix at pressures of 25 to 200 bar, preferably above 30 bar and especially compressed at pressures from 50 to 180 bar, plasticized, in shape fine strands through the perforated nozzle plate in the extruder head and finally that Extrudate by means of a rotating knives preferably in spherical to cylindrical granules reduced.
  • the hole diameter in the hole nozzle plate and the strand cut length are matched to the selected granule dimension.
  • the production of granules in a substantially uniformly predeterminable particle size, with the absolute Particle sizes can be adapted to the intended application. in the particle diameters of up to at most 0.8 cm are generally preferred.
  • the chopped off primary granulate lies in Range from 1: 1 to about 3: 1. It is further preferred that the still plastic, moist To supply primary granulate to a further shaping processing step; there edges present on the raw granulate are rounded off, so that ultimately spherical or at least approximately spherical granules can be obtained. If Desired or required, small amounts of dry powder, for example zeolite powder, such as zeolite NaA powder, can also be used. This Shaping can be done in standard rounding machines, for example in rounding machines with rotating bottom disc. The granules are then preferably one Drying step, for example a fluidized bed dryer, supplied.
  • zeolite powder such as zeolite NaA powder
  • extruded granules which contain peroxy compounds as bleaching agents, for example perborate monohydrate, can be 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 back zeolite NaA powder, but also precipitated or pyrogenic silica, as obtainable, for example, as Aerosil ® or Sipernat ® (products of Degussa) in trade, and mixtures with zeolite. Preference is also given here to highly concentrated, at least 90% by weight fatty alcohol sulfate powders which essentially, that is to say at least 90% by weight, consist of particles with a particle size of less than 100 ⁇ m.
  • Tablets can, for example, be prepared in such a way that the Builder substances, preferably amorphous, partially crystalline and / or crystalline layered Sodium silicates and possibly all other ingredients in a mixer mixed together and the mixture using conventional tablet presses For example, eccentric presses, hydraulic presses or rotary presses Pressing pressures in the range from 1 to 300 bar, advantageously in the range from about 5 to 200 bar and in particular between 10 and 150 bar pressed. This is preferably done Compression without the addition of water.
  • the premixes intended for compression can be obtained by mixing the individual ingredients, which at least partially in pre-assembled form as granular compound are produced.
  • a tablet produced in this way preferably has a weight from 10 to 120 g, in particular from 20 to 100 g, the diameter of the Tablets is usually less than 100 mm.
  • the Diameter / height ratio of the tablets should be optimized so that a as little abrasion as possible on the vertical walls of the tabletting apparatus (higher Diameter / low height) with sufficient stability and not too large Surface (small diameter / high height) is guaranteed.
  • Preferred diameter / height ratios the cylindrical compacts are about 0.5: 1 to 10: 1, especially at 1: 1 to 8: 1.
  • the fatty acid alkyl ester alkoxylates of the formulas (I) and (II) used in the compressed solid detergents according to the invention can be prepared by conventional methods, for example by esterification of fatty acids with alkoxylated lower alkyl alcohols or lower hydroxyalkyl alcohols.
  • the fatty acid alkyl ester alkoxylates of the formulas (I) and (II) can also be prepared by heterogeneously catalyzed direct alkoxylation of fatty acid alkyl esters with alkylene oxide, in particular ethylene oxide. This synthesis process is described in detail in WO-A-90/13533 and WO-A-91/15441.
  • fatty acid alkyl ester alkoxylates of the formula (1) which are formed by ethoxylation of fatty acid alkyl esters, ie in which AO in the formula (I) for an ethylene oxide unit and R 3 for a short-chain alkyl group having 1 to 6 carbon atoms, in particular for a methyl, Ethyl, propyl or butyl group or their isomers.
  • the fatty acid alkyl esters used as starting materials can be obtained from natural oils and fats or produced synthetically.
  • the partial glyceride alkoxylates according to formula (III) can, for example, by Alkoxylation of triglycerides in the presence of polyols, here in particular in Presence of glycerol.
  • ethoxylated fatty acid alkyl esters of the formula (I), methyl C 12 -C 18 fatty acids with 1 to 30 EO and in particular with 3 to 12 being particularly preferred.
  • Ethoxylated fatty acid alkyl esters can be introduced into the process in liquid, pasty or solid, compounded form.
  • fatty acid alkyl ester alkoxylates are preferred with a low degree of ethoxylation in the range according to the invention; should Removing hydrophilic soiling is the use of Fatty acid alkyl ester ethoxylates with higher ones in the range according to the invention Degree of ethoxylation expedient.
  • the compounds of the formulas I, II or III can be used alone or in combination with other nonionic surfactants can be used.
  • alkylglycosides of the general formula RO (G) X , in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C 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 are characterized by the fact that they are easily degradable and therefore ecologically harmless.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula IV, in which R 7 CO for an aliphatic acyl radical with 6 to 22 carbon atoms, R 8 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands.
  • Alkoxylated, advantageously ethoxylated, alcohols can also be used as further nonionic surfactants.
  • the ethoxylated alcohols are derived from primary alcohols with preferably 9 to 18 carbon atoms and have an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol.
  • EO ethylene oxide
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • the alcohol radical can be linear or methyl-branched in the 2-position, or contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohol with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 5 EO.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • ethoxylated fatty alcohols those with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. In a preferred embodiment of the present invention, the use of ethoxylated alcohols is dispensed with.
  • the nonionic surfactants can be used in an amount of 1 to 25% by weight, preferably 2 to 20 wt .-% be included. In a preferred embodiment, contains the finished agent compounds with the formulas I, II or III in an amount of 2 to 20 % By weight.
  • nonionic surfactants used of which at least 50% by weight of fatty acid alkyl ester alkoxylates with the Formula I and the remainder alkoxylated alcohols and / or alkyl polyglycosides and / or polyhydroxy fatty acid amides of the general formula IV, the weight ratio of Fatty acid alkyl ester alkoxylates to the alkoxylated alcohols and / or alkyl polyglycosides and / or polyhydroxy fatty acid amides 1: 1 to 9: 1, preferably 1: 1 to 3: 1 can.
  • Structure breakers can be used as further components, but they are not necessary in the extrudates according to the invention in order to improve the processability of extrudates.
  • Suitable structure breakers are particularly ethoxylated C 8 -C 18 fatty alcohols with 20 to 45 EO, preferably tallow fatty alcohols with 30 and 40 EO, polyethylene glycol or polypropylene glycol, sulfates and / or disulfates of polyethylene glycol or polypropylene glycol, sulfosuccinates and / or disulfosuccinates of polyethylene glycol or polypropylene glycol or mixtures of these.
  • the nonionic surfactants and the structure breakers can be used in a ratio of nonionic surfactant to structure breaker of 1: 1 to 15: 1.
  • the detergents or cleaning agents produced by the process according to the invention show an improved dissolving speed and an improved induction behavior Temperatures between 15 and 60 ° C and especially between 20 and 45 ° C.
  • detergents produced by the process according to the invention preferred which contain 15 to 55 wt .-%, in particular 20 to 55 wt .-%, surfactants.
  • anionic surfactants can also be present.
  • the anionic surfactants can be selected from the group of C 6 -C 18 alkyl sulfates, C 9 -C 13 alkyl benzene sulfonates, C 6 -C 18 alkane sulfonates, C 6 -C 18 alkyl polyglycol ether sulfates, ⁇ -olefin sulfonates, C 6 -C 18 -Alkylpolyglykolethersulfonate, glycerol ether, Glycerol ether, Hydroxymischethersulfate, monoglyceride sulfates, sulfosuccinates, sulfotriglycerides, C 6 -C 18 -Fettkladilureasulfate, C 6-18 alkyl carboxylates, fatty acid isethionates, NC 6 -C 18 acyl Sarconisate
  • disalts are caused by Implementation of saturated or unsaturated, mainly on natural raw materials based fatty acids by reaction with sulfur trioxide and subsequent Conversion into the alkali metal salts are obtained, the reaction being more saturated Fatty acids leads to disalts which are sulfonated in the ⁇ -position, while the reaction is unsaturated Fatty acid disalts results, which are predominantly internal to the formerly double-bound C atoms are sulfonated.
  • Preferred disalts are derived from fatty acids or fatty acid mixtures, in particular of natural origin, which have a C chain length have between 8 and 18 and preferably between 12 and 18.
  • the anionic surfactants can be in the form of their sodium, potassium and ammonium salts as well as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the content of anionic surfactants in the detergents produced according to the invention or of anionic surfactant mixtures is preferably 5 to 35, in particular 8 to 30% by weight.
  • the anionic surfactants can be in solid form, for example in spray-dried or granulated form, or used in liquid to pasty form become. So it is preferred to use at least some of the anionic surfactants used Anionic surfactants used in the form of an aqueous plasticizer and / or lubricant Introduce surfactant paste into the process.
  • nonionic and anionic surfactants can be used in any mixture.
  • a combination of the compounds of the formulas I and II and optionally further nonionic surfactants and C 6 -C 18 alkyl sulfates and / or C 9 -C 13 alkyl benzene sulfonates and / or monoglyceride sulfates is used.
  • the solid detergent produced according to the invention can be conventional builders contain.
  • the builders can in the agent according to the invention in an amount of 10 to 60 % By weight, preferably in an amount of 15 to 50% by weight, based on the agent, be included.
  • fine-crystalline, synthetic and bound water can be used as builders containing zeolite and alkali silicates are used.
  • zeolite As the zeolite, zeolite is of the A type or preferred of the P type. Mixtures of zeolite A or P and are also suitable X, the proportion of the zeolite NaX in such mixtures expediently below 30% lies.
  • Suitable zeolites have practically no particles larger than 30 ⁇ m and preferably consist of at least 80% of particles smaller than 10 microns. Suitable zeolites have an average particle size of less than 10 microns (Measurement method: Eisenhofer diffraction; mean volume distribution), preferred between 1.5 and 4.5 ⁇ m, in particular between 2.0 and 4.0 ⁇ m.
  • the content of funds finely divided, in particular crystalline, hydrated zeolite is preferably 30 to 65 wt .-% and in particular 32 to 45 wt .-%, based on anhydrous active substance.
  • the zeolite generally has a water content of 17 to 25% by weight, preferably 18 to 22% by weight, in particular 20 to 22% by weight.
  • alkali silicates are used as builders, these are usually added as a solid and not in the form of a solution. They can be amorphous or crystalline.
  • Preferred alkali silicates are the sodium silicates, especially the amorphous sodium silicates, with a Na2O: SiO2 molar ratio of 1: 2 to 1: 3.3.
  • Amorphous alkali metal silicates are available, for example under the name Portil ® (Henkel) in trade. Further preferred amorphous silicates are those which can be produced, for example, according to German patent applications 44 00 024, 44 15 362, 44 06 591, 44 06 592 and 44 08 359. Commercially available carbonate-silicate compounds can also be used.
  • Such crystalline layered silicates are described, for example, in European patent application 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 .yH 2 O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in the international patent application WO91 / 08171.
  • the content of alkali silicates in the compositions is preferably 1 to 15% by weight and in particular 2 to 8% by weight, based on the anhydrous active substance.
  • the weight ratio of zeolite: amorphous silicate, based in each case on anhydrous active substance, is preferably 4: 1 to 10: 1.
  • the crystalline layered silicates are preferably used in amounts of 1 to 15% by weight and in particular 2 to 7% by weight, the weight ratio of zeolite to crystalline layered silicate, in each case based on anhydrous active substance, being at least 5: 1.
  • the weight ratio of amorphous alkali silicate: crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.
  • Such silicates can also serve as carriers for nonionic surfactants.
  • Polymeric carboxylates or polymeric carboxylic acids can also be used as additional builders be included. These polymeric carboxylates or carboxylic acids can in detergents according to the invention are present in an amount of 2 to 15% by weight.
  • the relative molecular weight of the homopolymers is in the generally between 1000 and 100000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on free acid.
  • a special one preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000.
  • Suitable, albeit less preferred, compounds of these Class are copolymers of acrylic acid or methacrylic acid with vinyl ether, such as vinyl methyl ether, Vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight.
  • vinyl ether such as vinyl methyl ether
  • Vinyl esters such as vinyl methyl ether
  • ethylene, propylene and styrene in which the proportion of acid is at least 50% by weight.
  • Terpolymers or mixtures of copolymers and terpolymers can be used.
  • organic builders can be used in an amount of 2 to 20% by weight, preferably 5 up to 15% by weight, based on the agent.
  • Such polymers can be obtained, for example, from the company Stockhausen (Federal Republic of Germany) can be purchased.
  • polymers according to the patent applications DE-A-43 03 320 and P 44 17 734.6, which are monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate contain, are preferably used.
  • organic builders are, for example, those preferred in Form of their sodium salts used polycarboxylic acids, such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acid, aminocarboxylic acid, Nitrilotriacetic acid (NTA), unless such use for ecological reasons objectionable, and mixtures of these.
  • Preferred salts are the salts of Polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, Tartaric acid, sugar acids and mixtures of these.
  • the detergents produced according to the invention preferably contain peroxy bleaching agents and in particular peroxy bleaching agents in combination with bleach activators.
  • peroxy bleaching agents Among the compounds which serve as bleaching agents and which are H 2 O 2 in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other usable bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -containing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperoxyazelaic acid or diperoxydodecanedioic acid.
  • the detergents preferably contain 5 to 25% by weight and in particular 10 to 20% by weight of bleaching agent, sodium perborate monohydrate or tetrahydrate preferably being used.
  • bleach activators can be incorporated into the preparations which form organic peracids with H 2 O 2 .
  • these are N- or O-acyl compounds, for example multi-acylated alkylenediamines, in particular tetraacetylethylene diamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, triazines, urazoles, diketopiperazines, sulfurylamides and cyanuric acid hydrides, and also carboxylic acid hydrides , Carboxylic acid esters, especially sodium isonanoyloxybenzenesulfonate, and acylated sugar derivatives, especially pentaacetyl glucose.
  • N- or O-acyl compounds for example multi-acylated alkylenediamines, in particular tetraacetylethylene diamine, acylated glycolurils, in particular
  • the bleach activator can be coated with coating substances in a known manner or, if necessary with the aid of auxiliaries, granulated or extruded / pelletized and, if desired, contain further additives, for example dye.
  • Such granules preferably contain over 70% by weight, in particular from 90% by weight to 99% by weight, of bleach activator.
  • a bleach activator is preferably used which forms peracetic acid under the washing conditions.
  • TAED tetraacetylethylene diamine
  • carboxymethyl cellulose with average grain sizes from 0.01 to 0.8 mm
  • DADHT 1,5- Diacetyl-2,4-dioxohexahydro-1,3,5-triazine
  • Extruded TAED which contains 70 70% by weight of TAED, 15 to 25% by weight of C 12-18 fatty alcohol sulfate and 2 to 6% by weight of soda can also be used.
  • the content of bleach activators in the detergents containing bleach is in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.
  • Suitable ingredients of the agents according to the invention are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these; in particular alkali carbonate and alkali silicate, especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5.
  • the sodium carbonate content of the agents is preferably up to 20% by weight, advantageously 5 and 15% by weight.
  • the sodium silicate content of the agents is generally up to 10% by weight and preferably between 2 and 8% by weight.
  • the other detergent ingredients include foam inhibitors, optical brighteners, Enzymes, fabric softening agents, colors and fragrances.
  • Neutral salts can also be used be contained in an amount up to 20 wt .-%, their proportion is preferably ⁇ 10 wt .-%.
  • the agent can also contain additional graying inhibitors in an amount of 0.1 to 5 % By weight, based on the composition.
  • additional graying inhibitors are Suitable water-soluble colloids mostly organic, for example soluble Starch preparations and e.g. B. degraded starch, aldehyde starches, etc. carboxymethyl cellulose (Na salt), methyl cellulose, methyl hydroxyethyl cellulose and their mixtures as well Polyvinyl pyrrolidone are preferably used.
  • Enzymes come from the class of proteases, lipases, amylases, Cellulases or their mixtures in question. Are particularly well suited Strains of bacteria or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus and Humicola insolens obtained enzymatic agents. Preferably are proteases of the subtilisin type and in particular proteases derived from Bacillus lentus are used.
  • Enzyme mixtures are, for example, from Protease and amylase or protease and lipase or protease and cellulase or from Cellulase and lipase or from protease, amylase and lipase or protease, lipase and Cellulase, but especially cellulase-containing mixtures of particular interest. Peroxidases or oxidases have also proven to be suitable in some cases.
  • the Enzymes can be adsorbed on carriers and / or embedded in coating substances, to protect them against premature decomposition.
  • the percentage of enzymes Enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2% by weight.
  • Suitable 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. With advantage Mixtures of various foam inhibitors can also be used, e.g. such made of silicone oil, paraffin oil or wax.
  • the foam inhibitors are preferably attached to one granular, water-soluble or dispersible carrier substance bound.
  • the solid detergents produced according to the invention can, for example, derivatives of the optical brighteners Contain diaminostilbenedisulfonic acid or its alkali metal salts, which are good in the Let the dispersion work in.
  • the maximum amount of brightener in the agents according to the invention is 0.5% by weight, amounts of 0.02 are preferred up to 0.25% by weight.
  • the salts come from as stabilizers, in particular for per-compounds and enzymes Polyphosphonic acids, especially 1-hydroxyethane-1,1-diphosphonic acid (HEDP) in Consideration.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • the washing or cleaning agents can be produced uniformly from extrudates, which have the above-mentioned ingredients.
  • the funds can also come from a mixture of several different granules are obtained, of which the extrudates according to the invention form the main component.
  • the Bleach activator, the enzymes as well as colors and fragrances after the extrudates be added It is preferred in each case to use the bleach activator and the enzymes compacted granular form, for example as extrudates produced separately, which by means of a kneader of the configuration described above or via a Pellet press can be obtained.
  • low-foaming Detergents or dishwashing detergents especially for machine use, manufactured.
  • foaming Detergents or cleaning agents especially for manual use.
  • the comparison formulations contain fatty alcohol derivatives.
  • Table 1 contains the various fatty acid alkyl ester alkoxylates and anionic surfactants and the fatty alcohol derivatives used in the comparison formulations.
  • compositions with the compositions given in Table 1 were extruded in accordance with the teaching of international patent application WO91 / 02047.
  • the enzyme and the bleach activator in granular form were subsequently added to the extrudate.
  • component Quantity (% by weight) Anionic surfactant 12.0 Fatty acid alkyl ester alkyloxylate or fatty alcohol derivative 13.0 Na soap 0.8
  • Polyethylene glycol (molecular weight 400) 2.0 Zeolite A (anhydrous active substance) 28.0 Citrate 3.0 amorphous sodium disilicate 2.0 Sodium perborate monohydrate 20.0 Bleach activator (TAED) 6.0 Protease 1.24 Lipase 1.00 Perfume 0.45 Silicone defoamer 0.6 Water and salts from raw materials ad 100 Recipe no.
  • Nonionic surfactant Anionic surfactant Fatty alcohol derivative Fatty acid alkyl ester alkoxylate 1 C 12/18 fatty acid methyl ester x 5 EO C 12/18 fatty alcohol sulfate 2nd C 12/18 fatty acid methyl ester x 4.5 EO " 3rd C 12/18 fatty acid methyl ester x 6 EO " 4th C 12/18 fatty acid methyl ester x 12 EO " 5 C 12/18 fatty acid n-butyl ester x 12 EO " 6 C 16/18 fatty acid methyl ester x 5 EO " 7 C 12/18 fatty acid monoglyceride x 9 EO " 8th Soybean fatty acid triglyceride x 25 EO (double bonds in soybean fatty acid are epoxidized) " V1 (compare) Na-C 12/18 fatty alcohol X 5 EO - " 9 - C 12/18 fatty acid ethyl ester x 12 EO C 11/13 alkylbenz
  • the agents according to the invention all had excellent washability.
  • washing performance was checked under practical conditions in household washing machines.
  • the machines were loaded with 3.0 kg of normally soiled household linen (bed linen, table linen, underwear) and 0.5 kg of test fabric.
  • Strips of standardized cotton fabric (Krefeld laundry research institute), nettle, knitwear (cotton tricot) and terry cloth were used as the test fabric.
  • Washing conditions tap water of 23 ° d (equivalent to 230 mg CaO / l), main wash cycle 8.0 g / l at 30 ° C (heating up time 60 minutes, 15 minutes at 90 ° C), liquor ratio (kg of laundry: liters of wash water in the main wash cycle) 1: 4, rinse five times with tap water, draining and drying.
  • the test fabrics were soiled with grease / pigment.
  • the washing effect is determined by measuring the remission. (Measurement of whiteness: Zeiss reflectometer, 465 nm, suppression of the brightener effect).
  • the trials were each repeated six times.
  • the specified remission values are the Average values across all measurements.
  • the washed test fabric was placed on the Residual fat content examined. The determined values are in the following table reproduced. This table shows that with the invention Detergent the largest amount of fat on the test fabric could be removed.
  • the foaming behavior can be achieved, for example, by using others Surfactants or the surfactants in other weight ratios can be set specifically. In this way, more foaming agents could be obtained especially suitable for manual use.

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  • Wood Science & Technology (AREA)
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  • Detergent Compositions (AREA)

Claims (11)

  1. Procédé de production de détergents ou de nettoyants comprimés à densité en vrac élevée, dans lequel un prémélange des constituants de détergents, renfermant des surfactifs anioniques, des tensioactifs non ioniques, des substances adjuvantes et, le cas échéant, un agent d'alcalisation, est fabriqué et comprimé, caractérisé en ce que plus de 50 % en poids des tensioactifs non ioniques mis en oeuvre sont des alcoxylates d'alkylesters d'acides gras des formules I, II ou III, R1-CO2-(AO)m-R2 R2-CO2-(AO)m-R1
    Figure 00320001
    dans lesquelles
    R1
    représente un groupe alkyle à chaíne ramifiée ou droite, saturé ou insaturé, comportant 5 à 21 atomes de C,
    R2
    correspond à l'hydrogène ou à un groupe alkyle à chaíne droite ou ramifiée, présentant 1 à 6 atomes de C,
    R3, R4 et R5
    peuvent être identiques ou différents et représenter l'hydrogène ou
    Figure 00320002
    dans laquelle R6 peut être un groupe alkyle à chaíne ramifiée ou droite, saturé ou insaturé, comportant 5 à 21 atomes de C, à condition que R3, R4 et R5 ne représentent pas simultanément l'hydrogène,
    AO
    est une unité d'oxyde d'alkylène en C2-C4,
    m, n, o et p
    peuvent être identiques ou différents et représenter un nombre de 1 à 60.
  2. Procédé selon la revendication 1, caractérisé en ce que m, n, o et p peuvent représenter un nombre de 1 à 30 et en particulier de 3 à 12.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que le prémélange est pressé en boudins, sous adjonction d'un plastifiant et/ou d'un lubrifiant, via des moules perforés avec des largeurs d'ouverture de la dimension de granulé prédéterminée, à des pressions élevées comprises entre 25 et 200 bars et en ce que le boudin est découpé à la dimension de granulé prédéterminée au moyen d'un dispositif de coupe, directement après la sortie du moule perforé
  4. Procédé selon la revendication 1 ou 2, caractérisé en ce que le prémélange est pressé en comprimés.
  5. Procédé selon une des revendications 1 à 4, caractérisé en ce que l'on met en oeuvre des esters méthyliques d'acides gras en C12-C18 avec 1 à 30 EO et en particulier, avec 3 à 12 EO.
  6. Procédé selon une des revendications 1 à 5, caractérisé en ce que l'on met en oeuvre un compound solide, renfermant les surfactifs anioniques et les esters méthyliques d'acides gras éthoxylés et/ou un compound solide contenant les tensioactifs, en particulier un compound renfermant du silicate, qui est imprégné avec des alkylesters d'acides gras éthoxylés.
  7. Procédé selon une des revendications 1 à 6, caractérisé en ce que l'on met en oeuvre au moins 50 % en poids des tensioactifs non ioniques utilisés comme alcoxylates d'alkylesters d'acides gras de la formule (I) et comme autres surfactifs non ioniques, des alcools alcoxylés et/ou des alkylpolyglycosides et/ou des amides d'acides gras polyhydroxyliques, le rapport pondéral entre les alcoxylates d'alkylesters d'acides gras et les alcools alcoxylés et/ou les alkylpolyglycosides et/ou les amides d'acides gras polyhydroxyliques atteignant 1:1 à 9:1.
  8. Procédé selon une des revendications 1 à 7, caractérisé en ce que l'on met en oeuvre les surfactifs anioniques sous forme solides ou liquide à pâteuse.
  9. Procédé selon une des revendications 1 à 8, caractérisé en ce que l'on ajuste la densité en vrac des détergents ou des nettoyants entre 600 et 1000 g/l.
  10. Procédé selon une des revendications 1 à 9, caractérisé en ce que l'on fabrique un détergent ou un nettoyant à mousse freinée, en particulier pour l'utilisation en machine.
  11. Procédé selon une des revendications 1 à 9, caractérisé en ce que l'on fabrique un détergent ou un nettoyant moussant, en particulier pour l'utilisation manuelle.
EP96906756A 1995-03-17 1996-03-08 Procede de fabrication d'un detergent ou nettoyant en poudre Expired - Lifetime EP0815196B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE19509752 1995-03-17
DE19509752A DE19509752A1 (de) 1995-03-17 1995-03-17 Verfahren zur Herstellung eines pulverförmigen Waschmittels
PCT/EP1995/004950 WO1996020269A1 (fr) 1994-12-23 1995-12-14 Silicate alcalin amorphe contenant des substances impregnees
WOPCT/EP95/04950 1995-12-14
PCT/EP1996/000994 WO1996029389A1 (fr) 1995-03-17 1996-03-08 Procede de fabrication d'un detergent ou nettoyant en poudre

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EP0815196B1 true EP0815196B1 (fr) 1999-08-11

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DE19624416A1 (de) * 1996-06-19 1998-01-02 Henkel Kgaa Verfahren zur Herstellung von festen Wasch- oder Reinigungsmitteln
DE19624415A1 (de) * 1996-06-19 1998-01-02 Henkel Kgaa Verfahren zur Herstellung von festen Wasch- oder Reinigungsmitteln
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DE19746781A1 (de) * 1997-10-23 1999-04-29 Henkel Kgaa Verfahren zur Herstellung duftverstärkter Wasch- oder Reinigungsmittel
DE19754289A1 (de) * 1997-12-08 1999-06-10 Henkel Kgaa Wasch- und Reinigungsmittelformkörper mit verbesserten Zerfallseigenschaften
GB9726824D0 (en) * 1997-12-19 1998-02-18 Manro Performance Chemicals Lt Method of manufacturing particles
DE19807321A1 (de) * 1998-02-20 1999-08-26 Henkel Kgaa Wasch- und Reinigungsmittelformkörper mit verbessertem Eigenschaftsprofil
DE19850223A1 (de) * 1998-10-31 2000-05-04 Clariant Gmbh Wasch- und Reinigungsmittel enthaltend alkoxylierte Fettsäurealkylester
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DE19939805A1 (de) * 1999-08-21 2001-02-22 Cognis Deutschland Gmbh Schaumkontrollierte feste Waschmittel
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DE19956960A1 (de) * 1999-11-26 2001-05-31 Henkel Kgaa Tensidhaltige Zubereitung
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DE59602716D1 (de) 1999-09-16
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ES2136391T3 (es) 1999-11-16
DE19509752A1 (de) 1996-09-19

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