EP0815196A1 - Procede de fabrication d'un detergent ou nettoyant en poudre - Google Patents

Procede de fabrication d'un detergent ou nettoyant en poudre

Info

Publication number
EP0815196A1
EP0815196A1 EP96906756A EP96906756A EP0815196A1 EP 0815196 A1 EP0815196 A1 EP 0815196A1 EP 96906756 A EP96906756 A EP 96906756A EP 96906756 A EP96906756 A EP 96906756A EP 0815196 A1 EP0815196 A1 EP 0815196A1
Authority
EP
European Patent Office
Prior art keywords
fatty acid
weight
washing
chain
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.)
Granted
Application number
EP96906756A
Other languages
German (de)
English (en)
Other versions
EP0815196B1 (fr
Inventor
Ansgar Behler
Monika Böcker
Thomas Förster
Manfred Greger
Peter Krings
Amerigo Pastura
Renate Pfennig-Dahmen
Peter Sandkühler
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
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
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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 cleaning agents.
  • Granular washing or cleaning agents with high bulk densities and high surfactant contents are known and are described, for example, in European patent applications EP 340 013, EP 352 892 and EP 460 925.
  • the agents described in these publications are obtained by granulation processes.
  • the washing or cleaning agents produced in the international patent application mentioned above contain anionic and nonionic surfactants as well as optionally soap and other conventional ingredients such as builder substances and optionally alkalizing agents.
  • Alkylbenzenesulfonates and alkylsulfates are mentioned as anionic surfactants.
  • alkylbenzenesulfonates have the disadvantage that they are obtained from petrochemical raw materials.
  • alkyl sulfates, especially fatty alkyl sulfates are based on renewable oleochemical raw materials, it is known, on the other hand, that higher amounts, and especially in combination with nonionic surfactants, can lead to unacceptable dissolving and flushing behavior.
  • the international patent application WO 94/13771 describes granular washing or cleaning agents with a bulk density of 700 g / l and above, which contain a high surfactant content and anionic surfactants with good degradation behavior.
  • the granular detergents and cleaning agents contain 20 to 55% by weight of anionic and nonionic surfactants and optionally including soap, the content of the agents being C 3 -C 4-alcohol sulfates, ethoxylated Alcohol sulfates, ⁇ -sulfofatty acid esters and mixtures thereof are above 8% by weight and the weight ratio of these anionic sulfates and / or sulfofatty acid esters to nonionic surfactants should be 10: 1 to 1: 1.25.
  • Japanese patent application Heisei 6-116599 describes granular detergents with a bulk density of 0.5 to 1.2 g / cm 3. To improve their solubility, the detergents contain fatty acid alkyl ester alkoxylates as nonionic surfactants.
  • Another goal in the manufacture of detergents or cleaners is to provide detergents with high levels of detergent.
  • detergents or cleaning agents with a lower foaming capacity are to be produced, it is possible to add foam inhibitors, but this increases the costs or reduces the surfactant content of the products, but this leads to a considerable loss in washing performance.
  • the present invention was based on the object of developing a process for the production of solid detergents or cleaning agents with a high bulk density, which show good solubility and good washing-in behavior in conventional household washing machines, with an at least equally good washing power compared to those from the prior art Detergents or cleaning agents known in the art are obtained, and that the solid washing or cleaning agents can be produced as extrudates or tablets with an increased nonionic surfactant content without them sticking.
  • the present invention relates to a process for the production of pressed detergents or cleaning agents with a high bulk density, in which a premix of detergent constituents containing anionic surfactants, nonionic surfactants, builder substances and, if appropriate, alkalizing agents is produced and compressed, more than 50% by weight of those used
  • Nonionic surfactants are fatty acid alkyl ester alkoxylates with the formulas I, II or III,
  • R 1 represents a branched or straight-chain, saturated or unsaturated alkyl group having 5 to 21 C atoms
  • R 2 represents hydrogen or a straight-chain or branched-chain alkyl group with 1 to
  • R3, R 4 and R5 may be the same or different and represent hydrogen or O.
  • R can be a branched or straight-chain, saturated or unsaturated alkyl group having 5 to 21 C atoms, with the proviso that R 3 , R 4 and R 5 are not simultaneously hydrogen,
  • AO stands for a C2-C4 alkylene oxide unit
  • m, n, o and p can be the same or different and stand for a number from 1 to 60, preferably 1 to 30, in particular 3 to 12.
  • a premix of detergent components is first prepared.
  • This solid, preferably free-flowing premix is strand-shaped with the addition of a plasticizer and / or lubricant via hole shapes with opening widths of the predetermined granule dimension at high pressures between 25 and 200 bar.
  • the strand is cut to the predetermined pellet dimension immediately after exiting the hole shape by means of a cutting device.
  • the application of the high working pressure causes the premix to be plasticized during the formation of the granulate and ensures the cutting ability of the freshly extruded strands.
  • the premix consists at least in part of solid, preferably finely divided, conventional ingredients of detergents and cleaning agents, to which liquid constituents may have been added.
  • the solid ingredients can be tower powders obtained by spray drying, but also agglomerates, the mixture components selected in each case as pure substances which are mixed with one another in the finely divided state, and mixtures of these. Subsequently, the liquid ingredients are optionally added and then the plasticizer and / or lubricant selected according to the invention is mixed in.
  • Preferred plasticizers and / or lubricants are aqueous solutions of polymeric polycarboxylates, as well as highly concentrated anionic surfactant pastes and nonionic surfactants.
  • the liquid nonionic surfactants can also be added to the solid premix as a liquid constituent or as a plasticizer and / or lubricant, or they are part of a solid mixture component of the premix, which solid mixture component can consist of a carrier bead, which has been treated with the nonionic surfactant or an aqueous dispersion of the nonionic surfactant.
  • the liquid component can be added in liquid form at any point in the process, for example in the preparation of the premix, but also in the processing of the plasticized premix, but before it passes through the perforated mold (perforated nozzle plate).
  • Kneaders of any configuration can preferably be selected as the homogenizing device.
  • the intensive mixing process can in itself lead to a desired temperature increase. Moderately elevated temperatures of, for example, 60 to 70 ° C. are generally not exceeded.
  • the premix is preferably fed continuously to a 2-screw kneader (extruder), the housing and the extruder granulation head of which are heated to the predetermined extrusion temperature, for example heated to 40 to 60 ° C.
  • the premix is compressed at pressures from 25 to 200 bar, preferably above 30 bar and in particular at pressures from 50 to 180 bar, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally by means of the extrudate a rotating knives preferably reduced in spherical to cylindrical granules.
  • the hole diameter in the perforated nozzle plate and the strand cut length are matched to the selected granule dimension.
  • the production of granules of an essentially uniformly predeterminable particle size succeeds, wherein in particular the absolute particle sizes can be adapted to the intended use. In general, 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 0.8 to 3 mm.
  • the length / diameter ratio of the chopped-off primary granules is in the range from 1: 1 to about 3: 1. It is also preferred to feed the still plastic, moist primary granules to a further shaping processing step; the edges on the raw granules 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, can also be used in this step.
  • 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 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 again zeolite-NaA powder, but also precipitated or pyrogenic silica, as are commercially available, for example, as Aerosil® or Sipemat (products from Degussa), and mixtures with zeolite.
  • Tablets can, for example, be produced in such a way that the builder substances, preferably amorphous, partially crystalline and / or crystalline layered sodium silicates and optionally all other constituents are mixed with one another in a mixer and the mixture by means of conventional tablet presses, for example eccentric presses, hydraulic presses or rotary presses with pressures in the range of 1 to 300 bar, advantageously in the range from about 5 to 200 bar and in particular between 10 and 150 bar.
  • the pressing takes place without the addition of water.
  • the premixes provided for the vaporizing can be prepared by mixing the individual ingredients, which are at least partially present in a pre-assembled form as a granular compound.
  • a tablet produced in this way preferably has a weight of 10 to 120 g, in particular 20 to 100 g, the diameter of the tablets usually being less than 100 mm.
  • Preferred detergent tablets have a maximum diameter of 80 mm and in particular from 30 to 80 mm.
  • These tablets preferably have a weight of 10 to 40 g, with diameters of 20 to 50 mm being preferred.
  • the diameter / height ratio of the tablets should be optimized in such a way that the least possible abrasion on the vertical walls of the tabletting apparatus (high diameter / low height) is ensured with sufficient stability and a surface that is not too large (small diameter / high height) .
  • Preferred diameter / height ratios of the cylindrical compacts are about 0.5: 1 to 10: 1, in particular 1: 1 to 8: 1.
  • the fatty acid alkyl ester alkoxylates of the formulas (I) and (II) used in the powdered detergents according to the invention can be prepared by conventional methods, such as, 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 method is described in detail in WO 90/13533 and WO 91/15441.
  • fatty acid alkyl ester alkoxylates of the formula (I) 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, as well as produced synthetically.
  • the partial glyceride alkoxylates according to formula (III) can be obtained, for example, by alkoxylation of triglycerides in the presence of polyols, here in particular in the presence of glycerol.
  • ethoxylated fatty acid alkyl esters of the formula (I), methyl C.rCi ⁇ fatty acid esters with 1 to 30 EO and in particular 3 to 12 being particularly preferred.
  • Ethoxylated fatty acid alkyl esters can be introduced into the process in liquid, pasty or solid, compounded form. It is therefore preferred to use a solid compound containing anionic surfactants and ethoxylated fatty acid alkyl esters, and / or a builder-containing solid compound, in particular a silicate-containing compound, which is impregnated with ethoxylated fatty acid alkyl esters.
  • the powder detergents according to the invention are to be used to remove lipophilic soiling, preference is given to choosing fatty acid alkyl ester alkoxylates with a low degree of ethoxylation in the range according to the invention; if hydrophilic soiling is to be removed, the use of fatty acid alkyl ester ethoxylates with a higher degree of ethoxylation in the range according to the invention is expedient.
  • the compounds of the formulas I, II or III can be used alone or in combination with other nonionic surfactants.
  • alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the oligomerization degree 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,
  • R for an aliphatic acyl radical having 6 to 22 carbon atoms
  • 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
  • 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 on average 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, Cg-C- * - (- alcohol with 7 EO, C-
  • 4 alcohol with 3 EO and C ⁇ i2-Ci8 " Alkono ' m ' t 5 - 0 * 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 of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • the use of ethoxylated alcohols is dispensed with.
  • the non-ionic surfactants can be present in the finished agent in an amount of 1 to 25% by weight, preferably 2 to 20% by weight.
  • the finished composition contains compounds of the formulas I, II or III in an amount of 2 to 20% by weight.
  • nonionic surfactants are used, of which at least 50% by weight of fatty acid alkyl ester alkoxylates having the formula I and the remainder being alcohols and / or alkyl polyglycosides and / or polyhydroxy fatty acid amides of the general formula IV, the weight ratio of the 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.
  • 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.
  • Particularly suitable structure breakers are ethoxylated Cs-C ⁇ - 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 from Poly ⁇ ethylene 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 washing or cleaning agent prepared by the process of this invention show an improved dissolution rate and an improved dispensing behavior at temperatures between 15 and 60 ⁇ C and especially between 20 and 45 ° C.
  • detergents produced by the process according to the invention which contain 15 to 55% by weight, in particular 20 to 55% by weight, of surfactants are preferred.
  • anionic surfactants can also be present.
  • the anionic surfactants can be selected from the group of the CQ-Ci ⁇ - alkyl sulfates, Cg-Co-alkylbenzenesulfonates, C ⁇ -C-J ⁇ -alkanesulfonates, CQ-C- ⁇ Q-alkyl polyglycol ether sulfates, ⁇ -olefin sulfonates, Cg-Ci 8-alkyl polyglycol ether sulfonates , Glycerol ether sulfonates, glycerol ether sulfates, hydroxy mixed ether sulfates,
  • disalts are obtained by reacting saturated or unsaturated fatty acids based predominantly on natural raw materials by reacting with sulfur trioxide and then converting them to the alkali metal salts, the reaction of saturated fatty acids leading to disalts which are in the ⁇ -position are sulfonated, while the conversion of unsaturated fatty acids results in salts which are predominantly sulfonated internally on the formerly double-bonded carbon atoms.
  • disalts are derived from fatty acids or fatty acid mixtures, in particular of natural origin, which have a C chain length 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 and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the content of anionic surfactants or anionic surfactant mixtures in the detergents produced according to the invention is preferably 5 to 35, in particular 8 to 30,% 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. Thus, it is preferred to introduce at least some of the anionic surfactants used as plasticizers and / or lubricants into the process in the form of an aqueous surfactant paste.
  • nonionic and anionic surfactants can be used in any mixture.
  • 8-alkyl sulfates and / or Cg-C ⁇ -alkylbenzenesulfonates and / or monoglyceride sulfates is used.
  • the powder detergent produced according to the invention can contain conventional builders.
  • the builders can be present 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.
  • finely crystalline, synthetic and bound water-containing zeolite and alkali silicates can be used as builders.
  • A-type or P-type zeolite is preferred as the zeolite.
  • Mixtures of zeolite A or P and X are also suitable, the proportion of the zeolite NaX in such mixtures advantageously being below 30% lies.
  • Suitable zeolites have practically no particles larger than 30 ⁇ m and preferably consist at least 80% of particles smaller than 10 ⁇ m.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m
  • the fine-particle, in particular crystalline, hydrated zeolite content of the agents is preferably 30 to
  • 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, in particular the amorphous sodium silicates, with a Na2O: SiO2 molar ratio of 1: 2 to 1: 3.3.
  • Such amorphous alkali silicates are commercially available, for example, under the name Portil (Henkel).
  • 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.
  • crystalline sheet silicates of the formula NaMSi ⁇ 2x + iy H2 ⁇ are preferably used, in which M represents sodium, x is a number from 1, 9 to 4 and y is a number from 0 to Is 20 and preferred values for x are 2, 3 or 4.
  • M represents sodium
  • x is a number from 1, 9 to 4
  • y is a number from 0 to Is 20 and preferred values for x are 2, 3 or 4.
  • 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 Na2Si2 ⁇ 5 yH2 ⁇ are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in 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, in each case based 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 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 may also be present as further builders. These polymeric carboxylates or carboxylic acids can be present in the detergent according to the invention in an amount of 2 to 15% by weight.
  • Polymeric carboxylates or polymeric carboxylic acids with a relative molecular weight of at least 350 in the form of their water-soluble salts, in particular in the form of the sodium and or potassium salts, are considered, such as polyacrylates, polyhydroxyacrylates, polymethacrylates, polymaleates and in particular copolymers of acrylic acid Maleic acid or maleic anhydride, preferably those composed of 50 to 70% acrylic acid and 50 to 10% maleic acid.
  • the relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, 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 of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers. Vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight.
  • organic builders can be contained in an amount of 2 to 20% by weight, preferably 5 to 15% by weight, based on the composition.
  • Polymers with more than 2 different monomer units, in particular those that are biodegradable, are also preferably used.
  • Such polymers can be purchased, for example, from Stockhausen (Federal Republic of Germany).
  • Polymers according to patent applications DE-A-43 03 320 and P 44 17 734.6, which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers, are preferably used.
  • organic builders are, for example, the polyca ⁇ onic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acid, aminocarboxylic acid, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these this.
  • 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.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other usable bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H2O2-containing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperoxyazelaic acid or dipperoxydodecanedioic acid.
  • the detergents preferably contain 5 to 25% by weight and in particular 10 to 20% by weight of bleaching agent, preferably sodium perborate monohydrate or tetrahydrate being used.
  • bleach activators can be introduced into the preparations that form organic peracids with H2O2.
  • these are N- or O-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylethylene diamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, triazines, urazoles, diketopiperazines, sulfurylamides and cyanuric acidides, and also carboxylic acid hydrides , Carboxylic acid esters, especially sodium isononoyloxybenzenesulfonate, and acylated sugar derivatives, especially pentaacetyl glucose.
  • N- or O-acyl compounds for example multiply acylated alkylenediamines, in particular tetraacetylethylene diamine, acylated glycolurils, in particular tetraace
  • 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 tetraacetylethylenediamine
  • DADHT 5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazine
  • TAED extruded TAED
  • the content of. Bleicheptato ⁇ ren in the bleach-containing detergents is in the usual range, preferably between 1 and 10 wt .-% and in particular between 3 and 8 wt .-%.
  • Suitable ingredients of the agents according to the invention are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures thereof; in particular alkali carbonate and alkali silicate, especially sodium silicate with a molar ratio N ⁇ 2 ⁇ : S.O2 from 1: 1 to 1: 4.5, preferably from 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.
  • detergent components include foam inhibitors, optical brighteners, enzymes, fabric softening agents, colorants and fragrances.
  • Neutral salts can also be present in an amount of up to 20% by weight, the proportion of which is preferably ⁇ 10% by weight.
  • the agent can also contain additional graying inhibitors in an amount of 0.1 to 5% by weight, based on the agent.
  • additional graying inhibitors water-soluble colloids, mostly of an organic nature, are suitable, for example soluble starch preparations and z.
  • Carboxymethyl cellulose (sodium salt), methyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof and polyvinylpyrrolidone are preferably used.
  • 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 subtiiis, Bacillus licheniformis and Streptomyces griseus and Humicola insolens 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.
  • 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 in order to protect them against premature decomposition.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • Suitable foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally signed silica and paraffins, Waxes, microcrystalline waxes and their mixtures with signed silica. Mixtures of different foam inhibitors can also be used with advantage, for example those made from silicone oil, paraffin oil or waxes.
  • the foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.
  • the powder detergents can contain, for example, derivatives of diaminostilbenedisulfonic acid or the alkali metal salts thereof as optical brighteners, which can be readily incorporated into the dispersion.
  • the maximum content of brighteners in the agents according to the invention is 0.5% by weight, preferably from 0.02 to 0.25% by weight.
  • the salts of polyphosphonic acids are suitable as stabilizers, in particular for per-compounds and enzymes.
  • 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 agents can also be obtained from a mixture of several different granules, of which the extrudates according to the invention form the main constituent.
  • 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 each in compacted granular form, for example as extrudates produced separately, which are obtained by means of a kneader of the configuration described above or via a pellet press.
  • low-foaming detergents or dishwashing detergents are produced, in particular for machine use.
  • foaming washing or cleaning agents in particular for manual use, are produced.
  • the comparison formulations contain fatty alcohol derivatives.
  • the basic formulation is shown in Table 1, Table 2 contains the various fatty acid alkyl ester alkoxylates and anionic surfactants as well as 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.
  • Polyethylene glycol (relative molecular weight 2.0 mass 400)
  • Zeolite A (anhydrous active substance) 28.0
  • the solubility was determined at different grain sizes K:
  • the foam test was carried out at a temperature of 60 ° C and a water hardness of 16 + 2 ° d.
  • the agent was dosed in a concentration of 45.9 g / l water.
  • the amount of foam formed was rated with grades from 0 to 6, the grades being assigned as follows:
  • the agents according to the invention all had excellent washability.
  • both the solubility and the flushability of pressed granules (extrudates) have been decisively improved. Analogous results were also obtained for tablets.
  • the 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: liter of washing solution in Main wash) 1: 4, rinse five times with tap water, spin off and dry.
  • the test fabrics were soiled with grease / pigment.
  • the washing effect is determined by measuring the reflectance. (Measurement of the whiteness: Zeiss reflectometer, 465 nm, suppression of the brightener effect). The experiments were repeated six times each. The specified remission values are the average values over all measurements.
  • the washed test fabric was examined for the residual fat content. The values determined are shown in the following table. This table shows that the greatest amount of fat on the test fabric could be removed with the detergent according to the invention.
  • the foaming behavior can be specifically adjusted, for example, by using other surfactants or the surfactants in other weight ratios. In this way, more foaming agents could be obtained, which were particularly suitable for manual use.

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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)
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

Publications (2)

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EP0815196A1 true EP0815196A1 (fr) 1998-01-07
EP0815196B1 EP0815196B1 (fr) 1999-08-11

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EP (1) EP0815196B1 (fr)
AT (1) ATE183230T1 (fr)
DE (2) DE19509752A1 (fr)
ES (1) ES2136391T3 (fr)
WO (1) WO1996029389A1 (fr)

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WO2013056898A1 (fr) 2011-10-21 2013-04-25 Jenavalve Technology Inc. Système de cathéter pour l'introduction d'un stent expansible pour valvule cardiaque dans le corps d'un patient, système d'insertion avec un système de cathéter et dispositif médical pour le traitement d'un défaut d'une valvule cardiaque

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DE19624415A1 (de) * 1996-06-19 1998-01-02 Henkel Kgaa Verfahren zur Herstellung von festen Wasch- oder Reinigungsmitteln
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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
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ATE183230T1 (de) 1999-08-15
DE59602716D1 (de) 1999-09-16
WO1996029389A1 (fr) 1996-09-26
EP0815196B1 (fr) 1999-08-11
ES2136391T3 (es) 1999-11-16
DE19509752A1 (de) 1996-09-19

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