WO2000060047A1 - Agent mouillant particulaire et produit de lavage pour lave-vaisselle - Google Patents

Agent mouillant particulaire et produit de lavage pour lave-vaisselle Download PDF

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Publication number
WO2000060047A1
WO2000060047A1 PCT/EP2000/002462 EP0002462W WO0060047A1 WO 2000060047 A1 WO2000060047 A1 WO 2000060047A1 EP 0002462 W EP0002462 W EP 0002462W WO 0060047 A1 WO0060047 A1 WO 0060047A1
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WO
WIPO (PCT)
Prior art keywords
weight
rinse aid
particulate
substances
acid
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PCT/EP2000/002462
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German (de)
English (en)
Inventor
Thomas Holderbaum
Jürgen Härer
Christian Nitsch
Bernd Richter
Oliver Kurth
Markus Semrau
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to AU41067/00A priority Critical patent/AU4106700A/en
Publication of WO2000060047A1 publication Critical patent/WO2000060047A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0034—Fixed on a solid conventional detergent ingredient
    • 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
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means

Definitions

  • the present invention is in the field of machine dishwashing detergents for household dishwashers. It relates in particular to particulate machine dishwashing detergents (MGSM) which contain rinse aid particles.
  • MGSM particulate machine dishwashing detergents
  • the automatic cleaning of dishes in household dishwashers usually comprises a pre-wash, a main wash and a rinse cycle, which are interrupted by intermediate wash cycles.
  • the pre-wash cycle for heavily soiled dishes can be activated, but is only selected by the consumer in exceptional cases, so that in most machines a main wash cycle, an intermediate rinse cycle with pure water and a rinse cycle are carried out.
  • the temperature of the main wash cycle varies between 40 and 65 ° C depending on the machine type and program level selection.
  • rinse aids are added from a dosing tank in the machine, which usually contain non-ionic surfactants as the main component. Such rinse aids are in liquid form and are widely described in the prior art. Your main task is to prevent limescale and deposits on the cleaned dishes. In addition to water and low-foaming nonionic surfactants, these rinse aids often also contain hydrotopes, pH regulators such as citric acid or scale-inhibiting polymers.
  • the storage tank in the dishwasher must be filled with rinse aid at regular intervals, with one filling sufficient for 10 to 50 rinse cycles, depending on the machine type. If the refilling of the tank is forgotten, glasses in particular unsightly due to limescale and deposits. In the prior art there are therefore some proposed solutions for integrating a rinse aid into the detergent for machine dishwashing. These proposed solutions are tied to the offer form of the compact molded body.
  • European patent application EP-A-0 851 024 (Unilever) describes two-layer detergent tablets, the first layer of which contains peroxy bleach, builder and enzyme, while the second layer contains acidifying agents and a continuous medium with a melting point between 55 and 70 ° C. and scale inhibitors contains. Due to the high-melting continuous medium, the acid (s) and scale inhibitor (s) should be released with a delay and cause a rinse aid effect. Powdered machine dishwashing detergents or surfactant-containing rinse aid systems are not mentioned in this document.
  • German patent application DE 198 51 426.3 (Henkel KGaA) describes a process for the production of multiphase detergent tablets, in which a particulate premix is pressed to give moldings which have a trough, which is subsequently made from a melt suspension or emulsion produced separately Envelope and one or more active substances dispersed or suspended in it) is filled.
  • the teaching of this document is also tied to the "tablet” offer. Powdery cleaners containing a "second phase", which achieve certain effects through controlled release of ingredients, are not disclosed.
  • the object of the present invention was to make the advantages of the controlled release of ingredients, in particular a rinse aid effect, also usable for powdered cleaning agents. It should be possible to dispense with complex process steps such as coating or multiple coating. Rather, an offer form should be provided which can be used both separately and in solid form as rinse aid to be metered by the consumer and as an admixture component for powdered machine dishwashing detergents. It has now been found that melt dispersions or emulsions made from coating substances with melting points above 30 ° C., active substances and optionally further ingredients such as emulsifiers, colorants and fragrances etc. can be converted into a particulate form after application to carrier materials, which form the above mentioned criteria is sufficient.
  • the present invention relates to a particulate rinse aid for machine dishwashing
  • Preferred particulate rinse aids include substances from the group of water-soluble detergent and cleaning agent ingredients, preferably carbonates, hydrogen carbonates, sulfates, phosphates and organic oligocarboxylic acids which are solid at room temperature in amounts of 55 to 85% by weight as carrier materials. , preferably from 60 to 80 wt .-% and in particular from 65 to 75 wt .-%, each based on the particle weight.
  • the coating substances that are used in the rinse aid particles according to the invention, not only the melting or solidification behavior, but also the material properties of the coating in the solidified state, ie in the rinse aid particles. Since the rinse aid particles are to be permanently protected against environmental influences during transport or storage, the coating substance must have a high stability with respect to the shock loads which occur, for example, during packaging or transport. The coating substance should therefore either have at least partially elastic or at least plastic properties in order to react to an impact load caused by elastic or plastic deformation and not to break.
  • the coating substance should have a melting range (solidification range) in such a temperature range in which the active substances to be coated are not exposed to excessive thermal stress. On the other hand, however, the melting range must be sufficiently high to still provide effective protection for the enclosed active substances at at least a slightly elevated temperature. According to the invention, the coating substances have a melting point above 30 ° C.
  • the coating substance does not have a sharply defined melting point, as usually occurs with pure, crystalline substances, but instead has a melting range that may include several degrees Celsius.
  • the coating substance preferably has a melting range which is between approximately 45 ° C. and approximately 75 ° C. In the present case, this means that the melting range occurs within the specified temperature interval and does not indicate the width of the melting range.
  • the width of the melting range is preferably at least 1 ° C., preferably about 2 to about 3 ° C.
  • waxes are understood to mean a number of natural or artificially obtained substances which generally melt above 40 ° C. without decomposition and which are relatively low-viscosity and not stringy even a little above the melting point. They have a strongly temperature-dependent consistency and solubility.
  • Natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, walnut, lanolin (wool wax), or broom wax, mineral wax or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin waxes or micro waxes.
  • vegetable waxes such as candelilla wax, carnauba wax, japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, or montan wax
  • animal waxes such as beeswax, shellac wax, walnut, lanolin (wool wax), or broom wax, mineral wax or ozokerite (earth wax), or
  • the chemically modified waxes include hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.
  • Synthetic waxes are generally understood to mean polyalkylene waxes or polyalkylene glycol waxes. Compounds from other classes of material which meet the stated requirements with regard to the softening point can also be used as covering materials.
  • suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl, which is commercially available under the name Unimoll 66 ® (Bayer AG), proved.
  • suitable Synthetic waxes of lower carboxylic acids and fatty alcohols such as dimyristyl tartrate, sold under the name Cosmacol ® ETLP (Condea).
  • synthetic or partially synthetic esters from lower alcohols with fatty acids from native sources can also be used.
  • Tegin ® 90 (Goldschmidt), a glycerol monostearate palmitate, falls into this class of substances.
  • Shellac for example Shellac-KPS-Dreiring-SP (Kalkhoff GmbH), can also be used as a coating material according to the invention.
  • wax alcohols are also included in the waxes in the context of the present invention, for example.
  • Wax alcohols are higher molecular weight, water-insoluble fatty alcohols with usually about 22 to 40 carbon atoms.
  • the wax alcohols occur, for example, in the form of wax esters of higher molecular fatty acids (wax acids) as the main component of many natural waxes.
  • wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol.
  • the coating of the solid particles coated according to the invention can optionally also contain wool wax alcohols, understood to be triterpenoid and steroid alcohols, for example lanolin understood, which is obtainable for example under the trade name Argowax ® (Pamentier & Co).
  • wool wax alcohols understood to be triterpenoid and steroid alcohols, for example lanolin understood, which is obtainable for example under the trade name Argowax ® (Pamentier & Co).
  • fatty acid glycerol esters or fatty acid alkanolamides can also be used, at least in part, as a constituent of the casing, but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds.
  • the coating substance contained in the rinse aid particles according to the invention preferably contains the majority of paraffin wax. This means that at least 50% by weight of the total contained substances, preferably more, consist of paraffin wax. Paraffin wax contents (based on the total coating substance) of approximately 60% by weight, approximately 70% by weight or approximately 80% by weight are particularly suitable, with even higher proportions of, for example, more than 90% by weight being particularly preferred. In a special embodiment of the invention, the total amount of the coating substance used consists exclusively of paraffin wax.
  • paraffin waxes have the advantage over the other natural waxes mentioned that there is no hydrolysis of the waxes in an alkaline cleaning agent environment (as is to be expected, for example, from the wax esters), since paraffin wax contains no hydrolyzable groups.
  • Paraffin waxes consist mainly of alkanes and low levels of iso- and cycloalkanes.
  • the paraffin to be used according to the invention preferably has essentially no constituents with a melting point of more than 70 ° C., particularly preferably of more than 60 ° C. Portions of high-melting alkanes in the paraffin can leave undesired wax residues on the surfaces to be cleaned or the goods to be cleaned if the melting temperature in the detergent solution drops below this. Such wax residues usually lead to an unsightly appearance on the cleaned surface and should therefore be avoided.
  • Preferred particulate rinse aid contain at least one paraffin wax with a melting range of 50 ° C to 60 ° C as the coating substance.
  • the paraffin wax content of alkanes, isoalkanes and cycloalkanes which are solid at ambient temperature is as high as possible.
  • the more solid wax components present in a wax at room temperature the more useful it is within the scope of the present invention.
  • With increasing proportion of solid wax components the resilience of the rinse aid particles against impacts or friction on other surfaces increases, which leads to a longer-lasting protection of the particles of active substances.
  • High proportions of oils or liquid wax components can weaken the particles, opening pores and exposing the active substances to the environmental influences mentioned above.
  • the coating substance can also contain one or more of the above-mentioned waxes or wax-like substances as the main constituent.
  • the mixture forming the coating substance should be such that the rinse aid particles are at least largely water-insoluble.
  • the solubility in water should not exceed about 10 mg / 1 at a temperature of about 30 ° C. and should preferably be below 5 mg / 1.
  • the coating should have the lowest possible solubility in water, even in water at an elevated temperature, in order to avoid as far as possible a temperature-independent release of the active substances.
  • Preferred particulate rinse aid according to the invention are characterized in that they contain one or more substances with a melting range of 40 ° C to 75 ° C in amounts of 6 to 30% by weight, preferably 7.5 to 25% by weight and in particular from 10 to 20% by weight, based in each case on the particle weight.
  • the active ingredients to be incorporated into the rinse aid particles according to the invention can be in both solid and liquid form at the processing temperature (i.e. at the temperature at which the particles are produced).
  • the active substances contained in the rinse aid particles fulfill certain tasks.
  • the cleaning performance can be improved by separating certain substances or by accelerating or delaying the release of additional substances.
  • Active ingredients, which are preferably incorporated into the rinse aid particles, are therefore those ingredients of detergents and cleaning agents that are crucially involved in the washing or cleaning process.
  • Preferred rinse aid particles therefore contain one or more substances from the groups of surfactants, enzymes, bleach, bleach activator, corrosion inhibitors, scale inhibitors, cobuilders and / or fragrances in amounts of 6 to 30% by weight, preferably 7.5 to 25 Wt .-% and in particular from 10 to 20 wt .-%, each based on the particle weight.
  • a melt suspension or emulsion can be produced, which in the finished rinse aid particle or in the ready-made detergent; which contains rinse aid particles according to the invention, provides additional detergent substance at a predetermined time.
  • rinse aid particles according to the invention for machine dishwashing can be produced in this way, which only release the additional surfactant at temperatures which household dishwashers only reach in the final rinse cycle. In this way, additional surfactant is available in the rinse cycle the drainage of the water accelerates and effectively prevents stains on the wash ware.
  • the use of additional rinse aid customary today can be dispensed with.
  • the active substance (s) is / are selected from the group of nonionic surfactants, in particular alkoxy-etherified alcohols. These substances are described in detail below.
  • bleaching agents Another class of active substances that can be incorporated particularly advantageously into the rinse aid particles according to the invention are bleaching agents. Particles can be produced here that release the bleaching agent only when certain temperatures are reached, for example ready-made cleaning agents that clean enzymatically in the pre-rinse cycle and only release the bleaching agent in the main rinse cycle. Cleaning agents for automatic dishwashing can also be produced in such a way that additional bleaching agents are released in the rinse cycle and are more effective in removing difficult stains, for example tea stains.
  • the active substance (s) is / are selected from the group of oxygen or halogen bleaches, in particular chlorine bleaches. These substances are also described in detail below.
  • Rinse aid particles preferred in the context of the present invention contain bleach activators as active substance, in particular from the groups of the polyacylated alkylenediamines, in particular tetraacetylethylene diamine (TAED), the N-acylimides, in particular N-nonanoylsuccinimide (NOSI), the acylated phenolsulfonates, in particular n-nonanoyl - or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA).
  • TAED tetraacetylethylene diamine
  • NOSI N-nonanoylsuccinimide
  • acylated phenolsulfonates in particular n-nonanoyl - or isononanoyloxybenzenesulfonate (n- or iso-NOBS)
  • MMA n
  • Fragrances can also be incorporated into the rinse aid particles according to the invention as active substances. All fragrances described in detail below can be used as an active substance.
  • cleaning agents result that release all or part of the perfume with a time delay.
  • cleaning agents for machine dishwashing can be produced according to the invention, in which the consumer experiences the perfume note even after the dishes have been cleaned when the machine is opened. In this way, the undesirable "alkaline smell" that is inherent in many automatic dishwashing detergents can be eliminated.
  • Corrosion inhibitors can also be incorporated as active ingredients in the rinse aid particles, it being possible to use the substances familiar to the person skilled in the art.
  • a combination of an enzyme (e.g. lipase) and lime soap dispersant has proven itself as a coating inhibitor.
  • the rinse aid particle can break under impact or friction.
  • additives can optionally be added to the coating substances. Suitable additives must be able to be mixed completely with the molten wax, must not significantly change the melting range of the coating substances, must improve the elasticity of the coating at low temperatures, must not generally increase the permeability of the coating to water or moisture and must not increase the viscosity of the melt Do not increase the wrapping material to such an extent that processing becomes difficult or even impossible.
  • Suitable additives which reduce the brittleness of a sheath consisting essentially of paraffin at low temperatures are, for example, EVA copolymers, hydrogenated resin acid methyl ester, polyethylene or copolymers of ethyl acrylate and 2-ethylhexyl acrylate.
  • a further useful additive in the use of paraffin as the sheath is the addition of a small amount of a surfactant, for example a C ,, _ 18 fatty alcohol sulfate. This addition results in a better wetting of the material to be embedded through the covering. It is advantageous to add the additive in an amount of about ⁇ 5% by weight, preferably ⁇ about 2% by weight, based on the coating substance.
  • the addition of an additive can in many cases lead to the fact that active substances can also be encased which, without the addition of an additive, generally form a tough, plastic body made of paraffin and partially dissolved active substance after the encapsulation material has melted.
  • anti-settling agents that can be used for this purpose, which are also referred to as floating agents, are known from the prior art, for example from the manufacture of lacquers and printing inks.
  • silicone oils dimethylpolysiloxanes, methylphenylpolysiloxanes, polyether-modified methylalkylpolysiloxanes
  • oligomeric titanates and silanes polyamines, salts from long-chain polyamines and polycarboxylic acids, Amine / amide-functional polyesters or amine / amide-functional polyacrylates are referred to.
  • Additives from the substance classes mentioned are commercially available in a wide variety.
  • the commercial products in the context of advantageous of the method according to the invention can be added as an additive, for example, Aerosil ® 200 (fumed silica, Degussa), Bentone ® SD-1, SD-2, 34, 52 and 57 (bentonite, Rheox) Bentone ® SD-3, 27 and 38 (hectorite, Rheox), Tixogel ® EZ 100 or VP-A (organically modified smectite, Südchemie), Tixogel ® VG, VP and VZ (montmorillonite loaded with QAV, Südchemie), Disperbyk ® 161 (block copolymer, Byk Chemistry), Borchigen ® ND (sulfo-free ion exchanger, Borchers), Ser-Ad ® FA 601 (servo), Solsperse ® (aromatic ethoxylate, ICI), Surfynol ®
  • auxiliaries mentioned can be used in varying amounts in the rinse aid particles according to the invention, depending on the coating material and active substance.
  • Usual use concentrations for the abovementioned anti-settling, anti-floating, thioxotropic and dispersing agents are in the range from 0.5 to 8.0% by weight, preferably between 1.0 and 5.0% by weight, and particularly preferably between 1.5 and 3.0% by weight, based in each case on the total amount of coating substance and active substances.
  • Particulate rinse aids preferred in the context of the present invention contain further auxiliaries from the group of anti-settling agents, floating agents, anti-floating agents, thixotropic agents and dispersing agents in amounts of 0.5 to 9% by weight, preferably between 1 and 7.5% by weight. , and particularly preferably between 1.5 and 5% by weight, in each case based on the particle weight.
  • emulsifiers from the group of fatty alcohols, fatty acids, polyglycerol esters and polyoxyalkylene siloxanes are particularly suitable. Further details on the production of the rinse aid particles according to the invention follow below.
  • Fatty alcohols are understood to mean the alcohols with 6 to 22 carbon atoms obtainable from native fats or oils via the corresponding fatty acids (see below). Depending on the origin of the fat or oil from which they are obtained, these alcohols can be substituted in the alkyl chain or partially unsaturated.
  • emulsifiers in the rinse agent according to the invention therefore preferably C 6 _ 22 fatty alcohols, C 8 _ 22 preferably fatty alcohols and especially C 12 _ 18 fatty alcohols, with particular preference to C 16. ] 8 fatty alcohols.
  • fatty acids obtained from vegetable or animal oils and fats can also be used as emulsifiers.
  • the fatty acids can be saturated or mono- to polyunsaturated regardless of their physical state. In the case of unsaturated fatty acids too, the species which are solid at room temperature are preferred over the liquid or pasty ones.
  • pure fatty acids can be used, but also the technical fatty acid mixtures obtained from the cleavage of fats and oils, these mixtures again being clearly preferred from an economic point of view.
  • individual species or mixtures of the following acids can be used as emulsifiers in the context of the present invention: caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, octadecan-12-ol-acid, arachic acid, behenic acid, lignoceric acid, cerotinic acid , Melissic acid, 10-undecenoic acid, petroselinic acid, petroselaidic acid, oleic acid, elaidic acid, ricinoleic acid, linolaidic acid, and ß-eläosterainic acid, gadoleic acid, erucic acid, brassidic acid.
  • fatty acids with an odd number of carbon atoms for example undecanoic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, nonadecanoic acid, heneicosanoic acid, tricosanic acid, pentacosanic acid, heptacosanoic acid.
  • emulsifier C 6 _ 22 fatty acids, C preferably g. 22 fatty acids and in particular C 12-0 8 fatty acids with particular preference for the C 16 . I8 - fatty acids used.
  • Particularly preferred emulsifiers in the context of the present invention are polyglycerol esters, in particular esters of fatty acids with polyglycerols. These preferred polyglycerol esters can be described by the general formula I.
  • R 1 in each glycerol unit is independently H or a fatty acyl radical having 8 to 22 carbon atoms, preferably having 12 to 18 carbon atoms, and n is a number between 2 and 15, preferably between 3 and 10.
  • This standard cosmetic work contains, for example, information on the keywords POLYGLYCERYL-3-BEESWAX, POLYGLYCERYL-3-CETYL ETHER, POLYGLYCERYL-4-COCOATE, POLYGLYCERYL-10-DECALINOLEATE, POLY- GLYCERYL-10-DECAOLETELARY POLYGLYTE GLYCERYL-2-DIISOSTEARATE, POLYGLYCERYL-3-DIISOSTEARATE, POLY- GLYCERYL-10-DIISOSTE ARATE, POLYGLYCERYL-2-DIOLEATE, POLY-
  • emulsifiers which can be used in the rinse aid particles according to the invention are substituted silicones which carry side chains reacted with ethylene or propylene oxide.
  • Such polyoxyalkylene siloxanes can be described by the general formula II
  • the polyoxyalkylenesiloxanes mentioned can also be etherified or esterified on the free OH groups of the polyoxyethylene or polyoxypropylene side chains.
  • the unetherified and unesterified polymer made from dimethylsiloxane with polyoxyethylene and / or polyoxypropylene is referred to in the INCI nomenclature as DIMETHICONE COPOLYOL and is known under the trade names Abil ® B (Goldschmidt), Alkasil ® (Rhönen-Poulenc), Silwet ® (Union Carbide) or Belsil ® DMC 6031 commercially available.
  • the esterified with acetic acid DIMETHICONE COPOLYOL ACETATE (for example Belsil DMC 6032 ®, -33 and -35, Wacker) and the Dimethicone Copolyol Butyl Ether (bsp KF352A, Shin Etsu) are usable in the context of the present invention also as emulsifiers.
  • emulsifiers that they can be used over a wide range.
  • emulsifiers of the type mentioned make up 1 to 25% by weight, preferably 2 to 20% by weight and in particular 5 to 10% by weight of the weight of the sum of shell materials and active substances.
  • Particulate rinse aids preferred in the context of the present invention additionally contain emulsifiers from the group of fatty alcohols, fatty acids, polyglycerol esters and / or polyoxyalkylene siloxanes in amounts from 0.1 to 5% by weight, preferably from 0.2 to 3.5% by weight, particularly preferably from 0.5 to 2% by weight and in particular from 0.75 to 1.25% by weight, based in each case on the particle weight.
  • the particulate rinse aid according to the invention can be produced in various ways.
  • Another object of the present invention is also a process for the production of particulate rinse aid, in which a melt suspension or emulsion is made
  • melt suspension or emulsion is first prepared, which may contain other active ingredients and auxiliary substances. This is placed on a carrier material and processed to give a shape in a mixture with this carrier material.
  • the coating substance makes up 25 to 85% by weight, preferably 30 to 70% by weight and in particular 40 to 50% by weight of the melt suspension or emulsion.
  • the melt suspension or emulsion can be applied to the carrier material in all customary mixing devices.
  • the shaping processing step for the mixture of melt and carrier material is likewise not subject to any procedural restrictions, so that the person skilled in the art can also choose from the processes familiar to him. In attempts by the applicant, procedures ren as preferred, in which the shaping processing takes place by granulating, compacting, pelleting, extruding or tableting.
  • the method according to the invention comprises the application of melts from enveloping and active substances to carrier materials.
  • the melt and carrier (s) can be present in varying amounts in the resulting rinse aid particles.
  • Preferred processes are characterized in that a mixture of 5 to 50% by weight, preferably 10 to 45% by weight, particularly preferably 15 to 40% by weight and in particular 20 to 35% by weight of a melt suspension or emulsion and 50 to 95% by weight, preferably 55 to 90% by weight, particularly preferably 60 to 85% by weight and in particular 65 to 80% by weight of carrier material (s) is shaped.
  • melt suspension or emulsion to be produced preferably meets certain criteria.
  • Methods in which the melt suspension or emulsion contains at least one paraffin wax with a melting range from 50 ° C. to 55 ° C. as the coating substance are preferred according to the invention.
  • the melt suspension or emulsion as active substance comprises one or more substances from the groups of surfactants, enzymes, bleaching agents, bleach activator, corrosion inhibitors, scale inhibitors, cobuilders and / or fragrances in amounts of 10 to 70% by weight, preferably from 15 to 60% by weight and in particular from 20 to 50% by weight, based in each case on the melt suspension or emulsion.
  • the rinse aid particles according to the invention can be given directly to the consumer, so that he also adds them to the detergent as needed. Because of this additional dosing step, however, in addition to the fixed dosage form and the addition to the same dosing compartment, the advantages over liquid rinse aid would be minimized. It is therefore preferred to admix the rinse aid particles according to the invention with particulate machine dishwashing detergents.
  • Another object of the present invention is therefore also a particulate machine dishwashing detergent, containing builders and optionally further ingredients from the groups of surfactants, enzymes, bleaching agents, bleach activators, corrosion inhibitors, polymers, colorants and fragrances, which contains a particulate rinse aid according to the invention in amounts of 0 , 5 to 30% by weight, preferably from 1 to 25% by weight and in particular from 5 to 15% by weight, in each case based on the total agent.
  • ingredients of automatic dishwashing detergents are described below. Some of these can also be contained as active substances or carrier materials in the rinse aid particles according to the invention.
  • the detergents for machine dishwashing according to the invention can contain all builders usually used in detergents and cleaning agents, in particular thus zeolites, silicates, carbonates, organic cobuilders and - if there are no ecological concerns about their use - also the phosphates.
  • the builders mentioned below are all suitable as carrier materials for the rinse aid particles according to the invention, as has already been explained above.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + 1 ⁇ , O, 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-0 164 514.
  • 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, Si 2 O 5 'yH 2 O are preferred, with ⁇ -sodium disilicate being able to be obtained, for example, by the method described in international patent application WO-A-91/08171 .
  • Amorphous sodium silicates with a modulus Na, O: SiO 2 from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • amorphous is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ). which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX E and by the formula
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • the alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the detergent and cleaning agent industry.
  • Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO 3 ) n and orthophosphoric acid H 3 PO 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in tissues and also contribute to cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 like “3 , melting point 60 °) and as a monohydrate (density 2.04 like “ 3 ). Both salts are white, water-soluble powders, which lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H, P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below).
  • NaH 2 PO 4 is acidic; it occurs when phosphoric acid is adjusted to pH 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH 2 PO 4 , is a white salt with a density of 2.33 "3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) and is light soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HP0 4 , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 like “3 , water loss at 95 °), 7 mol. (Density 1.68 like “ 3 , melting point 48 ° with loss of 5 H 2 O) and 12 mol. Water (density 1.52 like “3 , melting point 35 ° with loss of 5 H 2 O), becomes anhydrous at 100 ° and changes to the diphosphate Na 4 P 2 O 7 when heated more strongly.
  • Disodium hydrogenphosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is easily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals that like a dodecahydrate a density of 1.62 "3 and a melting point of 73-76 ° C (decomposition), as a decahydrate (corresponding to 19-20% P 2 O 5 ) have a melting point of 100 ° C. and, in anhydrous form (corresponding to 39-40% P 2 O 5 ), a density of 2.536 ′′ 3 .
  • Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH.
  • Tripotassium phosphate (tertiary or triphase potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder with a density of 2.56 "3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction Heating of Thomas slag with coal and potassium sulfate Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 like “3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 like " 3 , melting point 94 ° with loss of water) .
  • Substances are colorless crystals that are soluble in water with an alkaline reaction.
  • Na 4 P 2 O 7 is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33, preferably 3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4. Condensation of the NaH 2 PO 4 or the KH 2 PO 4 produces higher moles.
  • Sodium and potassium phosphates in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate)
  • sodium tripolyphosphate sodium tripolyphosphate
  • n 3
  • Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate.
  • pentasodium triphosphate In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% by weight solution (> 23% P 2 O 5 , 25% K 2 O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:
  • these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; also mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and Sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can be used according to the invention.
  • Organic cobuilders which can be used in the dishwasher detergents according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.
  • Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
  • Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
  • the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M.
  • the respective acid form which was basically determined by means of gel permeation chromatography (GPC), a UV Detector was used.
  • the measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the investigated polymers. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard.
  • the molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
  • Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.
  • copolymeric polycarboxylates 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 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • allylsulfonic acids such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • biodegradable polymers made up of more than two different monomer units, for example those which are salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or which are used as monomers Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.
  • copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids their salts or their precursor substances.
  • Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A-195 40 086 that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups.
  • 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 organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol.
  • DE dextrose equivalent
  • Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used.
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 as well as international patent applications WO 92 / 18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608.
  • An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable.
  • a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
  • Ethylene diamine N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are 3 to 15% by weight in formulations containing zeolite and / or silicate.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • Such cobuilders are described, for example, in international patent application WO 95/20029.
  • phosphonates are, in particular, hydroxyalkane or aminoalkane phosphonates.
  • hydroxyalkane phosphonates l-hydroxyethane-l, l-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9).
  • Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher levels of mologist in question.
  • HEDP is preferably used as the builder from the class of the phosphonates.
  • the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • substances from the groups of surfactants, bleaching agents, bleach activators, enzymes, polymers and dyes and fragrances are particularly important ingredients of cleaning agents. Important representatives from the substance classes mentioned are described below.
  • the automatic dishwashing detergents according to the invention particularly preferably contain nonionic surfactants, it being again preferred that part, preferably a large part, of the total surfactant contained in the detergents is contained in the rinse aid particles. This is particularly advantageous, since in this way it is possible to provide particulate dishwashing detergents which develop their cleaning performance in the main wash cycle and only release the surfactant from the rinse aid particles in the rinse aid cycle.
  • the presence of surfactants in the rinse cycle of a machine dishwashing process has a positive effect on the gloss and the reduction of limescale deposits.
  • the cleaning agent according to the invention contains nonionic surfactants, in particular nonionic surfactants. side from the group of alkoxy alcohols.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12.14 alcohols with 3 EO or 4 EO, C 9 - ,, alcohol with 7 EO, C 13 - 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 - 18 alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C I2 - 14 alcohol with 3 EO and C 12th 18 - alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • alkyl glycosides of the general formula RO (G) can also be used as further nonionic surfactants, 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 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.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, 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 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 nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (III),
  • RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid 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.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (IV), R ! -OR 2nd
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • nonionic surfactants in addition to the pure nonionic surfactants, other substances from the group of the ionic surfactants, for example the anionic or cationic surfactants, can of course also be present in the automatic dishwashing agents according to the invention.
  • bleaching agents in W ater ⁇ H 2 O 2 compounds yielding sodium perborate tetrahydrate and sodium perborate monohydrate are particularly important.
  • Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • Cleaning agents according to the invention can also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
  • Peroxyacids are further typical organic bleaching agents, examples of which include alkylperoxyacids and arylperoxyacids.
  • Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ - Naphtoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, ⁇ - phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-
  • PAP phthaloiminoperoxyhexanoic acid
  • Chlorine or bromine-releasing substances can also be used as bleaching agents in the cleaning agents according to the invention for machine dishwashing.
  • Suitable chlorine or bromine-releasing materials include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium.
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
  • the bleaches mentioned can also be introduced in whole or in part via the rinse aid particles according to the invention into the automatic dishwasher detergents according to the invention in order to achieve “post-bleaching” in the rinse cycle.
  • Bleach activators that support the effect of the bleaching agents have already been mentioned above as a possible ingredient of the rinse aid particles.
  • Known bleach activators are compounds which contain one or more N- or O-acyl groups, such as substances from the class of anhydrides, esters, imides and acylated imidazoles or oximes. Examples are tetraacetylethylene diamine TAED, tetraacetylmethylene diamine TAMD and tetraacetylhexylene diamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-l, 3,5-triazine DADHT and isatoic anhydride ISA.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms. Atoms, and / or optionally substituted perbenzoic acid can be used. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • bleach catalysts can also be incorporated into the rinse aid particles.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.
  • Bleach activators from the group of multi-acylated alkylenediamines in particular tetraacetylethylene diamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or Isononanoyloxybenzenesulfonat (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), preferably in amounts up to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%, particularly 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-% based on the total agent used.
  • TAED tetraacetylethylene diamine
  • N-acylimides in particular N-nonanoylsuccinimide (NOSI)
  • NOSI
  • Bleach-boosting transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group consisting of manganese and / or cobalt salts and / or complexes, particularly preferably cobalt (ammin) - Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of manganese sulfate are used in conventional amounts, preferably in an amount of up to 5% by weight, in particular 0.0025% by weight .-% to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt .-%, each based on the total agent used. But in special cases, more bleach activator can be used.
  • Suitable enzymes in the cleaning agents according to the invention are, in particular, those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases help to remove stains such as protein, fat or starchy stains. Oxidoreductases can also be used for bleaching. Particularly well suited are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants.
  • lipolytic acting enzymes are the well-known cutinases.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • Suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases.
  • the enzymes can be adsorbed on carriers or embedded in coating 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 0.5 to about 4.5% by weight.
  • Dyes and fragrances can be added to the automatic dishwashing agents according to the invention in order to improve the aesthetic impression of the resulting products and to provide the consumer with a visually and sensorially "typical and unmistakable" product in addition to performance.
  • Individual fragrance compounds for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allylcyclohexyl benzylatepylpropylate, stylate propylate styrene.
  • the ethers include, for example, benzylethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, and the ketones, for example, the ionones, ⁇ -Isomethyl ionone and methyl cedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil. Neroliol, orange peel oil and sandalwood oil.
  • the fragrances can be incorporated directly into the cleaning agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release.
  • Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries. Incorporation of the fragrances into the rinse aid particles according to the invention is also possible and leads to a scent impression when the machine is opened (see above).
  • the agents produced according to the invention can be colored with suitable dyes.
  • Preferred dyes the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity to the substrates to be treated with the compositions, such as glass, ceramics or plastic dishes, so as not to stain them.
  • the cleaning agents according to the invention can contain corrosion inhibitors to protect the items to be washed or the machine, silver protection agents in particular being particularly important in the field of automatic dishwashing.
  • silver protection agents selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular.
  • Benzotriazole and / or alkylaminotriazole are particularly preferably to be used.
  • active chlorine-containing agents are often found in cleaner formulations, which can significantly reduce the corroding of the silver surface.
  • oxygen- and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds.
  • Salt-like and complex-like inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used.
  • transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides cobalt or manganese and manganese sulfate.
  • Zinc compounds can also be used to prevent corrosion on the wash ware.
  • composition of the rinse aid particles according to the invention is designed such that they do not dissolve, or only to a minor extent, in the main rinse cycle (and also in optional pre-rinse cycles). This ensures that the active substances are only released in the rinse cycle and develop their effect here.
  • physical assembly is required so that the rinse aid particles are not pumped out when the water is changed in the machine and are therefore no longer available for the rinse aid.
  • Standard household dishwashers contain a sieve insert in front of the drain pump, which pumps the water or cleaning solution out of the machine after the individual cleaning cycles, which is intended to prevent the pump from becoming blocked by dirt residues.
  • the size and shape of the rinse aid particles according to the invention are now preferably designed such that they do not pass the sieve insert of the dishwasher even after the cleaning cycle, ie after exposure to movement in the machine and the cleaning solution. This ensures that there are rinse aid particles in the dishwasher in the rinse cycle, which release the active substance (s) under the action of the warmer water and bring about the desired rinse aid effect.
  • Particulate machine dishwashing detergents preferred in the context of the present invention are characterized in that the particulate rinse aid has particle sizes between 1 and 20 mm, preferably between 1.5 and 15 mm and in particular between 2 and 12 mm.
  • the rinse aid articles with the above-mentioned sizes can protrude from the matrix of the other particulate ingredients, but the other particles can also have sizes that lie in the range mentioned, so that overall a cleaning agent is formulated that consists of large detergent and There are rinse aid particles.
  • the rinse aid particles according to the invention are colored, for example thus have a red, blue, green or yellow color, it is advantageous for the appearance of the product, ie the entire detergent, if the rinse aid particles are visibly larger than the matrix of the particles of other ingredients of the detergent.
  • particulate machine dishwashing agents according to the invention are preferred which (without taking into account the rinse aid articles) have particle sizes between 200 and 3000 ⁇ m, preferably between 300 and 2500 ⁇ m and in particular between 400 and 2000 ⁇ m.
  • the optical attraction of such compositions can also be increased by contrasting coloring of the powder matrix or by the shape of the rinse aid particles. Since technically uncomplicated processes can be used to manufacture the rinse aid articles, it is possible to offer them in a wide variety of forms without any problems.
  • particle shape which has an approximately spherical shape
  • cylindrical or cube-shaped particles for example, can be produced and used.
  • Other geometric shapes can also be realized.
  • Special product designs can contain, for example, star-shaped rinse aid articles. Disks or shapes which show plants and animal bodies, for example tree, flower, blossom, sheep, fish, etc., as base area can also be produced without problems.
  • interesting visual incentives can also be created in this way by producing the rinse aid articles in the form of a stylized glass in order to visually underline the rinse aid effect in the product. There are no limits to your imagination.
  • the cleaning agents according to the invention are formulated as a powder mixture, it is possible - especially in the case of very different sizes of rinse aid particles and cleaning agents.
  • detergent matrix - on the one hand partial separation occurs when the package is shaken, on the other hand the dosage can be different in two successive cleaning cycles, since the consumer does not always dose the same amount of detergent and rinse aid. If it is desired to technically always use the same amount per cleaning cycle, this can be achieved by packaging the agents according to the invention in bags made of water-soluble film, which is familiar to the person skilled in the art.
  • the present invention also relates to particulate machine dishwashing detergents in which a dosing unit is welded into a bag made of water-soluble film.
  • the cleaning agents according to the invention can be produced in a manner known per se.
  • a method of producing powdered machine dishwashing detergent with rinse aid effect, in which a powdered machine dishwashing agent known per se is mixed with rinse aid particles according to the invention, is therefore a further subject of the present invention.
  • kits-of-parts according to the invention in which the particle sizes of the automatic dishwashing detergent (taking into account the rinse aid articles) are in the range from 400 to 2500 ⁇ m, preferably from 500 to 1600 ⁇ m and in particular from 600 to 1200 ⁇ m.
  • kits-of-parts according to the invention are preferred, in which the mesh size or hole size of the sieve insert is 1 to 4 mm and the rinse aid articles are larger than this mesh size or hole size of the sieve insert.
  • the kit-of-parts according to the invention is not limited to the specific shape of the sieve insert in which it replaces or covers the insert located in the machine. According to the invention, it is also possible and preferred to include a sieve insert in the kit-of-parts which has the shape of a basket which can be hung in the dishwasher - for example on the cutlery basket - in a known manner. In this way, a sieve insert designed in this way replaces the dosing chamber, i.e. the consumer doses the automatic dishwashing agent according to the invention directly into this sieve insert, which acts in the cleaning and rinse cycle in the manner described above.
  • FIG. 1 and FIG. 2 show cleaning agents according to the invention for machine dishwashing, in which the matrix of cleaning agent particles has average particle sizes of 600 ⁇ m, while the rinse aid articles according to the invention contained in the cleaning agent have average particle sizes of 8 mm.
  • the rinse aid articles are colored blue for visually appealing contrasting, while the base powder is white and additionally has red colored spots, ie red colored particles of the same particle size.
  • the colors red and blue are interchanged, ie the base powder is white and has blue speckled particles, while the rinse aid articles are red.
  • FIGS. 3 and 4 show cleaning agents according to the invention, in which the cleaning agent particles, i.e. the “base powder” has a larger average particle size.
  • the powder matrix here has average particle sizes of 1800 ⁇ m, while the rinse aid articles according to the invention contained in the detergent again have average particle sizes of 8 mm.
  • the coloring of the particles was carried out analogously to FIGS. 1 and 2, ie in The rinse aid articles are colored blue in Figure 3, while the base powder is white and additionally have red color speckles, in Figure 4 the colors red and blue are in turn interchanged, ie the base powder is white and has blue speckle particles, while the rinse aid articles are red.
  • FIGS. 5, 6 and 7 show a cleaning agent according to the invention for machine dishwashing, in which the rinse aid articles have an average particle size which is in the same order of magnitude as that of the base powder.
  • Such cleaning agents are extremely suitable for use in the kit-of-parts according to the invention.
  • the powder matrix here has average particle sizes of 1800 ⁇ m, while the rinse aid articles according to the invention contained in the cleaning agent also have average particle sizes of 1800 ⁇ m.
  • the rinse aid articles are colored red, while the base powder is white.
  • the rinse aid articles are colored blue.
  • FIG. 7 finally shows a cleaning agent according to the invention in which both red and blue colored rinse aid articles are present.
  • sprinkles of color can of course also be used, for example as a replacement for the red or blue rinse aid articles in FIG. 7. Examples:
  • a melt emulsion was produced, which can be processed to form rinse aid articles either directly or after being placed on a carrier material.
  • melt emulsion SE 1 By heating the casing material and stirring in the active substances and optional auxiliaries, a melt emulsion SE 1 was produced, the composition (% by weight, based on the melt) of which is given in the table below:
  • This melt emulsion can be fed directly to a grooving or pastillation, which results in rinse aid articles of the specified composition.
  • mixing with carrier substances is also possible:
  • step a) The melt emulsion produced in step a) was added to calcined sodium carbonate in a Lödige laboratory mixer with the mixing tools running. The resulting premix contained 25% by weight of the melt emulsion and 75% by weight sodium carbonate. Rinse aid premixes containing 25% by weight of melt emulsion and 75% by weight of sodium tripolyphosphate can be produced completely analogously.
  • the premix was extruded through a 5 mm perforated plate in a laboratory extruder from Leistriz and subsequently rounded.
  • a commercially available powdered detergent for automatic dishwashing was used in a universal cleaning program.
  • the program was carried out under the same conditions once without a commercial rinse aid (storage tank in the dishwasher emptied), with a commercial rinse aid (dosage of 3 ml of commercial rinse aid from the storage tank in a rinse cycle) and once with the rinse aid articles according to the invention (addition of 3.3 g rinse aid articles) 20 g agent, dosage before the main wash).
  • the storage tank for the commercial rinse aid was of course empty, i.e. the rinse aid performance can only be attributed to the rinse aid articles according to the invention.
  • composition 30% protein / protein 30% starch 30% fat 10% water / emulsifier
  • the rinse aid effect was assessed by visual inspection of the objects in a box, the walls of which are lined with black velvet, with grades 0 to 8 being assigned; the top grade 8 refers to surfaces free of deposits and water droplets. If the grade is ⁇ 4, the deposits and drops can also be clearly recognized outside the box, ie they are perceived by the consumer as disturbing.
  • the drying (T) was assessed by counting the individual water drops on the items to be washed in the above. Box.
  • the top grade 0 shows no drops, other values indicate how many drops are visible on the dishes.
  • the data given in the following table are the mean values from 10 items of crockery that were contained in the relevant machine load.
  • the table shows that the agents according to the invention achieve or even exceed the rinse aid performance of the conventional combination of detergent and separately metered rinse aid through the use of the rinse aid articles according to the invention, although less rinse aid (based on active substance) is used and the particles according to the invention are already used in the main rinse cycle Are machine, so they are physically and chemically loaded.
  • the drop formation on the wash ware is only visible in the black box, brilliant shiny wash ware is observed outside the box.

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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

L'invention concerne des particules d'agent mouillant contenant entre 30 et 90 % en poids d'une ou de plusieurs substances support, entre 5 et 40 % en poids d'une ou de plusieurs substances enveloppantes ayant un point de fusion supérieur à 30 DEG C, entre 5 et 40 % en poids d'un ou de plusieurs principes actifs, ainsi qu'entre 0 et 10 % en poids d'autres principes actifs et auxiliaires. Ces particules d'agent mouillant s'utilisent pour parvenir à un effet mouillant dans des lave-vaisselle ménagers. Ces particules d'agent mouillant s'obtiennent avantageusement par procédé d'agglomération par compression. Ces particules d'agent mouillant peuvent être incorporés dans des produits pulvérulents pour laver la vaisselle.
PCT/EP2000/002462 1999-03-30 2000-03-21 Agent mouillant particulaire et produit de lavage pour lave-vaisselle WO2000060047A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU41067/00A AU4106700A (en) 1999-03-30 2000-03-21 Particulate clear rinse agent and dish washer detergent

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1999114364 DE19914364A1 (de) 1999-03-30 1999-03-30 Teilchenförmiger Klarspüler und maschinelle Geschirrspülmittel
DE19914364.1 1999-03-30

Publications (1)

Publication Number Publication Date
WO2000060047A1 true WO2000060047A1 (fr) 2000-10-12

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AU (1) AU4106700A (fr)
CA (1) CA2303588A1 (fr)
DE (1) DE19914364A1 (fr)
WO (1) WO2000060047A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1103599A1 (fr) * 1999-11-27 2001-05-30 Henkel Kommanditgesellschaft auf Aktien Agent de rinçage particulaire et composition pour lavage de la vaiselle en machine
WO2003006592A2 (fr) * 2001-07-11 2003-01-23 Reckitt Benckiser N.V. Composition de detergent a vaisselle

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10015289A1 (de) * 2000-03-28 2001-10-18 Henkel Kgaa Teilchenförmige maschinelle Geschirrspülmittel mit Klarspüleffekt

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3421940A (en) * 1961-01-27 1969-01-14 Bohme Fettchemie Gmbh Washing agents and process for machine washing of dishes
US3637509A (en) * 1970-02-10 1972-01-25 Grace W R & Co Chlorinated machine dishwashing composition and process
US4115292A (en) * 1977-04-20 1978-09-19 The Procter & Gamble Company Enzyme-containing detergent articles
FR2666349A1 (fr) * 1990-08-28 1992-03-06 Nln Sa Detergent en sachet-dose pour le nettoyage de la vaisselle.
US5453216A (en) * 1994-04-28 1995-09-26 Creative Products Resource, Inc. Delayed-release encapsulated warewashing composition and process of use
DE19817964A1 (de) * 1998-04-22 1999-10-28 Henkel Kgaa Umhüllte Reinigungsmittelkomponente

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3421940A (en) * 1961-01-27 1969-01-14 Bohme Fettchemie Gmbh Washing agents and process for machine washing of dishes
US3637509A (en) * 1970-02-10 1972-01-25 Grace W R & Co Chlorinated machine dishwashing composition and process
US4115292A (en) * 1977-04-20 1978-09-19 The Procter & Gamble Company Enzyme-containing detergent articles
FR2666349A1 (fr) * 1990-08-28 1992-03-06 Nln Sa Detergent en sachet-dose pour le nettoyage de la vaisselle.
US5453216A (en) * 1994-04-28 1995-09-26 Creative Products Resource, Inc. Delayed-release encapsulated warewashing composition and process of use
DE19817964A1 (de) * 1998-04-22 1999-10-28 Henkel Kgaa Umhüllte Reinigungsmittelkomponente

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1103599A1 (fr) * 1999-11-27 2001-05-30 Henkel Kommanditgesellschaft auf Aktien Agent de rinçage particulaire et composition pour lavage de la vaiselle en machine
WO2003006592A2 (fr) * 2001-07-11 2003-01-23 Reckitt Benckiser N.V. Composition de detergent a vaisselle
WO2003006592A3 (fr) * 2001-07-11 2003-05-22 Reckitt Benckiser Nv Composition de detergent a vaisselle

Also Published As

Publication number Publication date
CA2303588A1 (fr) 2000-09-30
DE19914364A1 (de) 2000-10-05
AU4106700A (en) 2000-10-23

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