WO2001044422A2 - Agent mouillant particulaire et produit de rinçage pour la vaisselle lavee en machine - Google Patents

Agent mouillant particulaire et produit de rinçage pour la vaisselle lavee en machine Download PDF

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Publication number
WO2001044422A2
WO2001044422A2 PCT/EP2000/012207 EP0012207W WO0144422A2 WO 2001044422 A2 WO2001044422 A2 WO 2001044422A2 EP 0012207 W EP0012207 W EP 0012207W WO 0144422 A2 WO0144422 A2 WO 0144422A2
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WIPO (PCT)
Prior art keywords
weight
rinse aid
particulate
acid
detergent
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PCT/EP2000/012207
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German (de)
English (en)
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WO2001044422A3 (fr
Inventor
Andreas Ferencz
Jürgen Härer
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Henkel Kommanditgesellschaft Auf Aktien
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Priority to AU17071/01A priority Critical patent/AU1707101A/en
Publication of WO2001044422A2 publication Critical patent/WO2001044422A2/fr
Publication of WO2001044422A3 publication Critical patent/WO2001044422A3/fr

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    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3726—Polyurethanes
    • 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
    • C11D17/04—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 domestic 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 switched on, but is only selected by the consumer in exceptional cases, so that in most machines a main wash cycle, an intermediate wash 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. Depending on the type of machine, one fill is sufficient for 10 to 50 wash cycles. If you forget to fill up the tank, glasses in particular become 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.
  • the European patent application EP-A-0 851 024 (Unilever) describes two-layer detergent tablets, the first layer of which is peroxy bleach. Builder and enzyme contains, while the second layer contains acidifying agents and a continuous medium with a melting point between 55 and 70 ° C and scale inhibitors. Due to the high-melting continuous medium, the acid (s) and deposit inhibitor (s) should be released with a delay and produce a rinse aid effect. Powdered machine dishwashing detergents or surfactant-containing rinse aid systems are not mentioned in this document.
  • 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. Rather, an offer form should be provided which can be used both separately and in solid form as a rinse aid to be metered by the consumer and as an admixture component for powdered machine dishwashing detergents.
  • the present invention relates to a particulate rinse aid for machine dishwashing, which a) 10 to 90% by weight of one or more matrix materials selected from polymers solid at room temperature, b) 90 to 10% by weight of one or more active substances, and c) Contains 0 to 10 wt .-% of other active ingredients and auxiliaries.
  • Suitable matrix materials are all substances which are solid at room temperature and which can serve as matrix material for the active substances and any further active substances and auxiliaries which may be present and which enable the release by means of a special solution kinetics of these substances in a rinse cycle.
  • the matrix materials are preferably meltable polymers or polymer mixtures.
  • Polyurethanes have proven to be particularly suitable polymers, which are preferably meltable and / or soluble or swellable in water.
  • the polyurethanes are usually obtained by reacting polyols with a di- or polyisocyanate compound.
  • polyol monomers are dihydric and polyhydric alkyl alcohols having 2 to 22, preferably 6 to 22 carbon atoms, polyether polyols such as polyalkylene glycols, e.g. Polyethylene glycol or polypropylene glycol, polyester polyols suitable. Crystallizing diols, in particular from the following group, are particularly suitable
  • Polyester diol in particular a polycaprolactone diol with a molecular weight of 200 to 50,000, in particular 200 to 5,000, optionally at least one diol which is capable of ion formation. in particular for the formation of carboxylate, sulfate or ammonium ions and optionally at least one 3- or higher-functional polyol such as glycerol and TMP and optionally at least one hydrophobic diol, in particular from the group:
  • Alkanediol with 1 to 100, in particular from 2 to 50, particularly preferably 5 to 30, carbon atoms.
  • Both aliphatic and aromatic isocyanates are suitable as the isocyanates.
  • aliphatic isocyanates are linear alkyl diisocyanates, where the alkyl group can have a chain length of 4 to 12 carbon atoms.
  • aromatic di- and polyisocyanates are ditolylene diisocyanates, xylylene diisocyanates, divinyialcan diisocyanates, naphthylene diisocyanates etc.
  • aromatic diisocyanates are 4,4'-methylene di (phenyl isocyanate) (MDI), hexamethylene diisocyanate (HDI) , 1-isocyanatomethyl-3-isocyanato-l, 5,5-trimethylcyclohexane (IPDI), toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, naphthylene-1, 5-diisocyanate, divinylmethane-4, 4'-isocyanate, tetramethylxylene diisocyanate (TMXDI); l, 3-bis (l-isocyanato-l-methylethyl) benzene, hydrogenated MDI (H ⁇ 2 MDI), xylene diisocyanate (XDI), 4,4'-diphenyldimethylmethane diisocyanate, di- and tetraalkyl-diphenylmethane diiso
  • Sulfur-containing polyisocyanates are obtained, for example, by reacting 2 mol of hexamethylene diisocyanate with 1 mol of thiodlycol or dihydroxydihexysulfide.
  • Other important diisocyanates are trimethyl xamethylendiisocyanat. 1, 4-diisocyanatobutane, 1, 12-diisocyanatododecane and dimer fatty acid diisocyanate.
  • tetramethylene hexamethylene, undecan, dodecamethylene, 2,2,4-trimethylhexane, 1,3-cyclohexane, 1,4-cyclohexane, 1,3, or 1,4-tetramethylxylene , Isophorone, 4,4-dicyclohexylmethane and lysine ester diisocyanate.
  • the isocyanates can be polymers of one polyol monomer and one polyisocyanate monomer or copolymers of several polyol monomers and isocyanate monomers.
  • An example of a suitable copolymer is a polyurethane that contains a polyethyleneglycol and a C 2 - 8 alkyldiol and TMXDI as isocyanate component as polyol monomers.
  • the ratio of the isocyanate groups to the hydroxyl groups can vary from 0.5 to 1.2: 1, in particular from 0.7 to 1: 1.
  • the matrix materials are contained in the particulate rinse aid according to the invention preferably in an amount of 10 to 70% by weight, particularly preferably in an amount of 25 to 60% by weight, based on the finished particulate rinse aid.
  • the active substances to be incorporated into the rinse aid articles according to the invention can be in solid as well as 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 articles 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 articles, are therefore those ingredients of detergents and cleaning agents that are crucially involved in the washing or cleaning process.
  • Preferred rinse aid articles therefore contain one or more substances from the groups of surfactants, bleaching agents, bleach activator, corrosion inhibitors, scale inhibitors and / or cobuilders in amounts of 6 to 30% by weight, preferably 7.5 to 25, as the active substance Wt .-% and in particular from 10 to 20 wt .-%, each based on the particle weight. Fragrances and enzymes can also be present as active substances, the components usually being present in amounts of up to 2% by weight.
  • rinse aid articles By incorporating surfactants into the melted matrix material, rinse aid articles can be produced which, for. B. in a ready-made cleaning agent; contains the rinse aid article according to the invention, provides additional wash-active substance at a predetermined time.
  • rinse aid articles according to the invention for machine dishwashing can be produced in this way, which release the additional surfactant only at temperatures which household dishwashers only reach in the final rinse cycle. In this way, additional surfactant is available in the rinse cycle, which accelerates the drainage of the water and thus 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 the nonionic surfactants, in particular the alkoxylated alcohols. These substances are described in detail below.
  • bleaching agents Another class of active substances that can be incorporated with particular advantage into the rinse aid articles 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 bleaching agents, in particular the chlorine bleach. These substances are also described in detail below.
  • Rinse aid articles preferred in the context of the present invention contain bleach activators as active substance, in particular from the groups of polyacylated alkyl diamines, in particular tetraacetyl ethylene diamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), of acylated phenolsulfonates, in particular n-nonanoyl - Or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-Mo ⁇ holinium-acetonitrile-methyl sulfate (MMA).
  • bleach activators as active substance, in particular from the groups of polyacylated alkyl diamines, in particular tetraacetyl ethylene diamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), of acylated phenolsulfonates, in particular n-nonano
  • 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.
  • the incorporation of fragrances into the rinse aid articles results in cleaning agents which release all or part of the perfume with a time delay. In this way, for example, 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 "alkali smell", which is inherent in many automatic dishwashing detergents, can be eliminated.
  • Corrosion inhibitors can also be introduced into the rinse aid as an active substance, 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 particulate rinse aid according to the invention can be coated with coating materials to protect the particles.
  • coating materials to protect the particles.
  • the purpose of the coating substances is to permanently protect the rinse aid particles against environmental influences during transport or storage.
  • the enveloping substance should therefore have a high stability against, for example, shock loads occurring 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 substances protect the active substances from premature release during the rinse cycles that take place before the actual rinse cycle.
  • the coating substances used in the rinse aid articles according to the invention are accordingly subject to various requirements with regard to melting and solidification behavior and / or dissolving behavior.
  • so-called LCST polymers are used as coating substances. These are substances that have better solubility at low temperatures than at higher temperatures. They are also referred to as substances with a lower critical segregation temperature. These substances are usually polymers. Depending on the application conditions, the lower critical separation temperature should be between room temperature and the temperature of the heat treatment, for example between 20 ° C., preferably 30 ° C. and 100 ° C., in particular between 30 ° C. and 50 ° C.
  • the LCST substances are preferably selected from alkylated and / or hydroxyalkylated polysaccharides, cellulose ethers, polyisopropyl acrylamide, copolymers of polyisopropylacrylamide and blends of these substances.
  • alkylated and / or hydroxyalkylated polysaccharides are hydroxypropyl methyl cellulose (HPMC), ethyl (hydroxyethyl) cellulose (EHEC), hydroxypropyl cellulose (HPC), methyl cellulose (MC), ethyl cellulose (EC), carboxymethyl cellulose (CMC), carboxymethyl methyl cellulose (CMMC), Hydroxybutylcellulose (HBC), Hydroxybutylmethylcellulose (HBMC), Hydrdoxyethylcellulose (HEC), Hydroxyethylcarboxymethylcellulose (HECMC), Hydroxyethylethylcellulose (HEEC), Hydroxypropylcellulose (HPC), hydroxypropylcarboxymethylcellulose (HPCMC), hydroxyethylmethylcellulose (HEMC), methylhydroxyethylcellulose (MHEC), methylhydroxyethylpropylcellulose (MHEPC), methylcellulose (MC) and propylcellulose (PC) and mixtures thereof, wherein carboxymethylcellulose
  • LCST substances are cellulose ethers and mixtures of cellulose ethers with carboxymethyl cellulose (CMC).
  • CMC carboxymethyl cellulose
  • Further polymers which show a lower critical segregation temperature in water and which are also suitable are polymers of mono- or di-N-alkylated acrylamides, copolymers of mono- or di-N-substituted acrylamides with acrylates and / or acrylic acids or mixtures of intertwined networks of the above (co) polymers.
  • polyethylene oxide or copolymers thereof such as ethylene oxide / propylene oxide copolymers and graft copolymers of alkylated acrylamides with polyethylene oxide, polymethacrylic acid, polyvinyl alcohol and copolymers thereof, polyvinyl methyl ether, certain proteins such as poly (VATGVV), a repeating unit in the natural protein elastin and certain alginates.
  • LCST lower critical separation temperature
  • coating substances are used which 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.
  • the melting range must be sufficiently high to still provide effective protection for the enclosed active substances at at least a slightly elevated temperature.
  • the coating substances preferably have a melting point above 30 ° C.
  • 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.
  • the waxes are divided into three groups according to their origin, natural waxes, chemically modified waxes and synthetic waxes.
  • 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 substances which meet the stated requirements with regard to the Meet softening point. Higher esters of phthalic acid, in particular dicyclohexyl phthalate, which is commercially available under the name Unimoll 66 (Bayer AG), have proven to be suitable synthetic compounds, for example. Are also suitable Synthetic waxes of lower carboxylic acids and fatty alcohols, such as dimyristyl tartrate, sold under the name Cosmacol ® ETLP (Condea). Conversely, 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 present invention the solid particles coated can optionally also contain wool wax alcohols which are understood to Trite ⁇ enoid- and steroid alcohols, for example lanolin understood, which is obtainable for example under the trade name Argowax ® (Pamentier & Co).
  • wool wax alcohols which are understood to Trite ⁇ enoid- 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.
  • washing agents contain predominantly 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.
  • the total amount of the coating substance used consists exclusively of paraffin wax.
  • Paraffin waxes have the advantage over the other natural waxes mentioned in the context of the present invention that there is no hydrolysis of the waxes in an alkaline detergent 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.
  • 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 an increasing proportion of solid wax components the resilience of the rinse aid articles to 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 articles at least are largely insoluble in water.
  • 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 principle described above serves to delay the release of ingredients at a certain point in the cleaning cycle and should be independent of the temperature of the cleaning cycle.
  • the particulate rinse aid is first coated with an LCST substance and then with a substance which has a melting range or melting point of 40 to 75 ° C.
  • a wax or a substance with wax-like properties is used as the second coating substance, it is preferably composed of one or more substances with a melting range from 40 ° C. to 75 ° C. in amounts of 6 to 30% by weight, preferably 7.5 up to 25% by weight and in particular from 10 to 20% by weight, in each case based on the particle weight.
  • the rinse aid article 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, and must the permeability of the coating to water or moisture generally do not increase and must not increase the viscosity of the melt of the coating material to such an extent that processing becomes difficult or even impossible.
  • Suitable additives which reduce the brittleness of an envelope 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.
  • Another useful additive when using paraffin as a coating is the addition of a small amount of a surfactant, for example one 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 from paraffin and partially dissolved active substance after the encapsulation material has melted.
  • the 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.
  • surface-active substances waxes dispersed in solvents, montmorillonites, organically modified bentonites, (hydrogenated) castor oil derivatives, soy lecithin, ethyl cellulose, low molecular weight polyamides , Calcium soaps or hydrophobized silicas.
  • Aerosil ® 200 flamed silica, Degussa
  • Bentone ® SD-1, SD-2, 34, 52 and 57 bentonite.
  • auxiliaries mentioned can be used in the rinse aid articles according to the invention in varying amounts 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.
  • Particle-shaped rinse aid 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 wt .-%, each based on the particle weight.
  • emulsifiers are particularly advantageous in the production of mixtures of molten matrix materials and active substances which are liquid at the processing temperature. It has been shown that, in particular, emulsifiers from the group of fatty alcohols, fatty acids, polyglycerol esters and polyoxy- alkylene siloxanes are extremely 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.
  • C 6 are therefore preferred as emulsifiers in the rinse aid articles according to the invention.
  • 22 fatty alcohols preferably C 8 .
  • 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-oleic acid, arachic acid, behenic acid, lignoceric acid, cerotic 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.
  • the fatty acids with an odd number of carbon atoms can also be used, for example undecanoic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, nonadecanoic acid, heneicosanoic acid, tricosanoic acid, pentacosanoic acid, heptacosanoic acid.
  • C 6-22 fatty acids preferably C 8-2 2 fatty acids and in particular, are used as emulsifier (s) with particular preference for the C ⁇ 6- ⁇ 8 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 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.
  • POLYGLYCERYL-2-OLEATE POLYGLYCERYL-3-OLEATE, POLYGL YCERYL-4-OLEATE. POLYGLYCERYL-6-OLEATE. POLYGLYCERYL-8 OLEATE.
  • emulsifiers which can be used in the rinse aid articles 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
  • each radical R 1 independently of one another for -CH or a polyoxyethylene or propylene group - [CH (R 2 ) -CH -O] x H group, R 2 for -H or -CH 3 , x for a number is between 1 and 100, preferably between 2 and 20 and in particular under 10. and n indicates the degree of polymerization of the silicone.
  • 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 can be used over a wide range. Usually, 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 of 0.1 to 5% by weight, preferably 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, in each case based 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 is selected from a) 10 to 90% by weight of one or more matrix materials selected from at room temperature solid polymers, in particular polyurethanes, with b) 90 to 10% by weight of one or more active substances and c) 0 to 20% by weight of further active ingredients and auxiliaries, mixed and the mixture processed to give shape.
  • a melt is first produced from the matrix materials, which is then mixed with the active substances and, where appropriate, active substances and auxiliaries, which are preferably in liquid or molten form. The mixture is then shaped.
  • the matrix materials can be mixed with the active substances and the further active substances and auxiliaries in all customary mixing devices.
  • the shaping processing step for the mixture of matrix material and active substances and further active substances and auxiliaries is likewise not subject to any procedural restrictions, so that the person skilled in the art can also select from the processes familiar to him. In tests by the applicant, methods have been found to be preferred in which the shaping processing is carried out by granulating, compacting, pelletizing, extruding or tableting.
  • the particles produced can be coated with the coating substances in a manner known per se. Coating can be carried out by immersion processes or by spraying on melts or solutions of the coating substances
  • the mixture produced contains one or more substances from the groups of the surfactants, enzymes, bleaching agents, bleach activator, corrosion inhibitors, scale inhibitors, cobuilders and / or fragrances as active substance.
  • the active substances are usually present in amounts of from 10 to 90% by weight, preferably from 15 to 80% by weight and in particular from 20 to 65% by weight, based in each case on the mixture, the enzymes and fragrances in the Usually in amounts up to 2 wt .-%, based on the mixture, are included.
  • the rinse aid articles according to the invention can be given directly to the consumer, so that he also adds them to the cleaning agent as required. Because of this additional dosing step, the advantages over liquid rinse aids would be minimized in addition to the fixed form of delivery and the addition to the same dosing compartment. It is therefore preferred to mix the rinse aid articles according to the invention in 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, dyes and fragrances, which is characterized in that it has an inventive contains particulate rinse aid in amounts of 0.5 to 30% by weight, preferably 1 to 25% by weight and in particular 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 in the rinse aid articles according to the invention.
  • the cleaning agents according to the invention for machine dishwashing can contain all builders commonly used in washing and cleaning agents, in particular thus zeolites, silicates, carbonates, organic cobuilders and - if there are no ecological concerns about their use - also the phosphates.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + ⁇ 'H 2 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.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 'yH 2 O are preferred.
  • Amorphous sodium silicates with a module Na 2 O: SiO 2 of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which are delayed in dissolution, can also be used 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 / compaction or by overdrying.
  • the term “amo ⁇ h” is also understood to mean “roentgenamo ⁇ h”.
  • 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.
  • Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray silicates.
  • 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 Augustusta SpA under the brand name VEGOBOND AX ® 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.
  • phosphates as builder substances, provided that such use should not be avoided for ecological reasons.
  • the alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of 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) n and orthophosphoric acid H 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 dihydrogenphosphate, 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 powders which are very easily soluble in water heating lose the water of crystallization and at 200 ° C in the weakly acidic diphosphate (disodium hydrogen, Na 2 HP 2 O 7), at a higher temperature into sodium (Na 3 P 3 ⁇ 9) and Maddrell's salt (see below), pass. NaH 2 PO 4 reacts acidic, it is formed when phosphoric acid is adjusted to pH 4.5 with sodium hydroxide solution and the mash is sprayed in.
  • Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH 2 PO 4 is a white one Salt with a density of 2.33 like "3 , has a melting point of 253 ° [decomposition with the formation of potassium polyphosphate (KPO 3 ) x ] and is easily soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO, is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gladly “3 , water loss at 95 °), 7 mol. (Density 1.68 gladly “ 3 , melting point 48 ° with loss of 5 H 2 O) and 12 mol. Water ( Density 1.52 "3 , melting point 35 ° with loss of 5 H 2 O), becomes anhydrous at 100 ° and changes to diphosphate Na_ t P 2 O when heated more. Disodium hydrogenphosphate is neutralized by Phosphoric acid made with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K HPO 4 , is an amorphous, white salt that is easily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 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% P2O 5 ) melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5) like to have a density of 2.536 '.
  • 3 trisodium phosphate is readily soluble in water with an alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mol of NaOH.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na4P O, 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 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 "3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.
  • 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. For the latter in particular, there are a large number of names in Use: Melting or glow phosphates, Graham's salt. Kurrolsches and Maddrellsches salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • Na 5 P 3 O ⁇ o sodium tripolyphosphate
  • Na 5 P 3 O ⁇ o sodium tripolyphosphate
  • is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] n -Na with n 3 that crystallizes with 6 H 2 O and is not hygroscopic.
  • 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 around 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate.
  • these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; 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 also 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 can be used. 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 w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used.
  • GPC gel permeation chromatography
  • the measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. 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 composed of more than two different monomer units, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers ,
  • copolymers are those which have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids their salts or their precursor substances.
  • Poly- Aspartic acids or their salts and derivatives which often have a bleach-stabilizing effect in addition to cobuilder properties.
  • 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 polyolcarboxylic 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
  • 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 carboxylic acid absorption.
  • 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 connection. Suitable amounts are 3 to 15% by weight in formulations containing zeolite and / or silicate.
  • Further usable 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 at most two acid groups.
  • 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 ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs.
  • 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 machine 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 articles. 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 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 from the group of the alkoxylated 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 1 -C 4 alcohols with 3 EO or 4 EO, C 9 _. 11 alcohol with 7 EO, C 13 - ⁇ s- alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C ⁇ ⁇ 2- 8 alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ⁇ 2 - ⁇ 4 alcohol containing 3 EO and C 12- 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) x can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl branched, in particular in the 2-position 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.
  • 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), Rl
  • 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 2
  • R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 represents a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, with C M - alkyl or phenyl radicals being preferred
  • [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated, derivatives of this rest.
  • [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.
  • 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 that can be used are, for example, sodium percarbonate, peroxyprophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecotacid.
  • 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.
  • organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
  • Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ - Naphtoic acid and magnesium monophthalate, (b) the aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, ⁇ - phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-
  • PAP phthaloiminoperoxyhexanoic acid
  • 1,12-diperoxycarboxylic acid 1, 9-diperoxyazelaic acid
  • diperocysebacic acid diperocysebacic acid
  • doxy-doxy-2-butoxy-diperbutyldiacid-4 N, N-terephthaloyl-di (6-aminopercapronic 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 articles 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 in the rinse aid articles.
  • Known bleach activators are compounds which contain one or more N- or O-acyl groups, such as substances from the class of the anhydrides, the esters, the imides and the acylated imidazoles or oximes.
  • Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, l, 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, give aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid.
  • 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.
  • Multi-acylated alkylenediamines in particular tetraacetylethylene diamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3.5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, are preferred.
  • TAED tetraacetylethylene diamine
  • DADHT 1,5-diacetyl-2,4-dioxohexahydro-1,3.5-triazine
  • TAGU tetraacetylglycoluril
  • N-acylimides are preferred.
  • N-nonanoylsuccinimide NOSI
  • acylated phenolsulfonates especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS)
  • carboxylic acid anhydrides especially phthalic anhydride
  • acylated polyhydric alcohols especially triacetin, 2-ethylene glycol diacetyl acetate, 5-dihydrofuran, n-methyl-Mo ⁇ holinium-acetonitrile-methyl sulfate (MMA), and acetylated sorbitol and mannitol or their mixtures (SORMAN)
  • acylated sugar derivatives in particular pentaacetyl glucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactyllactyllactyllactyl alkylated glucamine and
  • bleach catalysts can also be incorporated into the rinse aid articles.
  • 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 multiply acylated alkylenediamines in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n-) or iso-N-NOB are preferred -Methyl-Mo ⁇ holinium-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 tetraacetylethylenediamine
  • N-acylimides in particular N-nonanoylsuccin
  • Bleach-enhancing transition metal complexes especially with the central atoms Mn. Fe, Co, Cu, Mo, V, Ti and / or Ru. preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes. the cobalt (acetate) complexes. the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, the manganese sulfate are used in conventional amounts, preferably in an amount of up to 5% by weight, in particular from 0.0025% by weight to 1% by weight and particularly preferably from 0.01% by weight to 0.25% by weight, based in each case on the total agent. 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 contribute to the removal of stains such as stains containing protein, fat or starch. Oxidoreductases can also be used for bleaching. Particularly suitable 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.
  • hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as stains containing protein, fat or starch
  • protease and amylase or protease and lipase or lipolytically active enzymes for example of protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes, but especially protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest.
  • Known cutinases are examples of such lipolytically active enzymes.
  • 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 percentage of 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, in addition to the performance, to provide the consumer with a visually and sensorially "typical and unmistakable" product.
  • 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, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allylcyclohexylpropylylpropyl nylate propyl nylate propyl nylate propyl nylate propylamine.
  • the ethers include, for example, benzylethyl ether
  • the aldehydes include, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal
  • the ketones include, for example, the jonones, ⁇ -isomethylionone and methylcedryl ketone
  • the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and te ⁇ ineol
  • the hydrocarbons mainly include the te ⁇ enes such as lemon 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.
  • a slower fragrance release As such have backing materials Cyclodextrins, for example, have proven themselves, the cyclodextrin-perfume complexes additionally being able to be coated with further auxiliaries. Incorporation of the fragrances into the rinse aid articles 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 long shelf life and are not sensitive to the other ingredients of the compositions and to light, and have no pronounced substantivity to the substrates to be treated with the compositions, such as glass, ceramic 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 of particular importance in the field of automatic dishwashing.
  • the known substances of the prior art can be used.
  • silver protective agents selected from the group consisting of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used.
  • 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 consisting of manganese and / or cobalt salts and or complexes, particularly preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes.
  • Complexes chlorides of cobalt or manganese and manganese sulfate.
  • Zinc compounds can also be used to prevent corrosion on the wash ware.
  • the composition of the rinse aid articles according to the invention is such that they do not dissolve in the main rinse cycle (and also in optional pre-rinse cycles) or only to a minor extent. This ensures that the active substances are only released in the rinse cycle and develop their effect here.
  • 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. If heavily soiled crockery is washed by the consumer, this sieve insert must be cleaned regularly, which is easily possible due to the easy accessibility and removability.
  • the size and shape of the rinse aid articles 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.
  • 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 40 mm, preferably between 1, 5 and 25 mm and in particular between 2 and 20 mm.
  • the rinse aid articles are admixed with conventional powdered or granular machine dishwashing detergents.
  • the rinse aid articles are processed together with the ingredients of the machine dishwashing detergent to form a combination product of dishwashing detergent and rinse aid.
  • Such products preferably so-called molded bodies, also known as tablets in the prior art.
  • the combination products can be produced in a manner known per se.
  • the molded articles and the rinse aid articles are produced separately and then connected to one another, and the molded articles can have cutouts that are already prepared for the particles.
  • the connection can be made, for example, by simply inserting it into the recess or gluing the two fixed components.
  • the rinse aid articles or the premix for this purpose are processed in a suitable tabletting device with the premix for the dishwashing detergent to give shaped articles.
  • 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 Rinse aid article exists.
  • the rinse aid articles according to the invention are colored, for example thus have a red, blue, green or yellow color, it is important for the appearance of the product, i.e. of the entire cleaning agent is advantageous if the rinse aid particles are visibly larger than the matrix of the particles of the other ingredients of the cleaning agent.
  • particulate machine dishwashing detergents according to the invention are preferred which (without taking into account the rinse aid particles) 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 articles. Since technically uncomplicated processes can be used to manufacture the rinse aid articles, it is easy possible to offer them in various forms.
  • the 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, partial segregation can occur on the one hand when the package is shaken, in particular when the sizes of rinse aid particles and cleaning agent matrix are very different, on the other hand the dosage can be different in two successive cleaning cycles, since the consumer is not always mandatory dosed the same amount of detergent and rinse aid article. 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.
  • 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. On In this way, a sieve insert designed in this way replaces the dosing chamber, ie the consumer doses the automatic dishwasher detergent according to the invention directly into this sieve insert, which acts in the cleaning and rinse cycle in the manner described above.
  • the melt can be formulated from the ingredients a) to c) as a phase of a shaped body, which for example has the shape of a layer, a core-shaped insert, etc.
  • the present invention thus furthermore relates to a multi-phase detergent molded article for machine dishwashing, containing builders and optionally further detergent ingredients, in which at least one phase is selected from a) 10 to 90% by weight or one or more matrix materials Polymers which are solid at room temperature, in particular polyurethanes, b) 90 to 10% by weight of one or more active substances, and c) 0 to 20% by weight> other active substances and auxiliaries.
  • the individual phases of the molded body can have different spatial shapes within the scope of the present invention.
  • the simplest possible implementation is in two- or multi-layer tablets, with each layer of the molded body representing a phase.
  • ring core tablets coated tablets or combinations of the above-mentioned embodiments are possible, for example.
  • Examples of multi-phase molded bodies can be found in the illustrations in EP-A-0 055 100 (Jeyes), which describes toilet cleaning blocks.
  • the most widespread spatial form of multi-phase molded bodies is the two- or multi-layer tablet.
  • the phases of the molded body have the shape of layers and the molded body is 2-, 3- or 4-phase.
  • the shaped bodies according to the invention can take on any geometric shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segment-like, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, five, ellipsoid -, Hexagonal and octagonal-prismatic and rhombohedral shapes are preferred.
  • Completely irregular base areas such as arrow or animal shapes, trees, clouds, etc. can also be realized.
  • the shaped bodies according to the invention have corners and edges, they are preferably rounded. As an additional visual differentiation, an embodiment with rounded corners and chamfered (“chamfered”) edges is preferred.
  • molded bodies can also be produced which contain the cleaning agent component according to the invention in the form of other phases. It has proven useful here to produce base moldings which have one or more cavities and to fill the melt from the constituents a) to c) of the detergent component according to the invention into the cavity and to solidify it there. This manufacturing process results in preferred multi-phase detergent molded articles which consist of a basic molded article which has a cavity and an at least partially contained part of the cavity.
  • the cavity in the molded part of such molded bodies according to the invention can have any shape. It can divide the molded body, ie have an opening on different sides, for example on the top and bottom of the molded body, but it can also be a cavity that does not go through the entire molded body, the opening of which is only visible on one side of the molded body.
  • the shape of the cavity can also be freely selected within wide limits. For reasons of process economy, through holes, the openings of which lie on opposite surfaces of the molded body, and troughs with an opening on one side of the molded body have proven successful.
  • the cavity has the shape of a through hole, the openings of which are located on two opposing molding surfaces.
  • the shape of such a through hole can be chosen freely, preference being given to shaped bodies in which the through hole is circular, elliptical, triangular, rectangular, square, pentagonal, hexagonal, heptagonal or octagonal horizontal sections.
  • Completely irregular hole shapes such as arrow or animal shapes, trees, clouds etc. can also be realized.
  • those with rounded corners and edges or with rounded corners and chamfered edges are preferred.
  • Shaped bodies with a rectangular or square base and circular holes can be produced as well as round shaped bodies with octagonal holes, whereby there are no limits to the variety of possible combinations.
  • molded bodies with a hole are particularly preferred in which the molded body base area and the hole cross section have the same geometric shape, for example molded bodies with a square base area and a centrally incorporated square hole.
  • Ring-shaped bodies are particularly preferred, i.e. circular shaped body with a circular hole.
  • the shaped bodies according to the invention can also assume any geometric shape in this embodiment, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segment-like, disk-shaped, tetrahedral, dodecahedral, octahedral , pyramidal, ellipsoidal, five-, seven- and octagonal-prismatic as well as rhombohedral shapes are preferred.Also completely irregular base areas such as arrow or animal shapes, trees, clouds etc.
  • the shape of the trough can also be chosen freely, with preference being given to shaped bodies in which at least one trough has a concave, convex, cubic, tetragonal. orthorhombic, cylindrical, spherical, segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, pentagonal, pentagonal, octagonal, prismatic and rhombohedral.
  • Completely irregular trough shapes such as arrow or animal shapes, trees, clouds, etc. can also be realized.
  • troughs with rounded corners and edges or with rounded corners and chamfered edges are preferred.
  • the part at least partially contained in the cavity consists solely of the ingredients a) to c) of the rinse aid articles according to the invention.
  • carrier-based rinse aid articles into the cavity (s).
  • multi-phase detergent tablets are preferred in which the part contained in the cavity is selected from a) 10 to 90% by weight of one or more matrix materials selected from polymers solid at room temperature, in particular polyurethanes, b) 90 to 10% by weight. % of one or more active substances and, c) 0 to 20% by weight of further active substances and auxiliaries.
  • the size of the trough or the through hole in comparison to the entire molded body depends on the intended use of the molded body.
  • the size of the cavity can vary depending on whether a smaller or larger amount of detergent component is to be contained.
  • detergent tablets are preferred in which the volume ratio of the pressed part (“base tablet”) to the rinse aid is up to 100: 1, preferably 3: 1 to 80: 1, particularly preferably 4: 1 to 50: 1 and in particular 5 : 1 to 30: 1.
  • a mass ratio of the two parts can also be specified, the two values correlating with one another via the densities of the basic molded article or the rinse aid article.
  • detergent tablets according to the invention are preferred, in which the weight ratio of basic shaped body to pressed rinse aid article is up to 100: 1, preferably 2: 1 to 80: 1, particularly preferably 3: 1 to 50: 1 and in particular 4: 1 to 30: 1.
  • Analogous statements can also be made for the surfaces that are visible from the base mold or from the pressed rinse aid articles.
  • detergent tablets are preferred, in which the outwardly visible surface of the pressed rinse aid articles accounts for 1 to 25%, preferably 2 to 20%, particularly preferably 3 to 15% and in particular 4 to 10% of the total surface of the molded article
  • the pressed rinse aid articles and the basic molded article are preferably colored to be optically distinguishable.
  • application technology advantages can be achieved through different solubilities of the different molded body areas.
  • Detergent shaped articles in which the pressed rinse aid articles dissolve faster than the basic shaped article are preferred according to the invention. Incooration of certain components on the one hand can specifically accelerate the solubility of the pressed rinse aid articles, on the other hand the release of certain ingredients from the pressed rinse aid articles can lead to advantages in the washing or cleaning process.
  • detergent tablets according to the invention are also preferred, in which the pressed rinse aid articles dissolve later in the washing program than the basic tablet.
  • Performance advantages from this delayed release can be achieved, for example, in that active substance (s) are only released in later rinse cycles with the aid of slowly soluble, pressed rinse aid articles.
  • active substance (s) are only released in later rinse cycles with the aid of slowly soluble, pressed rinse aid articles.
  • additional substances such as non-ionic surfactants, acidifiers, soil-release polymers, etc. can be used to improve the rinse aid results.
  • Incorporation of perfume is also possible without any problems; due to its delayed release, the "lye smell" that often occurs in dishwashers Opening the machine can be eliminated.
  • the ingredients acidifying agent. Soil-release polymers etc. are then based on the pressed rinse aid articles according to the invention, ingredients c).
  • the basic molded body has a high specific weight.
  • Detergent shaped articles which are characterized in that the basic shaped article has a density above 1000 kgdm " , preferably above 1025 kgdm " , particularly preferably above 1050 kgdm “3 and in particular above 1 100 kgdm “ 3 , are preferred according to the invention ,
  • tablet disintegrants In order to facilitate the disintegration of highly compressed moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, in order to shorten the disintegration times.
  • tablet disintegrants or accelerators of decay are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in absorbable form.
  • Preferred shaped detergent bodies contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration aids, in each case based on the weight of the shaped body.
  • disintegration aids are inco ⁇ orated in the detergent components according to the invention, those count as ingredients c).
  • Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent tablets such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight .-% contain.
  • Pure cellulose has the formal gross composition (C 6 H ⁇ 0 ⁇ 5 ) n and formally represents a ß-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose.
  • Suitable celluloses consist of approx. 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions.
  • Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxyl hydrogen atoms have been substituted.
  • celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
  • the cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose.
  • the cellulose derivative content of these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the
  • the cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be treated.
  • Detergent and shaped body, the disintegrant in granular or, if appropriate Containing cogranulated form are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and international patent application WO98 / 40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated celiosis disintegrants.
  • the particle sizes of such disintegrants are usually above 200 ⁇ m, preferably at least 90% by weight between 300 and 1600 ⁇ m and in particular at least 90% by weight> between 400 and 1200 ⁇ m.
  • the above and described in more detail in the documents cited coarser disintegration aids, are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ® TF-30-HG from Rettenmaier available in the present invention.
  • Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component.
  • This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%>) undamaged.
  • a subsequent disaggregation of the microfine celluloses produced by the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 ⁇ m and can be compacted, for example, into granules with an average particle size of 200 ⁇ m.
  • Preferred detergent tablets in the context of the present invention additionally contain a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on the molded body weight.
  • a disintegration aid preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on the molded body weight.
  • the detergent molded articles according to the invention can also contain a gas-developing shower system both in the basic molded article and in the pressed rinse aid articles.
  • the gas-developing shower system can consist of a single substance that releases a gas when it comes into contact with water.
  • the gas-releasing bubble system itself consists of at least two components that react with one another to form gas. While a variety of systems are conceivable and executable here. which for example nitrogen. Release oxygen or hydrogen, the bubbling system used in the detergent tablets according to the invention can be selected on the basis of both economic and ecological aspects.
  • Preferred effervescent systems consist of alkali metal carbonate and / or hydrogen carbonate and an acidifying agent which is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution.
  • the alkali metal carbonates or bicarbonates the sodium and potassium salts are clearly preferred over the other salts for reasons of cost.
  • the pure alkali metal carbonates or bicarbonates in question do not have to be used; rather, mixtures of different carbonates and bicarbonates may be preferred for reasons of washing technology.
  • shaped detergent bodies 2 to 20% by weight, preferably 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or bicarbonate and 1 to 15, preferably 2 to 12 and in particular 3, are used as the effervescent system up to 10% by weight of an acidifying agent, based in each case on the entire molded body.
  • Acidifying agents which release carbon dioxide from the alkali salts in aqueous solution are, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts.
  • organic acidifying agents are preferably used, citric acid being a particularly preferred acidifying agent.
  • the other solid mono-, oligo- and polycarboxylic acids can also be used in particular. Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are preferred from this group.
  • Organic sulfonic acids such as amidosulfonic acid can also be used.
  • Sokalan ® DCS commercially available and as an acidifying agent in the men of the present invention also preferably be used is Sokalan ® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) and adipic acid (max. 33 by weight %).
  • detergent molded bodies are preferred. in which a substance from the group of the organic di-, tri- and oligocarboxylic acids or mixtures thereof are used as acidifying agents in the effervescent system.
  • a further aspect of the present invention is a combination of (a) particulate cleaning agent (s) according to the invention and / or (a) washing or cleaning agent shaped body (s) according to the invention and one containing the cleaning agent and / or the washing and cleaning agent shaped body Packaging system, the packaging system having a moisture vapor transmission rate of 0.1 g / m 2 / day to less than 20 g / m / day when the packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%.
  • the packaging system of the combination of detergent component and / or cleaning agent and or washing and cleaning agent shaped body (s) and packaging system has a moisture vapor permeability rate of 0.1 g / m / day to less than 20 g / m / day if the packaging system at 23 ° C and a relative equilibrium humidity of 85% is stored.
  • the specified temperature and humidity conditions are the test conditions that are mentioned in the DIN standard 53122, whereby according to DIN 53122 minimal deviations are permitted (23 ⁇ 1 ° C, 85 ⁇ 2% relative humidity).
  • the moisture vapor permeability rate of a given packaging system or material can be determined by further standard methods and is, for example, also in the ASTM standard E-96-53T ("Test for measuring Water Vapor transmission of Materials in Sheet form") and in the TAPPI standard T464 m-45 ("Water Vapor Permeability of Sheet Materials at high temperature and Humidity ").
  • the measuring principle of common procedures is based on the water absorption of anhydrous calcium chloride, which is stored in a container in the appropriate atmosphere, the container being closed at the top with the material to be tested. From the surface of the container, that is sealed with the material to be tested (permeation surface), the weight gain of the calcium chloride and the exposure time, the moisture vapor permeability rate can be measured
  • A is the area of the material to be tested in cm
  • x is the weight increase of calcium chloride in g
  • y is the exposure time in h.
  • the relative equilibrium humidity is 85% at 23 ° C. when measuring the moisture vapor permeability rate in the context of the present invention.
  • the capacity of air for water vapor increases with temperature up to a respective maximum content, the so-called saturation and is given in g / m. For example, 1 m of air at 17 ° is saturated with 14.4 g of water vapor, at a temperature of 11 ° there is saturation with just 10 g of water vapor Percentage expressed ratio of the actual water vapor content to the saturation content corresponding to the prevailing temperature.
  • the relative equilibrium humidity of 85% at 23 ° C can be set to +/- 2% RH, for example in laboratory chambers with moisture control, depending on the device type. Even over saturated solutions of certain salts form in closed Systems at a given temperature consist of constant and well-defined relative air humidities, which are based on the phase equilibrium between the partial pressure of the water, the saturated solution and the soil body.
  • the combinations according to the invention can of course in turn be packed in secondary packaging, for example cardboard boxes or trays, whereby no further requirements have to be made of the secondary packaging. Secondary packaging is therefore possible, but not necessary.
  • Packaging systems preferred in the context of the present invention have a moisture vapor permeability rate of 0.5 g / m 2 / day to less than 15 g / m 2 / day.
  • the packaging system of the combination according to the invention includes a certain amount of rinse aid particles according to the invention, a certain amount of a particulate detergent composition or one or more detergent tablets. It is preferred according to the invention either to design a shaped body in such a way that it comprises an application unit of the detergent and cleaning agent, and to individually package this shaped body, or to pack the number of shaped bodies in a packaging unit, which in total comprises one application unit.
  • the packaging system of the combination according to the invention can consist of a wide variety of materials and can take on any external shape.
  • the packaging system consists of a sack or pouch made of single-layer or laminated paper and / or plastic film.
  • the detergent tablets can be unsorted, i.e. as a loose fill, be filled into a bag made of the materials mentioned. However, for aesthetic reasons and for sorting the combinations in secondary packaging, it is preferred to fill the detergent and cleaning product tablets individually or in groups in sacks or bags. For individual application units of the detergent tablets that are in a sack or bag, the term "flow pack" has become common in technology. Such "flow packs" can then - again preferably sorted - be optionally packed in repackaging, which the compact offer form of the molded body underlines.
  • the sacks or bags made of single-layer or laminated paper or plastic film which are preferably to be used as a packaging system, can be designed in a wide variety of ways, for example as a blown-up bag without a central seam or as a bag with a central seam, which is sealed by heat (hot fusion), adhesives or adhesive tapes become.
  • Single-layer bag or sack materials are the known papers, which can optionally be impregnated, and plastic films, which can optionally be co-extruded.
  • Plastic films that can be used as a packaging system in the context of the present invention are given, for example, in Hans Domininghaus "The plastics and their properties", 3rd edition, VDI Verlag, Düsseldorf, 1988, page 193.
  • Combinations which are particularly preferred in the context of the present invention contain a sack or bag made of single-layer or laminated as the packaging system Plastic film with a thickness of 10 to 200 microns, preferably from 20 to 100 microns and in particular from 25 to 50 microns.
  • packaging system in the context of the present invention always denotes the primary packaging of the detergent component, detergent composition or molded article, i.e. the packaging that is in direct contact with the detergent component, detergent composition or molded body surface on the inside. No requirements are placed on an optional secondary packaging, so that all common materials and systems can be used here.
  • the rinse aid articles, detergent compositions or detergent tablets of the combination according to the invention contain, depending on their intended use, further detergent ingredients in varying amounts. Regardless of the intended use of the agent or molded article, it is preferred according to the invention that the agent or agents or the detergent and cleaning agent molded article has / have a relative equilibrium moisture content of less than 30% at 35 ° C.
  • the relative equilibrium moisture content of the detergent or detergent tablets can be determined using standard methods, the following procedure being chosen in the context of the present investigations: A water-impermeable 1-liter container with a lid, which has a closable opening for introducing samples has been filled with a total of 300 g of detergent tablets and kept at a constant 23 ° C. for 24 hours in order to ensure a uniform temperature of the vessel and substance.
  • the water vapor pressure in the space above the molded bodies can then be determined using a hygrometer (Hygrotest 6100, Testoterm Ltd., England). The water vapor pressure is now every 10 minutes measured until two consecutive values show no deviation (balance moisture).
  • the above-mentioned hygrometer allows a direct display of the recorded values in% relative humidity.
  • Combinations in which the packaging system has a microperforation can also be preferably implemented according to the invention.
  • a cleaning process for cleaning dishes in a dishwasher is characterized in that one or more particulate cleaning agents according to the invention and or one or more washing or cleaning agent shaped articles according to the invention, the dosing chamber of the dishwasher and a washing program can run in the course of which the metering chamber opens and the cleaning agent (s) and / or the molding body (s) are dissolved, another object of the present invention.
  • the metering chamber can be dispensed with and the rinse aid articles or detergent compositions according to the invention or the molded article (s) according to the invention can be inserted, for example, into the cutlery basket.
  • a dosing aid for example a basket, which is attached to the wash cabinet, is also possible without any problems.
  • a cleaning method for cleaning dishes in a dishwasher is characterized in that one or more particulate cleaning agent (s) according to the invention and / or one or more detergent tablets according to the invention with or without
  • a further object of the present invention is to place the dosing aid in the washing area of the dishwasher and to run a washing program in the course of which the cleaning agent (s) and / or the molded article (s) are dissolved.
  • a polyurethane consisting of 0.2 mol of polyethylene glycol with a molecular weight of 6000, 0.14 mol of 12-hydroxystearyl alcohol and 0.37 mol of TMXDI was used as the matrix material. which had a melt viscosity according to Kegel-Platte (Brookfield CAP 2000) of 91 Pas at 175 ° C, was used.
  • the polyurethane was melted together with an alcohol alkoxylate (Polytergent SLF-18B-45; commercially available from Olin Chemicals) in a weight ratio of 40:60 and then grooved.
  • an alcohol alkoxylate Polytergent SLF-18B-45; commercially available from Olin Chemicals
  • the matrix material used was a polyurethane composed of 0.2 mol of polyethylene glycol with a molecular weight of 6000, 0.412 mol of polytetrahydrofuran with a molecular wiping of 250 and 0.58 mol of TMXDI, which had a melt viscosity according to Kegel-Platte (Brookfield CAP 2000) of 133.5 Pas 150 ° C was used.
  • the polyurethane was melted together with an alcohol alkoxylate (Polytergent SLF-18B-45; commercially available from Olin Chemicals) in a weight ratio of 40:60 and then grooved.
  • the particles obtained were mixed with CULMINAL ® MHPC 25 (cellulose derivative, manufacturer: Aqualon) coated.
  • a commercially available powdery detergent for automatic dishwashing was used in a universal cleaning program.
  • the program was carried out under the same conditions once without a commercially available rinse aid (storage tank in the dishwasher was emptied), with a commercially available rinse aid (dosage of 3 ml commercially available Rinse aid from the storage tank in the rinse cycle) and once with the rinse aid articles according to the invention according to Example 1 (addition of 3.3 g rinse aid articles to 20 g agent, dosage before the main rinse cycle).
  • the storage tank for the commercial rinse aid was of course empty, ie the rinse aid performance can only be attributed to the rinse aid particles 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 that are free of deposits and water drops. 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 table shows that the agents according to the invention achieve or exceed the rinse aid performance of the conventional combination of detergent and rinse aid to be metered separately, although less rinse aid (based on active substance) is used and the particles according to the invention are already in the main rinse cycle in the machine are physically and chemically stressed.
  • 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 un agent mouillant particulaire pour le rinçage de la vaisselle en machine, qui comprend: (a) 10 à 90 % en poids d'au moins un matériau matriciel sélectionné parmi des polymères solides à la température ambiante; (b) 90 à 10 % en poids d'au moins un ingrédient actif; et (c) 0 à 10 % en poids d'autres substances actives et auxiliaires. L'agent mouillant particulaire revendiqué peut être mis sous une forme commerciale qui peut être utilisée aussi bien séparément comme agent mouillant sous forme solide à doser par le consommateur, que comme composant à mélanger avec des produits de rinçage pulvérulents pour la vaisselle lavée en machine.
PCT/EP2000/012207 1999-12-14 2000-12-05 Agent mouillant particulaire et produit de rinçage pour la vaisselle lavee en machine WO2001044422A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU17071/01A AU1707101A (en) 1999-12-14 2000-12-05 Particulate wetting agent and machine dishwashing agent

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19960096.1 1999-12-14
DE1999160096 DE19960096A1 (de) 1999-12-14 1999-12-14 Teilchenförmiger Klarspüler und maschinelle Geschirrspülmittel

Publications (2)

Publication Number Publication Date
WO2001044422A2 true WO2001044422A2 (fr) 2001-06-21
WO2001044422A3 WO2001044422A3 (fr) 2002-03-14

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PCT/EP2000/012207 WO2001044422A2 (fr) 1999-12-14 2000-12-05 Agent mouillant particulaire et produit de rinçage pour la vaisselle lavee en machine

Country Status (4)

Country Link
AU (1) AU1707101A (fr)
CA (1) CA2328258A1 (fr)
DE (1) DE19960096A1 (fr)
WO (1) WO2001044422A2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10225115A1 (de) * 2002-06-06 2003-12-24 Henkel Kgaa Verwendung wirkstoffhaltiger Polymermatrizes beim maschinellen Geschirrspülen
DE102008057739A1 (de) * 2008-11-17 2010-05-20 Buck-Chemie Gmbh Beschichteter Reinigungsmittelformförper

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2003238905A1 (en) * 2002-06-05 2003-12-22 The Procter And Gamble Company Surface treating compositions and methods for using same
EP2491842B1 (fr) 2011-02-22 2017-01-25 Miele & Cie. KG Procédé destiné à l'exécution d'un programme de lavage

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0397246A2 (fr) * 1989-05-11 1990-11-14 The Procter & Gamble Company Particules de parfum revêtues
WO1992020329A1 (fr) * 1991-05-17 1992-11-26 Fuisz Technologies Ltd. Systemes d'enzyme
EP0851024A2 (fr) * 1996-12-23 1998-07-01 Unilever N.V. Comprimés détergents pour le lavage de vaisselle en machine avec un effet de rinçage bénéfique
DE19851426A1 (de) * 1998-07-15 2000-01-20 Henkel Kgaa Verfahren zur Herstellung mehrphasiger Wasch- und Reinigungsmittelformkörper
DE19914363A1 (de) * 1999-03-30 2000-10-05 Henkel Kgaa Maschinelle Geschirrspülmittel mit teilchenförmigem Klarspüler

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0397246A2 (fr) * 1989-05-11 1990-11-14 The Procter & Gamble Company Particules de parfum revêtues
WO1992020329A1 (fr) * 1991-05-17 1992-11-26 Fuisz Technologies Ltd. Systemes d'enzyme
EP0851024A2 (fr) * 1996-12-23 1998-07-01 Unilever N.V. Comprimés détergents pour le lavage de vaisselle en machine avec un effet de rinçage bénéfique
DE19851426A1 (de) * 1998-07-15 2000-01-20 Henkel Kgaa Verfahren zur Herstellung mehrphasiger Wasch- und Reinigungsmittelformkörper
DE19914363A1 (de) * 1999-03-30 2000-10-05 Henkel Kgaa Maschinelle Geschirrspülmittel mit teilchenförmigem Klarspüler

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10225115A1 (de) * 2002-06-06 2003-12-24 Henkel Kgaa Verwendung wirkstoffhaltiger Polymermatrizes beim maschinellen Geschirrspülen
DE102008057739A1 (de) * 2008-11-17 2010-05-20 Buck-Chemie Gmbh Beschichteter Reinigungsmittelformförper

Also Published As

Publication number Publication date
DE19960096A1 (de) 2001-07-05
AU1707101A (en) 2001-06-25
WO2001044422A3 (fr) 2002-03-14
CA2328258A1 (fr) 2001-06-14

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