EP1103599B1 - Agent de rinçage particulaire et composition pour lavage de la vaiselle en machine - Google Patents

Agent de rinçage particulaire et composition pour lavage de la vaiselle en machine Download PDF

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Publication number
EP1103599B1
EP1103599B1 EP00125168A EP00125168A EP1103599B1 EP 1103599 B1 EP1103599 B1 EP 1103599B1 EP 00125168 A EP00125168 A EP 00125168A EP 00125168 A EP00125168 A EP 00125168A EP 1103599 B1 EP1103599 B1 EP 1103599B1
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EP
European Patent Office
Prior art keywords
weight
rinse aid
particulate
acid
substances
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EP00125168A
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German (de)
English (en)
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EP1103599A1 (fr
Inventor
Peter Dr. Schmiedel
Gerard Veldman
Thomas Otto Dr. Gassenmeier
Wolfgang Von Dr. Rybinski
Jürgen Dr. Härer
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets

Definitions

  • the present invention relates to particulate rinse aid for machine dishwashing containing from 95 to 5% by weight of one or more carrier materials and / or binders, and from 5 to 95% by weight of one or more active agents, and from 0 to 10% by weight of others Active ingredients and excipients, a process for its preparation and particulate machine dishwashing detergents (MGSM) containing the rinse aid particles.
  • MGSM particulate machine dishwashing detergents
  • European Patent Application EP-A-0 851 024 (Unilever) describes two-layer detergent tablets, the first layer of which comprises peroxy bleach, builder and enzyme while the second layer contains acidifying agent and a continuous medium having a melting point of between 55 and 70 ° C and scale inhibitors. Due to the high-melting continuous medium, the acid (s) and scale inhibitor (s) are to be released with a delay and bring about a clear rinse effect. Powdered automatic dishwashing or surfactant-containing rinse systems are not mentioned in this document.
  • support materials are zeolites, bentonites, silicates, carbonates, bicarbonates, sulfates, phosphates, as well as synthetic polymers, such as. cross-linked polycarboxylates, polyvinyl alcohols, and solid organic polycarboxylic acids used at room temperature. Natural or semi-synthetic polymers such as starch derivatives and cellulose derivatives can also be used.
  • the active ingredients of component a) or active ingredients and ingredients are in liquid form, they can first be applied to suitable carrier materials and, if necessary, mixed with a binder. Subsequently, the resulting mixture is compacted according to the invention.
  • the compression can be done in a conventional manner.
  • the compaction is carried out in a tablet press or in an extruder. Compression in a tablet press is particularly preferred, all common types of presses can be used, e.g. hydraulic presses, eccentric presses or rotary presses. Another possible compression method is the processing in roller presses.
  • the rinse aid particles according to the invention can be given to the consumer directly to the hand, so that they additionally added to the detergent as needed. Because of this additional metering step, however, the advantages over liquid rinse aids would be minimized except for the solid dosage form and the addition to the same dosing compartment. It is therefore preferred to combine the rinse aid particulate according to the invention particulate with automatic dishwashing detergents.
  • the most important ingredients of automatic dishwashing detergents are builders.
  • builders customarily used in detergents and cleaners it is possible for all builders customarily used in detergents and cleaners to be present, in particular zeolites, silicates, carbonates, organic cobuilders, the phosphates.
  • the builders mentioned below are all suitable as support materials for the rinse aid particles according to the invention, as has already been explained above.
  • amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties.
  • the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • the term "amorphous” is also understood to mean "X-ray amorphous”.
  • the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays which have a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm -3 , loss of water at 95 °), 7 moles (density 1.68 gcm -3 , melting point 48 ° with loss of 5 H 2 O) and 12 moles water ( Density 1.52 gcm -3 , melting point 35 ° with loss of 5 H 2 O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na 4 P 2 O 7 .
  • Disodium hydrogen phosphate is made by neutralization of phosphoric acid with soda solution prepared using phenolphthalein as an indicator.
  • Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is readily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which have a density of 1.62 gcm -3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -3 .
  • Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • 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 from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
  • biodegradable polymers of more than two different monomer units for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives ,
  • copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • 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, for example acid or enzyme catalyzed processes.
  • it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.
  • DE dextrose equivalent
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • the automatic dishwasher detergents according to the invention particularly preferably comprise nonionic surfactants, wherein it is again preferred that a part of the total amount of surfactant contained in the detergents is contained in the rinse aid particles. This is particularly advantageous, since in this way particulate dishwashing agents can be provided which unfold their cleaning performance in the main wash cycle and release the surfactant from the rinse aid particles only in the final 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 alkoxylated alcohols.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 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 linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants 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 having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.
  • polyhydroxy fatty acid amides of the formula (III) wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (IV) in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein C 1-4 alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
  • R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 is a linear, branched or cyclic alkyl radical or an aryl
  • nonionic surfactants for example the anionic or cationic surfactants
  • anionic or cationic surfactants may be present in the automatic dishwasher detergents according to the invention.
  • these may be contained both in the basic detergent and in the rinse aid particles.
  • alkyl sulphates may be present in the rinse aid particles.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • Cleaning agents according to the invention may also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
  • peroxyacids examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)] , o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diper
  • Chlorine or bromine-releasing substances can also be used as bleaching agents in the machine dishwashing detergents according to the invention.
  • suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • the said bleaching agents can also be introduced wholly or partly via the rinse aid particles according to the invention into the automatic dishwashing detergent according to the invention in order to achieve a "subsequent bleaching" in the final rinse cycle.
  • bleach activators which aid in the action of the bleaches have already been mentioned above as a possible ingredient of the rinse aid particles.
  • Known bleach activators are compounds which contain one or more N- or O-acyl groups, such as substances the class of anhydrides, esters, imides and acylated imidazoles or oximes.
  • Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (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, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran, n-methyl-morph
  • Bleach-enhancing transition metal complexes in particular having 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 of the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate are used in conventional amounts, preferably in an amount up to 5 wt .-%, in particular of 0.0025 wt % to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt .-%, each based on the total agent used. But in special cases, more bleach activator can be used.
  • Suitable enzymes in the detergents according to the invention are, in particular, those from the classes of the hydrolases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as proteinaceous, fatty or starchy stains. For bleaching and oxidoreductases can be used. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens, as well as enzymatically-derived variants derived from their genetically modified variants.
  • the hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as proteinaceous,
  • subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes, but in particular protease and / or lipase-containing mixtures or Mixtures with lipolytic enzymes of particular interest.
  • lipolytic enzymes are the known cutinases.
  • Peroxidases or oxidases have also proved suitable in some cases.
  • Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases.
  • the enzymes may be adsorbed to carriers or embedded in encapsulants to protect against premature degradation.
  • the proportion of enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5 wt.%, Preferably 0.5 to about 4.5 wt.%.
  • Dyes and fragrances can be added to the machine dishwasher detergents according to the invention in order to improve the aesthetic impression of the resulting products and to provide the consumer with a visually and sensory "typical and unmistakable" product in addition to performance.
  • perfume oils or fragrances individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are known e.g.
  • the ethers include, for example, benzyl ethyl ether, to the aldehydes e.g.
  • the linear alkanals having 8-18 C atoms citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the ionones, ⁇ -isomethylionone and methylcedryl ketone, among the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • fragrance oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.
  • the fragrances can also be incorporated into the rinse aid particles according to the invention, which leads to a fragrance impression when the machine is opened (see above).
  • compositions made according to the invention may (or parts thereof) be colored with suitable dyes.
  • suitable dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and against light and no pronounced substantivity to the substrates to be treated with the agents such as glass, ceramic or plastic dishes, not to stain them.
  • the detergents according to the invention may contain corrosion inhibitors for the protection of the items to be washed or the machine, with silver protectants in particular being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface.
  • chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used.
  • transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate.
  • zinc compounds can be used to prevent corrosion on the items to be washed.
  • the rinse aid particles according to the invention are designed in such a way that they do not disintegrate in the main rinse cycle (and also in optional pre-rinse cycles) or only to a lesser extent. This ensures that the active substances are largely released only in the rinse cycle and unfold their effect here.
  • physical packing is required in addition to this chemical preparation, so that the rinse aid particles are not pumped out when changing the water in the machine and thus are no longer available to the rinse cycle.
  • Domestic dishwashers contain before the drain pump, which pumps the water or the cleaning solution after each cleaning cycles out of the machine, a strainer, which is to prevent clogging of the pump by dirt residues.
  • the rinse aid particles according to the invention are now preferably designed with respect to their size and shape so that they do not pass through the sieve insert of the dishwasher even after the cleaning cycle, ie after loading by movement in the machine and the cleaning solution. In this way it is ensured that in the rinse cycle rinse aid particles are in the dishwasher, release the active substance (s) and bring the desired Klarillon soap.
  • Particulate rinse aid particles which are preferred in the context of the present invention are characterized in that the particulate rinse aid has particle sizes between 2 and 30 mm, preferably between 2.5 and 25 mm and in particular between 3 and 20 mm.
  • the rinse aid particles are admixed to conventional powdered or granular machine dishwashing compositions.
  • the rinse aid particles are processed together with the ingredients of the dishwasher detergents to a combination product of dishwashing detergent and rinse aid.
  • Such products are preferably so-called shaped bodies, which are also referred to as tablets in the prior art.
  • the preparation of the combination products can be done in a conventional manner.
  • the shaped bodies and the rinse aid particles are produced separately and then connected to one another, in which case the shaped bodies can already have prefabricated recesses for the particles.
  • the connection can be made for example by simply inserting into the recess or bonding the two fixed components.
  • the rinse aid particles or the premix therefor are processed in a suitable tabletting device with the premix for the dishwashing detergent to give moldings.
  • the rinse aid particles having the above-mentioned sizes may protrude from the matrix of the other particulate ingredients, but the other particles may likewise have sizes which are in the stated range, so that overall a detergent is formulated which consists of large detergent and cleaning agents Rinse aid particles.
  • the rinse aid particles according to the invention are dyed, that is, for example, have a red, blue, green or yellow color, it is for the appearance of the product, i. the entire cleaning agent advantageous if the rinse aid particles are visibly larger than the matrix of the particles of the remaining ingredients of the cleaning agent.
  • Particulate automatic dishwasher detergents according to the invention are preferred here which (without consideration of 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.
  • compositions can be increased not only by coloring the rinse aid particles but also by contrasting the powder matrix or by the shape of the rinse aid particles. Since it is possible to resort to technically uncomplicated methods in the production of the rinse aid particles, it is easily possible to offer these in a wide variety of forms.
  • approximately spherical or cube-shaped rinse aid particles can be prepared and used. Other geometric shapes can be realized.
  • Specific product embodiments may include, for example, star shaped rinse aid particles. Slices or forms that show as a base plant and animal body, such as tree, flower, flower, sheep, fish, etc., are easy to produce. Interesting visual incentives can be created in this way by making the rinse aid particles in the form of a stylized glass to underline the Klar Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff
  • the cleaning agents according to the invention are formulated as a powder mixture, partial segregation may occur, in particular in the case of very different sizes of rinse aid particles and detergent matrix, on the one hand with shake loading of the package, on the other hand, the dosage may be different in two successive cleaning cycles, since the consumer is not always compelling the same amount of detergent and rinse aid particles dosed. Should it be desired to use a technically the same amount per cleaning cycle, this can be done using the packaging familiar to the person skilled in the art agents according to the invention are realized in bags of water-soluble film. Particulate machine dishwashing detergents in which a dosing unit is packaged in a bag of water-soluble film are also the subject of the present invention.
  • the consumer has only one bag containing, for example, a detergent powder and a plurality of optically prominent rinse aid particles to insert in the dosing of his dishwasher.
  • This embodiment of the present invention is therefore an optically attractive alternative to conventional detergent tablets.
  • the cleaning agents according to the invention can be prepared in a manner known per se.
  • a method for producing powdered automatic dishwashing detergents with a clear rinse effect, in which a powdered machine dishwashing detergent which is known per se is mixed with rinse aid particles according to the invention, is therefore a further subject of the present invention.
  • the above-described desired restraint of the rinse aid particles in the machine even when changing water can be realized in addition to the above-mentioned increase in the rinse aid particles by reducing the size of the holes in the sieve insert.
  • automatic dishwashing detergents which have a uniform average particle size which is smaller than, for example, 4 to 12 mm.
  • the product according to the invention, in which also the rinse aid particles have smaller particle sizes is added to a sieve insert which replaces or covers the insert located in the machine.
  • Another object of the present invention is therefore a kit-of-parts comprising a powdered machine dishwashing detergent according to the invention and a sieve insert for household dishwashers.
  • the combination of agent and sieve insert according to the invention allows the formulation of agents in which the rinse aid particles also have smaller particle sizes.
  • the kit-of-parts according to the invention is not limited to the particular shape of the sieve insert, in which this substitutes or covers the insert located in the machine. It is also possible and preferred according to the invention to add a sieve insert to the kit-of-parts which has the shape of a basket which can be hung in the dishwasher in a known manner, for example on the cutlery basket. In this way, a sieve insert configured in this way replaces the dosing chamber, ie the consumer doses the machine dishwashing detergent according to the invention directly into this sieve insert, which acts in the cleaning and rinse cycle in the manner described above.
  • the support material was incorporated into the molten rinse aid surfactant until the resulting compound had a granular structure. Subsequently, the additive was incorporated and the mixture was pressed with a hydraulic press into compacts.
  • the composition of the mixture (wt .-%, based on the mixture) is given in the table below: 1 2 Polypore 1 E200 20 - water glass - 36 Poly Tergent SLF-18B-45 2 47 37 PEG 35000 33 27 1 support, allyl methacrylate crosspolymer (available from Chemdal Corp., USA) 2 Alcohol alkoxylate from Olin Chemicals, softening point 25-45 ° C.
  • the mass of the compacts can be between 0.5 g and 2 g.
  • the pressing force is chosen so that the compacts are decayed in the 65 ° C program of a dishwasher at the end of the rinse cycle.
  • the compacts were placed in a cylindrical trough in ordinary MGSM detergent tabs.
  • the surface tension of the rinse aid was measured in a 65 ° C. rinse test with the tablet according to the invention. A value of 28 mN / m was obtained, ie the maximum possible lowering of the surface tension with the surfactant used

Claims (19)

  1. Agent de rinçage en forme de particules pour le lavage de vaisselle en machine contenant
    a) 5 à 95% en poids d'une ou de plusieurs substances actives, au moins une des substances actives étant un agent tensioactif,
    b) 95 à 5% en poids d'un ou de plusieurs matériaux support du groupe des zéolithes, des bentonites, des silicates, des carbonates, des hydrogénocarbonates, des sulfates, des phosphates, des polycarboxylates réticulés, des poly(alcools vinyliques), des poly(acides carboxyliques) solides à température ambiante ou des dérivés d'amidon ou de cellulose et d'un ou de plusieurs liants du groupe des polyéthylèneglycols, des polyacrylates, des galactomannanes, des éthers de cellulose, des monosaccharides, des oligosaccharides ou des polysaccharides et/ou des résines ainsi que
    c) 0 à 10% en poids d'autres substances actives et adjuvants

    caractérisé en ce que
    - les composants a, b et le cas échéant c sont compactés de telle manière que les substances actives du composant a et le cas échéant les autres constituants du composant c sont libérés à un moment déterminé au préalable ou pendant un laps de temps défini au préalable dans le processus de nettoyage.
  2. Agent de rinçage en forme de particules selon la revendication 1, caractérisé en ce qu'il contient, comme substances actives, des agents tensioactifs, des agents de blanchiment, des activateurs de blanchiment, des inhibiteurs de corrosion, des inhibiteurs de tartre et/ou des builders en des quantités de 5 à 95% en poids, de préférence de 10 à 70% en poids et en particulier de 10 à 60% en poids, à chaque fois par rapport au poids des particules.
  3. Agent de rinçage en forme de particules selon les revendications 1 ou 2, caractérisé en ce qu'il contient comme substance active des agents tensioactifs, de préférence des agents tensioactifs non ioniques, en une quantité allant jusqu'à 95% en poids, de préférence de 7,5 à 70% en poids et en particulier de 10 à 60% en poids, à chaque fois par rapport au poids des particules.
  4. Agent de rinçage en forme de particules selon la revendication 3, caractérisé en ce que des agents tensioactifs non ioniques, de préférence des alcools alcoxylés sont contenus comme agents tensioactifs.
  5. Agent de rinçage en forme de particules selon l'une quelconque des revendications 1 à 4, caractérisé en ce qu'il contient comme substance active des agents de blanchiment du groupe constitué par les agents de blanchiment oxygénés ou halogénés, en particulier les agents de blanchiment chlorés.
  6. Agent de rinçage en forme de particules selon l'une quelconque des revendications 1 à 5, caractérisé en ce qu'il contient comme substance active des activateurs de blanchiment, en particulier des groupes constitués par les alkylènediamines polyacylées, en particulier la tétraacétyléthylènediamine (TAED), les N-acylimides, en particulier le N-nonanoylsuccinimide (NOSI), les phénolsulfonates acylés, en particulier le n-nonanoyloxybenzènesulfonate ou l'isononanoyloxybenzènesulfonate (n-NOBS ou iso-NOBS), le n-méthyl-morpholinium-acétonitrile-méthylsulfate (MMA).
  7. Procédé pour la préparation d'un agent de rinçage en forme de particules contenant
    a) 5 à 95% en poids d'une ou de plusieurs substances actives, au moins une des substances actives étant un agent tensioactif,
    b) 95 à 5% en poids d'un ou de plusieurs matériaux support du groupe des zéolithes, des bentonites, des silicates, des carbonates, des hydrogénocarbonates, des sulfates, des phosphates, des polycarboxylates réticulés, des poly(alcools vinyliques), des poly(acides carboxyliques) solides à température ambiante ou des polymères naturels ou semi-synthétiques tels que des dérivés d'amidon ou de cellulose et/ou d'un ou de plusieurs liants du groupe des polyéthylèneglycols, des polyacrylates, des galactomannanes, des éthers de cellulose, des monosaccharides, des oligosaccharides ou des polysaccharides et/ou des résines ainsi que
    c) 0 à 10% en poids d'autres substances actives et adjuvants

    caractérisé en ce que
    - les composants a, b et le cas échéant c sont compactés de telle manière que les substances actives du composant a et le cas échéant les autres constituants du composant c sont libérés à un moment déterminé au préalable ou pendant un laps de temps défini au préalable dans le processus de nettoyage.
  8. Procédé selon la revendication 7, caractérisé en ce que le compactage des particules a lieu dans une presse ou par extrusion.
  9. Procédé selon l'une quelconque des revendications 7 ou 8, caractérisé en ce que les composants a) sont appliqués sur les composants b) et sont ensuite compactés, le cas échéant avec addition d'autres substances.
  10. Procédé selon l'une quelconque des revendications 7 à 9, caractérisé en ce que le mélange à compacter contient, comme substance active une ou plusieurs substances des groupes constitués par les agents de blanchiment, les activateurs de blanchiment, les inhibiteurs de corrosion, les inhibiteurs de tartre et/ou les co-builders en des quantités de 5 à 80% en poids; de préférence de 10 à 70% en poids et en particulier de 10 à 60% en poids, à chaque fois par rapport au poids des particules.
  11. Agent pour le lavage de vaisselle en machine, en forme de particules, contenant des builders ainsi qu'éventuellement d'autres constituants des groupes des agents tensioactifs, des enzymes, des agents de blanchiment, des activateurs de blanchiment, des inhibiteurs de corrosion, des polymères, des colorants et des parfums, caractérisé en ce qu'il contient un agent de rinçage en forme de particules selon l'une quelconque des revendications 1 à 6 en des quantités de 0,5 à 30% en poids, de préférence de 1 à 25% en poids et en particulier de 2 à 15% en poids, à chaque fois par rapport à l'agent total.
  12. Agent pour le lavage de vaisselle en machine en forme de particules selon la revendication 11, caractérisé en ce que l'agent de rinçage en forme de particules présente des grosseurs de particules entre 2 et 30 mm, de préférence entre 2,5 et 25 mm et en particulier entre 3 et 20 mm.
  13. Agent pour le lavage de vaisselle en machine en forme de particules selon l'une quelconque des revendications 11 ou 12, caractérisé en ce qu'il présente, sans prendre en considération les particules d'agent de rinçage, des grosseurs de particules entre 0,2 et 3 mm, de préférence entre 0,3 et 2,5 mm et en particulier entre 0,4 et 2 mm.
  14. Agent pour le lavage de vaisselle en machine en forme de particules selon l'une quelconque des revendications 11 1 à 13, caractérisé en ce qu'il contient les particules d'agent de rinçage selon l'une quelconque des revendications 1 à 8 en mélange avec les autres constituants usuels pour les agents de lavage de vaisselle en machine.
  15. Agent pour le lavage de vaisselle en machine en forme de particules selon l'une quelconque des revendications 11 à 14, caractérisé en ce qu'il s'agit d'un corps façonné qui contient les particules d'agent de rinçage selon l'une quelconque des revendications 1 à 8 et des constituants usuels pour les agents de lavage de vaisselle en machine.
  16. Agent pour le lavage de vaisselle en machine en forme de particules selon l'une quelconque des revendications 11 à 15, caractérisé en ce qu'une unité de dosage se trouve dans un sachet constitué par une feuille soluble dans l'eau.
  17. Kit de parties comprenant un agent pour le lavage de vaisselle en machine sous forme de poudre selon l'une quelconque des revendications 11 à 16 et un insert de tamis pour les lave-vaisselle domestiques.
  18. Kit de parties selon la revendication 17, caractérisé en ce que les grosseurs des particules de l'agent pour le lavage de vaisselle en machine, en prenant en considération les particules d'agent de rinçage se situent dans la plage de 0,4 à 2,5 mm, de préférence de 0,5 à 1,6 mm et en particulier de 0,6 à 1,2 mm.
  19. Kit de parties selon l'une quelconque des revendications 17 ou 18, caractérisé en ce que la largeur des mailles ou la taille des trous de l'insert de tamis est de 1 à 4 mm et les particules d'agent de rinçage sont plus grandes que cette largeur des mailles ou cette taille des trous de l'insert de tamis.
EP00125168A 1999-11-27 2000-11-18 Agent de rinçage particulaire et composition pour lavage de la vaiselle en machine Revoked EP1103599B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19957262 1999-11-27
DE19957262A DE19957262A1 (de) 1999-11-27 1999-11-27 Teilchenförmiger Klarspüler und maschinelle Geschirrspülmittel

Publications (2)

Publication Number Publication Date
EP1103599A1 EP1103599A1 (fr) 2001-05-30
EP1103599B1 true EP1103599B1 (fr) 2006-03-08

Family

ID=7930640

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00125168A Revoked EP1103599B1 (fr) 1999-11-27 2000-11-18 Agent de rinçage particulaire et composition pour lavage de la vaiselle en machine

Country Status (4)

Country Link
EP (1) EP1103599B1 (fr)
AT (1) ATE319806T1 (fr)
DE (2) DE19957262A1 (fr)
ES (1) ES2259970T3 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11905493B2 (en) 2019-09-27 2024-02-20 Ecolab Usa Inc. Concentrated 2 in 1 dishmachine detergent and rinse aid

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10015289A1 (de) * 2000-03-28 2001-10-18 Henkel Kgaa Teilchenförmige maschinelle Geschirrspülmittel mit Klarspüleffekt
GB2377451A (en) † 2001-07-11 2003-01-15 Reckitt Benckiser Nv Delayed release cleaning composition for automatic dishwashers
DE20320615U1 (de) * 2002-02-26 2005-01-13 Rational Ag Reinigungsmittel für Gargeräte in Tabform
GB2386612A (en) * 2002-03-22 2003-09-24 Reckitt Benckiser Nv Cleaning method
ES2287836T3 (es) 2005-04-29 2007-12-16 MKN MASCHINENFABRIK KURT NEUBAUER GMBH & CO. Aparato de cocinado con una salida del recinto de cocinado y un sifon.
EP2014757A1 (fr) * 2007-07-05 2009-01-14 JohnsonDiversey, Inc. Produit de rinçage
PL2392639T3 (pl) * 2010-06-04 2018-07-31 Dalli-Werke Gmbh & Co. Kg Mieszanina środka powierzchniowo czynnego zawierająca stały związek dla polepszania działania ułatwiającego płukanie detergentów do automatycznych zmywarek do naczyń
US9796947B2 (en) 2014-03-07 2017-10-24 Ecolab Usa Inc. Detergent composition comprising a polymer that performs both a cleaning and rinsing function
US9969959B2 (en) 2014-03-07 2018-05-15 Ecolab Usa Inc. Detergent composition that performs both a cleaning and rinsing function
JP7091454B2 (ja) 2017-11-14 2022-06-27 エコラボ ユーエスエー インコーポレイティド 固形制御放出苛性洗剤組成物

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5453216A (en) * 1994-04-28 1995-09-26 Creative Products Resource, Inc. Delayed-release encapsulated warewashing composition and process of use
US5783540A (en) * 1996-12-23 1998-07-21 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing tablets delivering a rinse aid benefit
DE19914364A1 (de) * 1999-03-30 2000-10-05 Henkel Kgaa Teilchenförmiger Klarspüler und maschinelle Geschirrspülmittel
DE19914363A1 (de) * 1999-03-30 2000-10-05 Henkel Kgaa Maschinelle Geschirrspülmittel mit teilchenförmigem Klarspüler

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11905493B2 (en) 2019-09-27 2024-02-20 Ecolab Usa Inc. Concentrated 2 in 1 dishmachine detergent and rinse aid

Also Published As

Publication number Publication date
DE19957262A1 (de) 2001-05-31
DE50012350D1 (de) 2006-05-04
EP1103599A1 (fr) 2001-05-30
ATE319806T1 (de) 2006-03-15
ES2259970T3 (es) 2006-11-01

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