EP2931859B1 - Surfactant combination for improved drying - Google Patents

Surfactant combination for improved drying Download PDF

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Publication number
EP2931859B1
EP2931859B1 EP13802967.3A EP13802967A EP2931859B1 EP 2931859 B1 EP2931859 B1 EP 2931859B1 EP 13802967 A EP13802967 A EP 13802967A EP 2931859 B1 EP2931859 B1 EP 2931859B1
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EP
European Patent Office
Prior art keywords
carbon atoms
functional group
surfactant
branched
independently
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP13802967.3A
Other languages
German (de)
French (fr)
Other versions
EP2931859A1 (en
Inventor
Thomas Eiting
Nina Mussmann
Thorsten Bastigkeit
Konstantin Benda
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Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to PL13802967T priority Critical patent/PL2931859T3/en
Publication of EP2931859A1 publication Critical patent/EP2931859A1/en
Application granted granted Critical
Publication of EP2931859B1 publication Critical patent/EP2931859B1/en
Not-in-force legal-status Critical Current
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L15/00—Washing or rinsing machines for crockery or tableware
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04—Cleaning involving contact with liquid
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols

Definitions

  • the present application relates to a dishwashing detergent containing a combination of different nonionic surfactants, a machine dishwashing process using this dishwashing detergent and the use of this dishwashing detergent to improve drying in automatic dishwashing.
  • Dishwashing detergents are available to the consumer in a variety of forms. In addition to the traditional liquid hand dishwashing detergents, with the spread of household dishwashers in particular the automatic dishwashing detergents have become very important. These automatic dishwashing agents are typically offered to the consumer in solid form, for example as a powder or as a tablet, but increasingly also in liquid form.
  • the WO 2011/151188 A1 discloses a machine dishwashing detergent containing the combination of a nonionic surfactant and polyvinylpyrrolidone particles which results in improved cleaning performance and drying.
  • This application was based on the object to provide a dishwashing detergent, which leads to an improved drying of the items to be washed, in particular plastic Spülgut.
  • nonionic surfactants B and C are selected from the group of hydroxy mixed ethers of the general formula C 4-22 -CH (OH) CH 2 O- (EO) 20-20 -C 2-26 , for example the C 8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ethers and the C 4-22 fatty alcohol (EO) 40-80 -2-hydroxyalkyl ethers.
  • the dishwashing agent contains 0.1 to 10 wt .-%, preferably 0.5 to 7 wt .-% and particularly preferably 1 to 5 wt .-% of surfactant A, 0.1 to 10 wt .-%, preferably 0.5 to 7 wt .-% and particularly preferably 1 to 5 wt .-% of surfactant B, 0.1 to 10 wt .-%, preferably 0.5 to 7 wt .-% and particularly preferably 1 to 5 wt % Of surfactant C and 0.1 to 10% by weight, preferably 0.5 to 7% by weight and more preferably 1 to 5% by weight of surfactant D.
  • Another object of the invention is a method for cleaning dishes in a dishwasher, using a special dishwashing detergent.
  • a dishwashing which is carried out at a liquor temperature below 60 ° C, preferably not above 50 ° C.
  • a reduced fleet temperature is expressly desired by the consumer from an economic and environmental point of view.
  • Another object of the invention is the use of a dishwashing detergent to improve the drying of Party Sharinggut in automatic dishwashing.
  • the special dishwashing detergent is preferably a machine dishwashing detergent.
  • Dishwashing compositions preferably automatic dishwashing compositions, in this application refer to compositions which can be used to clean soiled dishes in a dishwashing process.
  • the special dishwashing agents differ for example from so-called rinse aids, which can be used in combination with dishwashing detergents and do not develop their own cleaning action.
  • surfactant A may include (ex BASF), for example Dehypon ® DA, wherein surfactant A is in no way limited thereto.
  • the nonionic surfactant A is preferably used in amounts of from 0.1 to 10% by weight, more preferably in amounts of from 0.5 to 7% by weight and in particular in amounts of from 1 to 5% by weight in dishwashing detergent, wt .-% based on the total agent.
  • a dishwashing detergent containing the nonionic surfactants B and C, which are selected from the group of hydroxy mixed ethers of the general formula C 4-22 -CH (OH) CH 2 O- (EO) 20-120 -C 2- 26 .
  • the agent contains C 8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ether and the C 4-22 fatty alcohol (EO) 40-80 -2-hydroxyalkyl ethers as surfactants B and C.
  • surfactant B for example, Dehypon ® E127 include (ex BASF), and surfactant C Dehypon GRA ® (ex BASF), which neither surfactant B, nor surfactant C is limited thereto in any way.
  • the nonionic surfactants B and C are each preferably in amounts of from 0.1 to 10% by weight, more preferably in amounts of from 0.5 to 7% by weight and in particular in amounts of from 1 to 5% by weight in dishwashing detergent used, wt .-% based on the total agent.
  • surfactant D may include, for example Plurafac LF ® 7319 (ex BASF), said surfactant D is in no way limited thereto.
  • the nonionic surfactant D is preferably used in amounts of from 0.1 to 10% by weight, more preferably in amounts of from 0.5 to 7% by weight and in particular in amounts of from 1 to 5% by weight in dishwashing detergent, wt .-% based on the total agent.
  • the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.
  • the dishwashing detergent may contain, in addition to the nonionic surfactants already mentioned, further nonionic surfactants which may likewise correspond to one of the general formulas of the nonionic surfactants A to D, but are in no way limited thereto.
  • the proportion by weight of the nonionic surfactant in the total weight of the dishwashing agent in a preferred embodiment is 0.4 to 40 wt .-%, more preferably 1 to 30 wt .-%, particularly preferably 2 to 20 wt .-% and in particular 4 to 20 wt. -%.
  • the dishwashing detergent may contain surfactants as well as builders.
  • Builders are typically materials that help maintain the dishwashing detergent's performance by, inter alia, inhibiting the formation of limescale deposits on machine components, thereby enabling efficient transfer of energy to the water.
  • the proportion by weight of the builders in the total weight of the dishwashing agent is preferably 15 to 80 wt .-% and in particular 20 to 70 wt .-%.
  • the builders include in particular carbonates, phosphates, citrates, and silicates.
  • phosphate s
  • alkali metal phosphates with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are the most important in the detergent and cleaner industry.
  • Alkali metal phosphate is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acid (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts or lime incrustations on the objects to be cleaned and, moreover, contribute to the cleaning performance.
  • Particularly preferred phosphates are the pentasodium triphosphate, Na 5 P 3 O 10 (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate). Preference is furthermore given to using the sodium potassium tripolyphosphates.
  • phosphates are used as builders in dishwashing detergents in the context of the present application, this contains phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of from 5 to 70% by weight .-%, preferably from 15 to 55 wt .-% and in particular from 20 to 50 wt .-%, each based on the total weight of the dishwashing detergent.
  • phosphate preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate)
  • Polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals and dextrins are also used as preferred builders. This class of substances is also referred to as organic cobuilders and described below.
  • a polycarboxylic acid can be used in the form of the free acid and / or its alkali metal salts, in particular sodium salts, polycarboxylic acid meaning that carboxylic acid which carries more than one acid function.
  • polycarboxylic acid meaning that carboxylic acid which carries more than one acid function.
  • NTA nitrilotriacetic acid
  • the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • the dishwashing detergent may contain citrate as the builder, preferably sodium citrate.
  • the dishwashing detergent may preferably contain from 2 to 40% by weight, preferably from 5 to 30% by weight and in particular from 7 to 20% by weight, of citrate, in particular sodium citrate, based on the total weight of the dishwashing detergent.
  • the citrates are preferably used with carbonates and / or bicarbonates.
  • Preferred dishwashing detergents therefore contain a builder combination of phosphate and carbonate / bicarbonate or of citrate and carbonate / bicarbonate or of phosphate, citrate and carbonate / bicarbonate.
  • a particularly preferred dishwashing detergent is characterized in that it contains at least two builders from the group of phosphates, carbonates and citrates, wherein the proportion by weight of these builders, based on the total weight of the dishwashing agent, preferably 5 to 80 wt .-%, preferably 15 to 75 Wt .-% and in particular 30 to 70 wt .-% is.
  • the combination of two or more builders from the above-mentioned group has proven to be advantageous for the cleaning and rinsing performance of the dishwashing detergent.
  • polymeric polycarboxylates are also suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a weight-average molar mass of from 500 to 70,000 g / mol.
  • Suitable polymers are, in particular, polyacrylates, which preferably have a weight average molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have a weight-average molar mass of from 2,000 to 10,000 g / mol, and particularly preferably from 3,000 to 5,000 g / mol, may again be preferred from this group.
  • the weight-average molar masses can be determined by means of gel permeation chromatography.
  • the content of (homo) polymeric polycarboxylates in dishwashing detergent is preferably 0.5 to 20 wt .-% and in particular 3 to 10 wt .-%.
  • the dishwashing detergent can be a builder crystalline layered silicates of the general formula NaMSi x O 2x + 1 ⁇ y H 2 O in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, particularly preferably 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20, stands.
  • 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 preferably delayed release and have secondary washing properties.
  • the content of silicates is limited to amounts of from 0 to 10% by weight, preferably from 0 to 5% by weight and in particular from 0 to 2% by weight.
  • a particularly preferred dishwashing detergent is free of silicates.
  • the dishwashing detergent may contain alkaline agents, preferably alkali metal hydroxides, in particular sodium hydroxide. These alkaline agents are preferred in the dishwashing detergent in amounts of 0 to 10 wt .-%, preferably from 0 to 5 wt .-%, particularly preferably between 0.1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, in each case based on the total weight of the dishwashing detergent used.
  • An alternative preferred dishwashing detergent is free of alkali metal hydroxides.
  • the dishwashing detergent may preferably contain enzymes. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases and preferably mixtures thereof. Enzymes may be present in the dishwashing detergent preferably in amounts of from 0.0001 to 10% by weight, preferably from 0.01 to 5% by weight, preferably from 0.1 to 4% by weight, more preferably between 0.2 and 4 wt .-%, each based on the total weight of the dishwashing detergent, are used.
  • enzymes include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases and preferably mixtures thereof. Enzymes may be present in the dishwashing detergent preferably in amounts of from 0.0001 to 10% by weight, preferably from 0.01 to 5% by weight, preferably from 0.1 to 4% by weight, more preferably between 0.2 and 4 w
  • the dishwashing agent is preferably a solid dishwashing detergent.
  • a "solid dishwashing detergent” is to be understood as meaning a dishwashing detergent which is in a solid state of aggregation at 25 ° C. and a pressure of 1 bar.
  • the dishwashing agent is preferably in the form of a shaped body, in particular a Kompaktats, especially as a tablet.
  • the shaped body may take any geometric shape such as concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylindrical, octahedral, conical, pyramidal, ellipsoidal, pentagonal, hexagonal, octagonal prismatic and rhombohedral shapes.
  • the preparation of the molding is preferably carried out by compression of particulate starting materials.
  • a premix is preferably compressed in a so-called matrix between two punches to form a solid compactate.
  • This process hereinafter referred to as tableting, is divided into four sections: dosing, compaction (elastic deformation), plastic deformation and ejection.
  • the tableting is preferably carried out on so-called rotary presses.
  • the ingredients provided for tabletting can be added in the form of a common particulate premix at the same time or in the form of individual, separate powders or granules offset in time or at the same time in the mold, the dosage of a prefabricated particulate premix is preferred.
  • the shaped body may contain a disintegrant in a further preferred embodiment.
  • the effect of disintegrants is usually that they increase their volume upon ingress of water, whereby on the one hand increases the intrinsic volume (swelling), or on the other hand, via the release of gases, a pressure can be generated, which disintegrate the tablet into smaller particles leaves.
  • cross-linked polyvinylpyrrolidone crospovidone
  • crospovidone cross-linked polyvinylpyrrolidone
  • the dishwashing detergent can be a disintegrating agent, in particular polyvinylpyrrolidone, preferably in an amount of from 0.1 to 5% by weight, in particular in an amount of from 0.2 to 3% by weight, in particular in an amount of from 0.3 to 1 , 8 wt .-%, based on the total weight of the dishwashing detergent.
  • a disintegrating agent in particular polyvinylpyrrolidone, preferably in an amount of from 0.1 to 5% by weight, in particular in an amount of from 0.2 to 3% by weight, in particular in an amount of from 0.3 to 1 , 8 wt .-%, based on the total weight of the dishwashing detergent.
  • further disintegrants may also be present in the moldings, for example carbonate / citric acid systems or carbonate in combination with other organic acids, synthetic polymers or natural polymers or modified natural substances such as cellulose and starch and their derivatives and Alginates or casein derivatives.
  • gas-evolving effervescent systems can also be used as further disintegrants.
  • Preferred effervescent systems consist of at least two constituents which react with one another to form gas, for example from alkali metal carbonate and / or bicarbonate and an acidifier which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution.
  • An acidifying agent which releases carbon dioxide from the alkali salts in aqueous solution is, for example, citric acid.
  • the shaped article may also be present in combination with other forms of offers, in particular in combination with solid forms such as powders, granules or extrudates or in combination with liquid formulations based on water and / or organic solvents.
  • the shaped body may, for example, also be a granulate which is contained in a bag or a casting mold.
  • the simplest realization possibility lies in two or more multilayer tablets, each layer of the molding representing a single phase.
  • the various constituents which fulfill the different functions of a dishwashing detergent can preferably be kept separate from one another such that they can not undesirably interact before the washing cycle.
  • the specific nonionic surfactants A to D may be present in each layer of the tablet either individually or in any desired combination.
  • certain surfactants or surfactant combinations may be preferred in one of the phases, but in a further embodiment of the invention, the surfactants may also be uniformly distributed to all phases.
  • one or more phases of the tablet are completely free of the specific nonionic surfactants A to D.
  • a two-phase or multi-phase tablet for example a two-layer tablet, in particular a two-layer tablet with a trough and a shaped body located in the trough, is particularly preferred.
  • a multiphase tablet be prepared in which the one phase is integrated in the form of a storage in the other (s) phase (s).
  • the dishwashing agent is preferably prefabricated to dosage units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g.
  • the volume of the aforementioned metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units is ensured via the metering chamber of a dishwasher.
  • the volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml and in particular between 15 and 25 ml.
  • the dishwashing detergent in particular the prefabricated metering units, may in a preferred embodiment have a water-soluble coating.
  • the dishwashing detergent may contain other additives such as washing or cleaning-active substances, preferably from the group of glass corrosion inhibitors, corrosion inhibitors, fragrances and perfume carriers.
  • the combinations of ingredients described above are preferably suitable for cleaning dishes in dishwashing processes, in particular in automatic dishwashing processes.
  • a further subject of the present application is a machine dishwashing process in which the dishwashing detergent is used.
  • the dishwashing detergent is preferably metered or introduced into the interior of a dishwasher during the passage of a dishwashing program, before the main wash cycle or during the main wash cycle.
  • the dispensing or the entry of the dishwashing detergent into the interior of the dishwasher can be done manually, but preferably the dishwashing detergent is metered into the interior of the dishwasher by means of the metering chamber of the dishwasher.
  • no additional water softener and no additional rinse aid is metered into the interior of the dishwasher.
  • a preferred embodiment is a machine dishwashing process using the preferably solid dishwashing agent, in particular in the form of a previously mentioned shaped body, in particular for the improved drying of plastic dishwashing product.
  • the dishwashing process is preferably carried out at a liquor temperature below 60 ° C., preferably not above 50 ° C., preferably at 35 to 45 ° C.
  • the dishwashing process takes 5 to 90 minutes, in particular 10 to 75 minutes, particularly preferably 20 to 60 minutes.
  • the dishwashing process takes a maximum of 50, 40 or 30 minutes.
  • the dishwashing detergent is distinguished from conventional dishwashing detergents by improved drying performance.
  • Another object of the present application is therefore the use of a special dishwashing detergent to improve the drying of Party Sharinggut in automatic dishwashing.
  • Formulations E1 and E2 correspond to a dishwasher detergent according to the invention, the formulations V1 to V3 are comparative examples.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Description

Die vorliegende Anmeldung betrifft ein Geschirrspülmittel, enthaltend eine Kombination verschiedener nichtionischer Tenside, ein maschinelles Geschirrspülverfahren unter Einsatz dieses Geschirrspülmittels sowie die Verwendung dieses Geschirrspülmittels zur Verbesserung der Trocknung beim maschinellen Geschirrspülen.The present application relates to a dishwashing detergent containing a combination of different nonionic surfactants, a machine dishwashing process using this dishwashing detergent and the use of this dishwashing detergent to improve drying in automatic dishwashing.

Geschirrspülmittel stehen dem Verbraucher in einer Vielzahl von Angebotsformen zur Verfügung. Neben den traditionellen flüssigen Handgeschirrspülmitteln, haben mit der Verbreitung von Haushaltsgeschirrspülmaschinen insbesondere die maschinellen Geschirrspülmittel eine große Bedeutung erlangt. Diese maschinellen Geschirrspülmittel werden dem Verbraucher typischerweise in fester Form, beispielsweise als Pulver oder als Tablette, zunehmend jedoch auch in flüssiger Form angeboten.Dishwashing detergents are available to the consumer in a variety of forms. In addition to the traditional liquid hand dishwashing detergents, with the spread of household dishwashers in particular the automatic dishwashing detergents have become very important. These automatic dishwashing agents are typically offered to the consumer in solid form, for example as a powder or as a tablet, but increasingly also in liquid form.

Ein Ziel der Hersteller maschineller Geschirrspülmittel ist die stetige Verbesserung der Reinigungsleistung dieser Mittel, wobei üblicherweise spezielle Tenside eingesetzt werden, wie beispielsweise nichtionische Tenside. Aus ökologischen und ökonomischen Gründen legt der Verbraucher in jüngster Zeit zusätzlich ein verstärktes Augenmerk auf die Reinigungsleistung bei Niedrigtemperatur-Reinigungsgängen, kurze Reinigungsgänge und/oder auf Reinigungsgänge mit verringertem Wasserverbrauch.One aim of the manufacturers of automatic dishwashing detergents is the continuous improvement of the cleaning performance of these compositions, usually using special surfactants, for example nonionic surfactants. For environmental and economic reasons, the consumer has recently been placing additional emphasis on the cleaning performance of low-temperature cleaning cycles, short cleaning cycles and / or cleaning cycles with reduced water consumption.

Diese Entwicklungen führen jedoch häufig dazu, dass das Spülgut nach dem Spülzyklus nicht ausreichend getrocknet wird und der Verbraucher manuell nachtrocknen muss, was wenig verbraucherfreundlich ist.However, these developments often mean that the items to be washed are not sufficiently dried after the rinsing cycle and the consumer has to manually dry them, which is less consumer-friendly.

Die WO 2011/151188 A1 offenbart ein maschinelles Geschirrspülmittel, das die Kombination aus einem nichtionischen Tensid und Polyvinylpyrrolidon-Partikeln enthält und zur Verbesserung der Reinigungsleistung und Trocknung führt.The WO 2011/151188 A1 discloses a machine dishwashing detergent containing the combination of a nonionic surfactant and polyvinylpyrrolidone particles which results in improved cleaning performance and drying.

Durch die Kombination von zwei nichtionischen Tensiden mit einem anionischen Copolymer konnte in der EP 2 358 853 eine Verbesserung der Reinigungs- und Klarspülleistung sowie eine verbesserte Trocknung des Spülguts beobachtet werden.The combination of two nonionic surfactants with one anionic copolymer enabled the EP 2 358 853 an improvement in the cleaning and rinsing performance and improved drying of the items to be washed are observed.

Obwohl durch die Gegenstände der genannten Schriften Fortschritte bei der Trocknungsleistung gemacht werden konnten, ist für die Trocknung des Spülguts, insbesondere von Plastik, weiterhin häufig noch ein manuelles Nachtrocknen durch den Verbraucher notwendig.Although progress could be made in the drying performance by the subjects of the cited documents, for the drying of the items to be washed, in particular of plastic, still often requires a manual post-drying by the consumer.

Dieser Anmeldung lag die Aufgabe zugrunde, ein Geschirrspülmittel bereitzustellen, das zu einer verbesserten Trocknung des Spülguts, insbesondere von Plastikspülgut, führt.This application was based on the object to provide a dishwashing detergent, which leads to an improved drying of the items to be washed, in particular plastic Spülgut.

Diese Aufgabe wird durch ein Geschirrspülmittel gelöst, das zumindest vier nichtionische Tenside A, B, C und D enthält, wobei

  1. I. Tensid A durch die allgemeine Formel

            R1O(AlkO)xM(OAlk)yOR2

    beschrieben wird, wobei
    • R1 und R2 unabhängig voneinander für einen verzweigten oder unverzweigten, gesättigten oder ungesättigten, gegebenenfalls hydroxylierten Alkylrest mit 4 bis 22 Kohlenstoffatomen stehen,
    • Alk für einen verzweigten oder unverzweigten Alkylrest mit 2 bis 4 Kohlenstoffatomen steht,
    • x und y unabhängig voneinander für Werte zwischen 1 und 70 stehen und
    • M für einen Alkylrest aus der Gruppe CH2, CHR3, CR3R4, CH2CHR3 und CHR3CHR4 steht, wobei R3 und R4 unabhängig voneinander für einen verzweigten oder unverzweigten, gesättigten oder ungesättigten, cyclischen oder acyclischen Alkyl- oder Alkenylrest mit 1 bis 18 Kohlenstoffatomen stehen;
  2. II. Tenside B und C, welche unterschiedlich sind, beide durch die allgemeine Formel

            R1O[CH2CH(CH3)O]x[CH2CH2O]y[CH2CH(CH3)O]zCH2CH(OH)R2

    beschrieben werden, in der
    • R1 für einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 4 bis 22 Kohlenstoffatomen steht,
    • R2 einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen bezeichnet,
    • x und z für Werte zwischen 0 und 40 stehen und
    • y für einen Wert von mindestens 15 steht; und
  3. III. Tensid D durch die allgemeine Formel

            R1O[CH2CH(R3)O]x[CH2CHO]y[CH2CH(R4)O]zC(O)R2

    beschrieben wird, wobei
    • R1 für einen verzweigten oder unverzweigten Alkylrest mit 8 bis 16 Kohlenstoffatomen steht,
    • R3 und R4 unabhängig voneinander für Wasserstoff oder einen verzweigten oder unverzweigten Alkylrest mit 1 bis 5 Kohlenstoffatomen stehen,
    • R2 für einen unverzweigten Alkylrest mit 5 bis 17 Kohlenstoffatomen steht,
    • x und z unabhängig voneinander für einen Wert von 1 bis 5 stehen und
    • y für einen Wert von 13 bis 35 steht.
This object is achieved by a dishwashing detergent containing at least four nonionic surfactants A, B, C and D, wherein
  1. I. Surfactant A by the general formula

    R 1 O (AlkO) x M (OAlk) y OR 2

    is described, wherein
    • R 1 and R 2 independently of one another represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms,
    • Alk is a branched or unbranched alkyl radical having 2 to 4 carbon atoms,
    • x and y independently represent values between 1 and 70, and
    • M is an alkyl group from the group CH 2 , CHR 3 , CR 3 R 4 , CH 2 CHR 3 and CHR 3 CHR 4 , wherein R 3 and R 4 are independently a branched or unbranched, saturated or unsaturated, cyclic or acyclic Alkyl or alkenyl radical having 1 to 18 carbon atoms;
  2. II. Surfactants B and C, which are different, both by the general formula

    R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (CH 3 ) O] z CH 2 CH (OH) R 2

    be described in the
    • R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 22 carbon atoms,
    • R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms,
    • x and z are values between 0 and 40 and
    • y is a value of at least 15; and
  3. III. Surfactant D by the general formula

    R 1 O [CH 2 CH (R 3 ) O] x [CH 2 CHO] y [CH 2 CH (R 4 ) O] z C (O) R 2

    is described, wherein
    • R 1 is a branched or unbranched alkyl radical having 8 to 16 carbon atoms,
    • R 3 and R 4 independently of one another represent hydrogen or a branched or unbranched alkyl radical having 1 to 5 carbon atoms,
    • R 2 is an unbranched alkyl radical having 5 to 17 carbon atoms,
    • x and z independently represent a value of 1 to 5 and
    • y stands for a value of 13 to 35.

Überraschenderweise wurde nun gefunden, dass ein Geschirrspülmittel, das zumindest vier unterschiedliche spezielle nichtionische Tenside enthält, zu einer vollständigeren Trocknung von Spülgut in einem maschinellen Geschirrspülverfahren führt.Surprisingly, it has now been found that a dishwashing detergent which contains at least four different special nonionic surfactants leads to a more complete drying of items to be washed in a machine dishwashing process.

Es ist dabei bevorzugt, dass das Geschirrspülmittel als nichtionisches Tensid A ein Tensid der allgemeinen Formel

        R1-CH(OH)CH2-O(CH2CH2O)xCH2CHR(OCH2CH2)yO-CH2CH(OH)-R2

enthält, in der

  • R1 und R2 unabhängig voneinander für einen Alkylrest oder Alkenylrest mit 6 bis 16 Kohlenstoffatomen und
  • R für einen linearen, gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, vorzugsweise 4 bis 10 Kohlenstoffatomen steht und
  • x und y unabhängig voneinander Werte von 5 bis 20 aufweisen.
It is preferred that the dishwashing detergent as nonionic surfactant A is a surfactant of the general formula

R 1 is -CH (OH) CH 2 -O (CH 2 CH 2 O) x CH 2 CHR (OCH 2 CH 2 ) y O-CH 2 CH (OH) -R 2

contains, in the
  • R 1 and R 2 independently represent an alkyl radical or alkenyl radical having 6 to 16 carbon atoms and
  • R is a linear, saturated alkyl radical having 2 to 12 carbon atoms, preferably 4 to 10 carbon atoms, and
  • x and y independently of one another have values of 5 to 20.

Es ist ebenfalls bevorzugt, dass das Geschirrspülmittel die nichtionischen Tenside B und C der allgemeinen Formel

        R1O[CH2CH2O]yCH2CH(OH)R2

aufweist, in der

  • R1 für einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 4 bis 22 Kohlenstoffatomen steht,
  • R2 einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen bezeichnet und
  • y für einen Wert zwischen 15 und 120, vorzugsweise 20 bis 100 und insbesondere 20 bis 80 steht.
It is also preferred that the dishwashing detergent comprises the nonionic surfactants B and C of the general formula

R 1 O [CH 2 CH 2 O] y CH 2 CH (OH) R 2

has, in the
  • R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 22 carbon atoms,
  • R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms, and
  • y is a value between 15 and 120, preferably 20 to 100 and in particular 20 to 80.

Dabei ist es besonders bevorzugt, dass die nichtionischen Tenside B und C ausgewählt sind aus der Gruppe der Hydroxymischether der allgemeinen Formel

        C4-22-CH(OH)CH2O-(EO)20-20-C2-26,

zum Beispiel die C8-12 Fettalkohol-(EO)22-2-hydroxydecylether und die C4-22 Fettalkohol-(EO)40-80-2-hydroxyalkylether.It is particularly preferred that the nonionic surfactants B and C are selected from the group of hydroxy mixed ethers of the general formula

C 4-22 -CH (OH) CH 2 O- (EO) 20-20 -C 2-26 ,

for example the C 8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ethers and the C 4-22 fatty alcohol (EO) 40-80 -2-hydroxyalkyl ethers.

Es ist zudem bevorzugt, dass in dem Geschirrspülmittel als nichtionisches Tensid D ein Tensid der allgemeinen Formel

        R1O[CH2CH(R3)O]x[CH2CHO]y[CH2CH(R4)O]zC(O)R2 eingesetzt wird, wobei

  • R1 für einen verzweigten oder unverzweigten Alkylrest mit 10 bis 15 Kohlenstoffatomen steht,
  • R3 und R4 unabhängig voneinander für Wasserstoff oder einen verzweigten oder unverzweigten Alkylrest mit 2 oder 3 Kohlenstoffatomen stehen,
  • R2 für einen unverzweigten Alkylrest mit 8 bis 16 Kohlenstoffatomen steht,
  • x und z unabhängig voneinander für einen Wert von 1 bis 5 stehen und
  • y für einen Wert von 20 bis 30 steht.
It is also preferred that in the dishwashing detergent as nonionic surfactant D, a surfactant of the general formula

R 1 O [CH 2 CH (R 3 ) O] x [CH 2 CHO] y [CH 2 CH (R 4 ) O] z C (O) R 2 is used, where

  • R 1 is a branched or unbranched alkyl radical having 10 to 15 carbon atoms,
  • R 3 and R 4 independently of one another represent hydrogen or a branched or unbranched alkyl radical having 2 or 3 carbon atoms,
  • R 2 is an unbranched alkyl radical having 8 to 16 carbon atoms,
  • x and z independently represent a value of 1 to 5 and
  • y stands for a value of 20 to 30.

In einer bevorzugten Ausführungsform enthält das Geschirrspülmittel 0,1 bis 10 Gew.-%, bevorzugt 0,5 bis 7 Gew.-% und besonders bevorzugt 1 bis 5 Gew.-% Tensid A, 0,1 bis 10 Gew.-%, bevorzugt 0,5 bis 7 Gew.-% und besonders bevorzugt 1 bis 5 Gew.-% Tensid B, 0,1 bis 10 Gew.-%, bevorzugt 0,5 bis 7 Gew.-% und besonders bevorzugt 1 bis 5 Gew.-% Tensid C und 0,1 bis 10 Gew.-%, bevorzugt 0,5 bis 7 Gew.-% und besonders bevorzugt 1 bis 5 Gew.-% Tensid D.In a preferred embodiment, the dishwashing agent contains 0.1 to 10 wt .-%, preferably 0.5 to 7 wt .-% and particularly preferably 1 to 5 wt .-% of surfactant A, 0.1 to 10 wt .-%, preferably 0.5 to 7 wt .-% and particularly preferably 1 to 5 wt .-% of surfactant B, 0.1 to 10 wt .-%, preferably 0.5 to 7 wt .-% and particularly preferably 1 to 5 wt % Of surfactant C and 0.1 to 10% by weight, preferably 0.5 to 7% by weight and more preferably 1 to 5% by weight of surfactant D.

Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Reinigung von Geschirr in einer Geschirrspülmaschine, unter Einsatz eines speziellen Geschirrspülmittels.Another object of the invention is a method for cleaning dishes in a dishwasher, using a special dishwashing detergent.

In einer bevorzugten Ausführungsform der Erfindung handelt es sich um ein Geschirrspülverfahren, das bei einer Flottentemperatur unterhalb 60°C, vorzugsweise nicht oberhalb von 50°C durchgeführt wird.In a preferred embodiment of the invention is a dishwashing, which is carried out at a liquor temperature below 60 ° C, preferably not above 50 ° C.

Eine verminderte Flottentemperatur ist vom Verbraucher aus ökonomischer und ökologischer Sicht ausdrücklich erwünscht.A reduced fleet temperature is expressly desired by the consumer from an economic and environmental point of view.

Ein weiterer Gegenstand der Erfindung ist die Verwendung eines Geschirrspülmittels zur Verbesserung der Trocknung von Plastikspülgut beim maschinellen Geschirrspülen.Another object of the invention is the use of a dishwashing detergent to improve the drying of Plastikspülgut in automatic dishwashing.

Bei der Verwendung des speziellen Geschirrspülmittels werden nach der Trocknung von Plastikspülgut signifikant weniger Wasserrückstände auf der Oberfläche des Plastikspülguts beobachtet.When using the special dishwashing detergent significantly less water residues are observed on the surface of the plastic dishwashing material after drying of Plastikspülgut.

Im Folgenden soll die Erfindung, unter anderem anhand von Beispielen, eingehender erläutert werden.In the following, the invention will be explained in more detail, inter alia, by way of examples.

Das spezielle Geschirrspülmittel ist vorzugsweise ein maschinelles Geschirrspülmittel.The special dishwashing detergent is preferably a machine dishwashing detergent.

Als Geschirrspülmittel, vorzugsweise maschinelles Geschirrspülmittel, werden in dieser Anmeldung Zusammensetzungen bezeichnet, die zur Reinigung verschmutzten Geschirrs in einem Geschirrspülverfahren eingesetzt werden können. Damit unterscheiden sich die speziellen Geschirrspülmittel beispielsweise von sogenannten Klarspülmitteln, die in Kombination mit Geschirrspülmitteln eingesetzt werden können und keine eigene Reinigungswirkung entfalten.Dishwashing compositions, preferably automatic dishwashing compositions, in this application refer to compositions which can be used to clean soiled dishes in a dishwashing process. Thus, the special dishwashing agents differ for example from so-called rinse aids, which can be used in combination with dishwashing detergents and do not develop their own cleaning action.

Das Geschirrspülmittel enthält als einen Bestandteil ein nichtionisches Tensid A der allgemeinen Formel

        R1O(AlkO)xM(OAlk)yOR2,

wobei

  • R1 und R2 unabhängig voneinander für einen verzweigten oder unverzweigten, gesättigten oder ungesättigten, gegebenenfalls hydroxylierten Alkylrest mit 4 bis 22 Kohlenstoffatomen stehen,
  • Alk für einen verzweigten oder unverzweigten Alkylrest mit 2 bis 4 Kohlenstoffatomen steht,
  • x und y unabhängig voneinander für Werte zwischen 1 und 70 stehen und
  • M für einen Alkylrest aus der Gruppe CH2, CHR3, CR3R4, CH2CHR3 und CHR3CHR4 steht, wobei R3 und R4 unabhängig voneinander für einen verzweigten oder unverzweigten, gesättigten oder ungesättigten, cyclischen oder acyclischen Alkyl- oder Alkenylrest mit 1 bis 18 Kohlenstoffatomen stehen.
The dishwashing detergent contains as one component a nonionic surfactant A of the general formula

R 1 O (AlkO) x M (OAlk) y OR 2 ,

in which
  • R 1 and R 2 independently of one another represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms,
  • Alk is a branched or unbranched alkyl radical having 2 to 4 carbon atoms,
  • x and y independently represent values between 1 and 70, and
  • M is an alkyl group from the group CH 2 , CHR 3 , CR 3 R 4 , CH 2 CHR 3 and CHR 3 CHR 4 , wherein R 3 and R 4 are independently a branched or unbranched, saturated or unsaturated, cyclic or acyclic Alkyl or alkenyl radical having 1 to 18 carbon atoms.

In einer bevorzugten Ausführungsform enthält das Geschirrspülmittel als nichtionisches Tensid A ein Tensid der allgemeinen Formel

        R1-CH(OH)CH2-O(CH2CH2O)xCH2CHR(OCH2CH2)yO-CH2CH(OH)-R2,

in der

  • R1 und R2 unabhängig voneinander für einen Alkylrest oder Alkenylrest mit 6 bis 16 Kohlenstoffatomen stehen und
  • R für einen linearen, gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, vorzugsweise 4 bis 10 Kohlenstoffatomen steht und
  • x und y unabhängig voneinander Werte von 5 bis 20 aufweisen.
In a preferred embodiment, the dishwashing detergent contains as nonionic surfactant A a surfactant of the general formula

R 1 is -CH (OH) CH 2 -O (CH 2 CH 2 O) x CH 2 CHR (OCH 2 CH 2 ) y O-CH 2 CH (OH) -R 2 ,

in the
  • R 1 and R 2 independently of one another represent an alkyl radical or alkenyl radical having 6 to 16 carbon atoms and
  • R is a linear, saturated alkyl radical having 2 to 12 carbon atoms, preferably 4 to 10 carbon atoms, and
  • x and y independently of one another have values of 5 to 20.

In einer möglichen Ausführungsform kann Tensid A beispielsweise Dehypon® DA (ex BASF) umfassen, wobei Tensid A in keiner Weise darauf limitiert ist.In one possible embodiment, surfactant A may include (ex BASF), for example Dehypon ® DA, wherein surfactant A is in no way limited thereto.

Das nichtionische Tensid A wird bevorzugt in Mengen von 0,1 bis 10 Gew.-%, weiter bevorzugt in Mengen von 0,5 bis 7 Gew.-% und insbesondere in Mengen von 1 bis 5 Gew.-% im Geschirrspülmittel eingesetzt, Gew.-% bezogen auf das gesamte Mittel.The nonionic surfactant A is preferably used in amounts of from 0.1 to 10% by weight, more preferably in amounts of from 0.5 to 7% by weight and in particular in amounts of from 1 to 5% by weight in dishwashing detergent, wt .-% based on the total agent.

Das Geschirrspülmittel enthält als weitere Bestandteile die nichtionischen Tenside B und C, welche unterschiedlich sind und beide durch die allgemeine Formel

        R1O[CH2CH(CH3)O]x[CH2CH2O]y[CH2CH(CH3)O]zCH2CH(OH)R2

beschrieben werden, in der

  • R1 für einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 4 bis 22 Kohlenstoffatomen steht,
  • R2 einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen bezeichnet,
  • x und z für Werte zwischen 0 und 40 und
  • y für einen Wert von mindestens 15 steht.
The dishwashing detergent contains as further constituents the nonionic surfactants B and C, which are different and both are represented by the general formula

R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (CH 3 ) O] z CH 2 CH (OH) R 2

be described in the
  • R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 22 carbon atoms,
  • R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms,
  • x and z for values between 0 and 40 and
  • y is a value of at least 15.

In einer bevorzugten Ausführungsform enthält das Geschirrspülmittel die nichtionischen Tenside B und C, die die allgemeine Formel

        R1O[CH2CH2O]yCH2CH(OH)R2

aufweisen, in der

  • R1 für einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 4 bis 22 Kohlenstoffatomen steht,
  • R2 einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen bezeichnet und
  • y für einen Wert zwischen 15 und 120, vorzugsweise 20 bis 100 und insbesondere 20 bis 80 steht.
In a preferred embodiment, the dishwashing detergent contains the nonionic surfactants B and C having the general formula

R 1 O [CH 2 CH 2 O] y CH 2 CH (OH) R 2

have, in the
  • R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 22 carbon atoms,
  • R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms, and
  • y is a value between 15 and 120, preferably 20 to 100 and in particular 20 to 80.

Besonders bevorzugt ist dabei ein Geschirrspülmittel, das die nichtionischen Tenside B und C enthält, die ausgewählt sind aus der Gruppe der Hydroxymischether der allgemeinen Formel C4-22-CH(OH)CH2O-(EO)20-120-C2-26. Ganz besonders bevorzugt enthält das Mittel C8-12 Fettalkohol-(EO)22-2-hydroxydecylether und die C4-22 Fettalkohol-(EO)40-80-2-hydroxyalkylether als Tenside B und C. In einer möglichen Ausführungsform kann Tensid B dabei beispielsweise Dehypon® E127 (ex BASF) umfassen und Tensid C Dehypon® GRA (ex BASF), wobei weder Tensid B, noch Tensid C in irgendeiner Weise darauf limitiert ist.Particularly preferred is a dishwashing detergent containing the nonionic surfactants B and C, which are selected from the group of hydroxy mixed ethers of the general formula C 4-22 -CH (OH) CH 2 O- (EO) 20-120 -C 2- 26 . Most preferably, the agent contains C 8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ether and the C 4-22 fatty alcohol (EO) 40-80 -2-hydroxyalkyl ethers as surfactants B and C. In one possible embodiment, surfactant B, for example, Dehypon ® E127 include (ex BASF), and surfactant C Dehypon GRA ® (ex BASF), which neither surfactant B, nor surfactant C is limited thereto in any way.

Die nichtionischen Tenside B und C werden jeweils bevorzugt in Mengen von 0,1 bis 10 Gew.-%, weiter bevorzugt in Mengen von 0,5 bis 7 Gew.-% und insbesondere in Mengen von 1 bis 5 Gew.-% im Geschirrspülmittel eingesetzt, Gew.-% bezogen auf das gesamte Mittel.The nonionic surfactants B and C are each preferably in amounts of from 0.1 to 10% by weight, more preferably in amounts of from 0.5 to 7% by weight and in particular in amounts of from 1 to 5% by weight in dishwashing detergent used, wt .-% based on the total agent.

Das Geschirrspülmittel enthält als weiteren Bestandteil das nichtionische Tensid D, welches durch die allgemeine Formel

        R1O[CH2CH(R3)O]x[CH2CHO]y[CH2CH(R4)O]zC(O)R2

beschrieben wird, wobei

  • R1 für einen verzweigten oder unverzweigten Alkylrest mit 8 bis 16 Kohlenstoffatomen steht,
  • R3 und R4 unabhängig voneinander für Wasserstoff oder einen verzweigten oder unverzweigten Alkylrest mit 1 bis 5 Kohlenstoffatomen stehen,
  • R2 für einen unverzweigten Alkylrest mit 5 bis 17 Kohlenstoffatomen steht,
  • x und z unabhängig voneinander für einen Wert von 1 bis 5 stehen und
  • y für einen Wert von 13 bis 35 steht.
The dishwashing detergent contains as further constituent the nonionic surfactant D, which is represented by the general formula

R 1 O [CH 2 CH (R 3 ) O] x [CH 2 CHO] y [CH 2 CH (R 4 ) O] z C (O) R 2

is described, wherein
  • R 1 is a branched or unbranched alkyl radical having 8 to 16 carbon atoms,
  • R 3 and R 4 independently of one another represent hydrogen or a branched or unbranched alkyl radical having 1 to 5 carbon atoms,
  • R 2 is an unbranched alkyl radical having 5 to 17 carbon atoms,
  • x and z independently represent a value of 1 to 5 and
  • y stands for a value of 13 to 35.

In einer bevorzugten Ausführungsform der Erfindung enthält das Geschirrspülmittel als nichtionisches Tensid D ein Tensid der allgemeinen Formel

        R'O[CH2CH(R3)O]x[CH2CHO]y[CH2CH(R4)O]zC(O)R2,

wobei

  • R1 für einen verzweigten oder unverzweigten Alkylrest mit 10 bis 15 Kohlenstoffatomen steht,
  • R3 und R4 unabhängig voneinander für Wasserstoff oder einen verzweigten oder unverzweigten Alkylrest mit 2 oder 3 Kohlenstoffatomen stehen,
  • R2 für einen unverzweigten Alkylrest mit 8 bis 16 Kohlenstoffatomen steht,
  • x und z unabhängig voneinander für einen Wert von 1 bis 5 stehen und
  • y für einen Wert von 20 bis 30.
In a preferred embodiment of the invention, the dishwashing detergent contains as nonionic surfactant D a surfactant of the general formula

R'O [CH 2 CH (R 3 ) O] x [CH 2 CHO] y [CH 2 CH (R 4 ) O] z C (O) R 2 ,

in which
  • R 1 is a branched or unbranched alkyl radical having 10 to 15 carbon atoms,
  • R 3 and R 4 independently of one another represent hydrogen or a branched or unbranched alkyl radical having 2 or 3 carbon atoms,
  • R 2 is an unbranched alkyl radical having 8 to 16 carbon atoms,
  • x and z independently represent a value of 1 to 5 and
  • y for a value of 20 to 30.

In einer möglichen Ausführungsform kann Tensid D beispielsweise Plurafac® LF 7319 (ex BASF) umfassen, wobei Tensid D in keiner Weise darauf limitiert ist.In one possible embodiment, surfactant D may include, for example Plurafac LF ® 7319 (ex BASF), said surfactant D is in no way limited thereto.

Das nichtionische Tensid D wird bevorzugt in Mengen von 0,1 bis 10 Gew.-%, weiter bevorzugt in Mengen von 0,5 bis 7 Gew.-% und insbesondere in Mengen von 1 bis 5 Gew.-% im Geschirrspülmittel eingesetzt, Gew.-% bezogen auf das gesamte Mittel.The nonionic surfactant D is preferably used in amounts of from 0.1 to 10% by weight, more preferably in amounts of from 0.5 to 7% by weight and in particular in amounts of from 1 to 5% by weight in dishwashing detergent, wt .-% based on the total agent.

Die angegebenen C-Kettenlängen sowie Ethoxylierungsgrade bzw. Alkoxylierungsgrade der vorgenannten Niotenside stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Aufgrund der Herstellverfahren bestehen Handelsprodukte der genannten Formeln zumeist nicht aus einem individuellen Vertreter, sondern aus Gemischen, wodurch sich sowohl für die C-Kettenlängen als auch für die Ethoxylierungsgrade bzw. Alkoxylierungsgrade Mittelwerte und daraus folgend gebrochene Zahlen ergeben können.The stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.

Das Geschirrspülmittel kann neben den bereits genannten nichtionischen Tensiden weitere nichtionische Tenside enthalten, die ebenfalls einer der allgemeinen Formeln der nichtionischen Tenside A bis D entsprechen können, aber in keiner Weise darauf limitiert sind.The dishwashing detergent may contain, in addition to the nonionic surfactants already mentioned, further nonionic surfactants which may likewise correspond to one of the general formulas of the nonionic surfactants A to D, but are in no way limited thereto.

Der Gewichtsanteil des nichtionischen Tensids am Gesamtgewicht des Geschirrspülmittels beträgt in einer bevorzugten Ausführungsform 0,4 bis 40 Gew.-%, weiter bevorzugt 1 bis 30 Gew.-%, besonders bevorzugt 2 bis 20 Gew.-% und insbesondere 4 bis 20 Gew.-%.The proportion by weight of the nonionic surfactant in the total weight of the dishwashing agent in a preferred embodiment is 0.4 to 40 wt .-%, more preferably 1 to 30 wt .-%, particularly preferably 2 to 20 wt .-% and in particular 4 to 20 wt. -%.

Das Geschirrspülmittel kann neben Tensiden auch Gerüststoffe enthalten. Gerüststoffe sind üblicherweise Stoffe, die zur Gewährleistung der Reinigungsleistung des Geschirrspülmittels beitragen, indem sie unter anderem die Bildung von Kalkbelägen auf Maschinenbauteilen hemmen und so eine effiziente Übertragen der Energie auf das Wasser ermöglichen.The dishwashing detergent may contain surfactants as well as builders. Builders are typically materials that help maintain the dishwashing detergent's performance by, inter alia, inhibiting the formation of limescale deposits on machine components, thereby enabling efficient transfer of energy to the water.

Der Gewichtsanteil der Gerüststoffe am Gesamtgewicht des Geschirrspülmittels beträgt vorzugsweise 15 bis 80 Gew.-% und insbesondere 20 bis 70 Gew.-%. Zu den Gerüststoffen zählen insbesondere Carbonate, Phosphate, Citrate, und Silikate.The proportion by weight of the builders in the total weight of the dishwashing agent is preferably 15 to 80 wt .-% and in particular 20 to 70 wt .-%. The builders include in particular carbonates, phosphates, citrates, and silicates.

Bevorzugt ist der Einsatz von Carbonat(en) und/oder Hydrogencarbonat(en), vorzugsweise Alkalicarbonat(en), besonders bevorzugt Natriumcarbonat, in Mengen von 2 bis 30 Gew.-%, vorzugsweise von 4 bis 28 Gew.-% und insbesondere von 8 bis 24 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Geschirrspülmittels.Preferably, the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate, in amounts of 2 to 30 wt .-%, preferably from 4 to 28 wt .-% and in particular of 8 to 24 wt .-%, each based on the total weight of the dishwashing detergent.

Bevorzugt ist weiterhin der Einsatz von Phosphat(en). Unter der Vielzahl der kommerziell erhältlichen Phosphate haben die Alkalimetallphosphate unter besonderer Bevorzugung von Pentanatrium- bzw. Pentakaliumtriphosphat (Natrium- bzw. Kaliumtripolyphosphat) in der Wasch- und Reinigungsmittelindustrie die größte Bedeutung.Preference is also the use of phosphate (s). Among the large number of commercially available phosphates, the alkali metal phosphates, with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are the most important in the detergent and cleaner industry.

Alkalimetallphosphat ist dabei die summarische Bezeichnung für die Alkalimetall- (insbesondere Natrium- und Kalium-) Salze der verschiedenen Phosphorsäuren, bei denen man Metaphosphorsäure (HPO3)n und Orthophosphorsäure H3PO4 neben höhermolekularen Vertretern unterscheiden kann. Die Phosphate vereinen dabei mehrere Vorteile in sich: Sie wirken als Alkaliträger, verhindern Kalkbeläge auf Maschinenteilen bzw. Kalkinkrustationen auf den zu reinigenden Gegenständen und tragen überdies zur Reinigungsleistung bei.Alkali metal phosphate is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acid (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts or lime incrustations on the objects to be cleaned and, moreover, contribute to the cleaning performance.

Besonders bevorzugte Phosphate sind das Pentanatriumtriphosphat, Na5P3O10 (Natriumtripolyphosphat) sowie das entsprechende Kaliumsalz Pentakaliumtriphosphat, K5P3O10 (Kaliumtripolyphosphat). Bevorzugt eingesetzt werden weiterhin die Natriumkaliumtripolyphosphate.Particularly preferred phosphates are the pentasodium triphosphate, Na 5 P 3 O 10 (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate). Preference is furthermore given to using the sodium potassium tripolyphosphates.

Werden im Rahmen der vorliegenden Anmeldung Phosphate als Gerüststoffe in dem Geschirrspülmitteln eingesetzt, so enthält dieses Phosphat(e), vorzugsweise Alkalimetallphosphat(e), besonders bevorzugt Pentanatrium- bzw. Pentakaliumtriphosphat (Natrium- bzw. Kaliumtripolyphosphat), in Mengen von 5 bis 70 Gew.-%, vorzugsweise von 15 bis 55 Gew.-% und insbesondere von 20 bis 50 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Geschirrspülmittels.If phosphates are used as builders in dishwashing detergents in the context of the present application, this contains phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of from 5 to 70% by weight .-%, preferably from 15 to 55 wt .-% and in particular from 20 to 50 wt .-%, each based on the total weight of the dishwashing detergent.

Als bevorzugte Gerüststoffe werden ebenfalls Polycarboxylate/Polycarbonsäuren, polymere Carboxylate, Asparaginsäure, Polyacetale und Dextrine eingesetzt. Diese Stoffklasse wird auch als organische Cobuilder bezeichnet und nachfolgend beschrieben.Polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals and dextrins are also used as preferred builders. This class of substances is also referred to as organic cobuilders and described below.

Wird eine Polycarbonsäure als Gerüststoff eingesetzt, kann diese in Form der freien Säure und/oder ihrer Alkalisalze, insbesondere Natriumsalze verwendet werden, wobei unter Polycarbonsäure solche Carbonsäure verstanden wird, die mehr als eine Säurefunktion trägt. Beispielhaft können hier Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Apfelsäure, Weinsäure, Maleinsäure, Fumarsäure, Zuckersäuren, Aminocarbonsäuren, Nitrilotriessigsäure (NTA), sofern ein derartiger Einsatz aus ökologischen Gründen nicht zu beanstanden ist, sowie Mischungen aus diesen, genannt werden. Die freien Säuren besitzen neben ihrer Builderwirkung typischerweise auch die Eigenschaft einer Säuerungskomponente und dienen somit auch zur Einstellung eines niedrigeren und milderen pH-Wertes von Wasch- oder Reinigungsmitteln.If a polycarboxylic acid is used as the builder, it can be used in the form of the free acid and / or its alkali metal salts, in particular sodium salts, polycarboxylic acid meaning that carboxylic acid which carries more than one acid function. By way of example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for environmental reasons, as well as mixtures thereof, may be mentioned here. In addition to their builder effect, the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.

Das Geschirrspülmittel kann als Gerüststoff Citrat enthalten, bevorzugt Natrium-Citrat. Das Geschirrspülmittel kann bevorzugt 2 bis 40 Gew.-%, vorzugsweise 5 bis 30 Gew.-% und insbesondere 7 bis 20 Gew.-% Citrat enthalten, insbesondere Natrium-Citrat, bezogen auf das Gesamtgewicht des Geschirrspülmittels.The dishwashing detergent may contain citrate as the builder, preferably sodium citrate. The dishwashing detergent may preferably contain from 2 to 40% by weight, preferably from 5 to 30% by weight and in particular from 7 to 20% by weight, of citrate, in particular sodium citrate, based on the total weight of the dishwashing detergent.

Die Citrate werden bevorzugt mit Carbonaten und/oder Hydrogencarbonaten eingesetzt. Bevorzugte Geschirrspülmittel enthalten daher eine Gerüststoffkombination aus Phosphat und Carbonat/Hydrogencarbonat oder aus Citrat und Carbonat/Hydrogencarbonat oder aus Phosphat, Citrat und Carbonat/Hydrogencarbonat.The citrates are preferably used with carbonates and / or bicarbonates. Preferred dishwashing detergents therefore contain a builder combination of phosphate and carbonate / bicarbonate or of citrate and carbonate / bicarbonate or of phosphate, citrate and carbonate / bicarbonate.

Ein besonders bevorzugtes Geschirrspülmittel ist dadurch gekennzeichnet, dass es mindestens zwei Gerüststoffe aus der Gruppe der Phosphate, Carbonate und Citrate enthält, wobei der Gewichtsanteil dieser Gerüststoffe, bezogen auf das Gesamtgewicht des Geschirrspülmittels, bevorzugt 5 bis 80 Gew.-%, vorzugsweise 15 bis 75 Gew.-% und insbesondere 30 bis 70 Gew.-% beträgt. Die Kombination von zwei oder mehr Gerüststoffen aus der oben genannten Gruppe hat sich für die Reinigungs- und Klarspülleistung des Geschirrspülmittels als vorteilhaft erwiesen.A particularly preferred dishwashing detergent is characterized in that it contains at least two builders from the group of phosphates, carbonates and citrates, wherein the proportion by weight of these builders, based on the total weight of the dishwashing agent, preferably 5 to 80 wt .-%, preferably 15 to 75 Wt .-% and in particular 30 to 70 wt .-% is. The combination of two or more builders from the above-mentioned group has proven to be advantageous for the cleaning and rinsing performance of the dishwashing detergent.

Als Gerüststoffe sind weiterhin polymere Polycarboxylate geeignet. Dies sind beispielsweise die Alkalimetallsalze der Polyacrylsäure oder der Polymethacrylsäure, beispielsweise solche mit einer gewichtsmittleren Molmasse von 500 bis 70000 g/mol.As builders, polymeric polycarboxylates are also suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a weight-average molar mass of from 500 to 70,000 g / mol.

Geeignete Polymere sind insbesondere Polyacrylate, die bevorzugt eine gewichtsmittlere Molmasse von 2000 bis 20000 g/mol aufweisen. Aufgrund ihrer überlegenen Löslichkeit können aus dieser Gruppe wiederum die kurzkettigen Polyacrylate, die eine gewichtsmittlere Molmasse von 2000 bis 10000 g/mol, und besonders bevorzugt von 3000 bis 5000 g/mol, aufweisen, bevorzugt sein.Suitable polymers are, in particular, polyacrylates, which preferably have a weight average molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have a weight-average molar mass of from 2,000 to 10,000 g / mol, and particularly preferably from 3,000 to 5,000 g / mol, may again be preferred from this group.

Die gewichtsmittleren Molmassen können mit Hilfe der Gelpermeationschromatografie bestimmt werden.The weight-average molar masses can be determined by means of gel permeation chromatography.

Der Gehalt an (homo)polymeren Polycarboxylaten im Geschirrspülmittel beträgt vorzugsweise 0,5 bis 20 Gew.-% und insbesondere 3 bis 10 Gew.-%.The content of (homo) polymeric polycarboxylates in dishwashing detergent is preferably 0.5 to 20 wt .-% and in particular 3 to 10 wt .-%.

Das Geschirrspülmittel kann als Gerüststoff kristalline schichtförmige Silikate der allgemeinen Formel

        NaMSixO2x+1·y H2O

enthalten, worin M Natrium oder Wasserstoff darstellt, x eine Zahl ist von 1,9 bis 22, vorzugsweise von 1,9 bis 4, besonders bevorzugt 2, 3 oder 4, und y für eine Zahl von 0 bis 33, vorzugsweise von 0 bis 20, steht.The dishwashing detergent can be a builder crystalline layered silicates of the general formula

NaMSi x O 2x + 1 · y H 2 O

in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, particularly preferably 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20, stands.

Einsetzbar sind auch amorphe Natriumsilikate mit einem Modul Na2O : SiO2 von 1:2 bis 1:3,3, vorzugsweise von 1:2 bis 1:2,8 und insbesondere von 1:2 bis 1:2,6, welche vorzugsweise löseverzögert sind und Sekundärwascheigenschaften aufweisen.It is also possible to use 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 preferably delayed release and have secondary washing properties.

In einem bevorzugten Geschirrspülmittel wird der Gehalt an Silikaten, bezogen auf das Gesamtgewicht des Geschirrspülmittels, auf Mengen von 0 bis 10 Gew.-%, vorzugsweise von 0 bis 5 Gew.-% und insbesondere von 0 bis 2 Gew.-% begrenzt. Ein besonders bevorzugtes Geschirrspülmittel ist frei von Silikaten.In a preferred dishwashing detergent, the content of silicates, based on the total weight of the dishwashing detergent, is limited to amounts of from 0 to 10% by weight, preferably from 0 to 5% by weight and in particular from 0 to 2% by weight. A particularly preferred dishwashing detergent is free of silicates.

In Ergänzung zu den vorgenannten Gerüststoffen kann das Geschirrspülmittel alkalische Mittel, bevorzugt Alkalimetallhydroxide, insbesondere Natriumhydroxid enthalten. Diese alkalischen Mittel werden in dem Geschirrspülmittel bevorzugt in Mengen von 0 bis 10 Gew.-%, vorzugsweise von 0 bis 5 Gew.-%, besonders bevorzugt zwischen 0,1 und 5 Gew.-% und insbesondere zwischen 0,5 und 5 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Geschirrspülmittels, eingesetzt. Ein alternativ bevorzugtes Geschirrspülmittel ist frei von Alkalimetallhydroxiden.In addition to the abovementioned builders, the dishwashing detergent may contain alkaline agents, preferably alkali metal hydroxides, in particular sodium hydroxide. These alkaline agents are preferred in the dishwashing detergent in amounts of 0 to 10 wt .-%, preferably from 0 to 5 wt .-%, particularly preferably between 0.1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, in each case based on the total weight of the dishwashing detergent used. An alternative preferred dishwashing detergent is free of alkali metal hydroxides.

Als weiteren Bestandteil kann das Geschirrspülmittel vorzugsweise Enzyme enthalten. Hierzu gehören insbesondere Proteasen, Amylasen, Lipasen, Hemicellulasen, Cellulasen, Perhydrolasen oder Oxidoreduktasen sowie vorzugsweise deren Gemische. Enzyme können in dem Geschirrspülmittel bevorzugt in Mengen von 0,0001 bis 10 Gew.-%, bevorzugt von 0,01 bis 5 Gew.-%, vorzugsweise von 0,1 bis 4 Gew.-%, besonders bevorzugt zwischen 0,2 und 4 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Geschirrspülmittels, eingesetzt werden.As a further ingredient, the dishwashing detergent may preferably contain enzymes. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases and preferably mixtures thereof. Enzymes may be present in the dishwashing detergent preferably in amounts of from 0.0001 to 10% by weight, preferably from 0.01 to 5% by weight, preferably from 0.1 to 4% by weight, more preferably between 0.2 and 4 wt .-%, each based on the total weight of the dishwashing detergent, are used.

Bei dem Geschirrspülmittel handelt es sich vorzugsweise um ein festes Geschirrspülmittel. Unter einem "festen Geschirrspülmittel" ist hierbei ein Geschirrspülmittel zu verstehen, das bei 25°C und einem Druck von 1 bar in festem Aggregatzustand vorliegt.The dishwashing agent is preferably a solid dishwashing detergent. A "solid dishwashing detergent" is to be understood as meaning a dishwashing detergent which is in a solid state of aggregation at 25 ° C. and a pressure of 1 bar.

Das Geschirrspülmittel liegt vorzugsweise in Form eines Formkörpers, insbesondere eines Kompaktats, vor allem als Tablette vor. Der Formkörper kann jedwede geometrische Form annehmen wie beispielsweise konkave, konvexe, bikonkave, bikonvexe, kubische, tetragonale, orthorhombische, zylindrische, sphärische, zylindrale, octahedrale, konische, pyramidale, ellipsoide, fünf-, sieben- und achteckig-prismatische sowie rhomboedrische Formen.The dishwashing agent is preferably in the form of a shaped body, in particular a Kompaktats, especially as a tablet. The shaped body may take any geometric shape such as concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylindrical, octahedral, conical, pyramidal, ellipsoidal, pentagonal, hexagonal, octagonal prismatic and rhombohedral shapes.

Die Herstellung des Formkörpers, insbesondere der Tablette, erfolgt bevorzugt durch Verpressung partikulärer Ausgangssubstanzen. Zur Herstellung der Tablette wird bevorzugt ein Vorgemisch in einer sogenannten Matrize zwischen zwei Stempeln zu einem festen Kompaktat verdichtet. Dieser Vorgang, der im Folgenden kurz als Tablettierung bezeichnet wird, gliedert sich in vier Abschnitte: Dosierung, Verdichtung (elastische Verformung), plastische Verformung und Ausstoßen. Die Tablettierung erfolgt dabei vorzugsweise auf sogenannten Rundläuferpressen.The preparation of the molding, in particular the tablet, is preferably carried out by compression of particulate starting materials. To prepare the tablet, a premix is preferably compressed in a so-called matrix between two punches to form a solid compactate. This process, hereinafter referred to as tableting, is divided into four sections: dosing, compaction (elastic deformation), plastic deformation and ejection. The tableting is preferably carried out on so-called rotary presses.

Die zur Tablettierung vorgesehen Inhaltsstoffe können in Form eines gemeinsamen teilchenförmigen Vorgemisches zeitgleich oder in Form einzelner, separater Pulver oder Granulate zeitlich versetzt oder zeitgleich in die Matrize eingefüllt werden, wobei die Dosierung eines vorgefertigten teilchenförmigen Vorgemisches bevorzugt ist.The ingredients provided for tabletting can be added in the form of a common particulate premix at the same time or in the form of individual, separate powders or granules offset in time or at the same time in the mold, the dosage of a prefabricated particulate premix is preferred.

Der Formkörper kann in einer weiteren bevorzugten Ausführungsform ein Sprengmittel enthalten. Die Wirkung von Sprengmitteln besteht in der Regel darin, dass sie bei Wasserzutritt ihr Volumen vergrößern, wobei sich einerseits das Eigenvolumen vergrößert (Quellung), oder andererseits aber auch über die Freisetzung von Gasen ein Druck erzeugt werden kann, der die Tablette in kleinere Partikel zerfallen lässt.The shaped body may contain a disintegrant in a further preferred embodiment. The effect of disintegrants is usually that they increase their volume upon ingress of water, whereby on the one hand increases the intrinsic volume (swelling), or on the other hand, via the release of gases, a pressure can be generated, which disintegrate the tablet into smaller particles leaves.

Beispielsweise kann als Sprengmittel quervernetztes Polyvinylpyrrolidon (Crospovidon) verwendet werden, bevorzugt in partikulärer Form.For example, cross-linked polyvinylpyrrolidone (crospovidone) can be used as disintegrant, preferably in particulate form.

Das Geschirrspülmittel kann ein Sprengmittel, insbesondere Polyvinylpyrrolidon, vorzugsweise in einer Menge von 0,1 bis 5 Gew.-%, insbesondere in einer Menge von 0,2 bis 3 Gew.-%, vor allem in einer Menge von 0,3 bis 1,8 Gew.-%, enthalten, bezogen auf das Gesamtgewicht des Geschirrspülmittels.The dishwashing detergent can be a disintegrating agent, in particular polyvinylpyrrolidone, preferably in an amount of from 0.1 to 5% by weight, in particular in an amount of from 0.2 to 3% by weight, in particular in an amount of from 0.3 to 1 , 8 wt .-%, based on the total weight of the dishwashing detergent.

Zusätzlich oder alternativ zu den Polyvinylpyrrolidon-Partikeln können auch weitere Sprengmittel in den Formkörpern enthalten sein, beispielsweise Carbonat/Citronensäure-Systeme oder Carbonat in Kombination mit anderen organischen Säuren, synthetische Polymere oder natürliche Polymere bzw. modifizierte Naturstoffe wie Cellulose und Stärke und ihre Derivate sowie Alginate oder Casein-Derivate. Weiterhin können als weitere Sprengmittel auch gasentwickelnde Brausesysteme eingesetzt werden. Bevorzugte Brausesysteme bestehen aus mindestens zwei Bestandteilen, die miteinander unter Gasbildung reagieren, beispielsweise aus Alkalimetallcarbonat und/oder - hydrogencarbonat sowie einem Acidifizierungsmittel, das geeignet ist, aus den Alkalimetallsalzen in wässriger Lösung Kohlendioxid freizusetzen. Ein Acidifizierungsmittel, das aus den Alkalisalzen in wässriger Lösung Kohlendioxid freisetzt, ist beispielsweise Citronensäure.In addition or as an alternative to the polyvinylpyrrolidone particles, further disintegrants may also be present in the moldings, for example carbonate / citric acid systems or carbonate in combination with other organic acids, synthetic polymers or natural polymers or modified natural substances such as cellulose and starch and their derivatives and Alginates or casein derivatives. Furthermore, gas-evolving effervescent systems can also be used as further disintegrants. Preferred effervescent systems consist of at least two constituents which react with one another to form gas, for example from alkali metal carbonate and / or bicarbonate and an acidifier which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution. An acidifying agent which releases carbon dioxide from the alkali salts in aqueous solution is, for example, citric acid.

In einer alternativ bevorzugten Ausführungsform kann der Formkörper jedoch auch in Kombination mit anderen Angebotsformen, insbesondere in Kombination mit festen Angebotsformen wie Pulver, Granulaten oder Extrudaten oder in Kombination mit flüssigen Angebotsformen auf Basis von Wasser und/oder organischen Lösungsmitteln vorliegen.
Bei dem Formkörper kann es sich beispielsweise auch um ein Granulat handeln, das in einem Beutel oder einer Gießform enthalten ist.In an alternatively preferred embodiment, however, the shaped article may also be present in combination with other forms of offers, in particular in combination with solid forms such as powders, granules or extrudates or in combination with liquid formulations based on water and / or organic solvents.
The shaped body may, for example, also be a granulate which is contained in a bag or a casting mold.

Die einfachste Realisierungsmöglichkeit liegt dabei in zwei oder mehrschichtigen Tabletten, wobei jede Schicht des Formkörpers eine einzelne Phase darstellt. Durch den phasen- oder schichtweisen Aufbau können bevorzugt die verschiedenen Bestandteile, welche die unterschiedlichen Funktionen eines Geschirrspülmittels erfüllen, so von einander getrennt gehalten werden, dass sie nicht vor dem Waschgang in unerwünschte Wechselwirkung treten können.The simplest realization possibility lies in two or more multilayer tablets, each layer of the molding representing a single phase. By virtue of the phase or layered structure, the various constituents which fulfill the different functions of a dishwashing detergent can preferably be kept separate from one another such that they can not undesirably interact before the washing cycle.

Die speziellen nichtionischen Tenside A bis D können in jeder Schicht der Tablette sowohl einzeln, als auch in beliebiger Kombination vorliegen. In einer bevorzugten Ausführungsform der Erfindung können bestimmte Tenside oder Tensidkombinationen in einer der Phasen bevorzugt sein, in einer weiteren Ausführungsform der Erfindung können die Tenside aber auch gleichmäßig auf alle Phasen verteilt sein. In noch einer weiteren Ausführungsform der Erfindung sind eine oder mehrere Phasen der Tablette komplett frei von den speziellen nichtionischen Tensiden A bis D.The specific nonionic surfactants A to D may be present in each layer of the tablet either individually or in any desired combination. In a preferred embodiment of the invention, certain surfactants or surfactant combinations may be preferred in one of the phases, but in a further embodiment of the invention, the surfactants may also be uniformly distributed to all phases. In yet another embodiment of the invention, one or more phases of the tablet are completely free of the specific nonionic surfactants A to D.

Besonders bevorzugt ist daher eine zwei- oder mehrphasige Tablette, beispielsweise Zweischichttablette, insbesondere Zweischichttablette mit Mulde und einem in der Mulde befindlichen Formkörper. Alternativ bevorzugt kann jedoch ebenfalls eine mehrphasige Tablette hergestellt werden, in der die eine Phase in Form einer Einlagerung in die andere(n) Phase(n) integriert wird.Therefore, a two-phase or multi-phase tablet, for example a two-layer tablet, in particular a two-layer tablet with a trough and a shaped body located in the trough, is particularly preferred. Alternatively preferred, however, may also be a multiphase tablet be prepared in which the one phase is integrated in the form of a storage in the other (s) phase (s).

Das Geschirrspülmittel wird vorzugsweise zu Dosiereinheiten vorkonfektioniert. Diese Dosiereinheiten umfassen vorzugsweise die für einen Reinigungsgang notwendige Menge an wasch- oder reinigungsaktiven Substanzen. Bevorzugte Dosiereinheiten weisen ein Gewicht zwischen 12 und 30 g, bevorzugt zwischen 14 und 26 g und insbesondere zwischen 15 und 22 g auf.The dishwashing agent is preferably prefabricated to dosage units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g.

Das Volumen der vorgenannten Dosiereinheiten sowie deren Raumform sind mit besonderem Vorzug so gewählt, dass eine Dosierbarkeit der vorkonfektionierten Einheiten über die Dosierkammer einer Geschirrspülmaschine gewährleistet ist. Das Volumen der Dosiereinheit beträgt daher bevorzugt zwischen 10 und 35 ml, vorzugsweise zwischen 12 und 30 ml und insbesondere zwischen 15 und 25 ml.The volume of the aforementioned metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units is ensured via the metering chamber of a dishwasher. The volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml and in particular between 15 and 25 ml.

Das Geschirrspülmittel, insbesondere die vorgefertigten Dosiereinheiten, kann in einer bevorzugten Ausführungsform eine wasserlösliche Umhüllung aufweisen.The dishwashing detergent, in particular the prefabricated metering units, may in a preferred embodiment have a water-soluble coating.

Neben den zuvor beschriebenen Inhaltsstoffen kann das Geschirrspülmittel weitere Zusatzstoffe wie wasch- oder reinigungsaktive Substanzen, vorzugsweise aus der Gruppe der Glaskorrosionsinhibitoren, Korrosionsinhibitoren, Duftstoffe und Parfümträger enthalten.In addition to the ingredients described above, the dishwashing detergent may contain other additives such as washing or cleaning-active substances, preferably from the group of glass corrosion inhibitors, corrosion inhibitors, fragrances and perfume carriers.

Die zuvor beschriebenen Kombinationen an Inhaltsstoffen eignen sich vorzugsweise zur Reinigung von Geschirr in Geschirrspülverfahren, insbesondere in maschinellen Geschirrspülverfahren.The combinations of ingredients described above are preferably suitable for cleaning dishes in dishwashing processes, in particular in automatic dishwashing processes.

Ein weiterer Gegenstand der vorliegenden Anmeldung ist ein maschinelles Geschirrspülverfahren, bei dem das Geschirrspülmittel zum Einsatz kommt. In dem Verfahren zur Reinigung von Geschirr in einer Geschirrspülmaschine unter Einsatz des Geschirrspülmittels wird das Geschirrspülmittel vorzugsweise während des Durchlaufens eines Geschirrspülprogramms, vor Beginn des Hauptspülgangs oder im Verlauf des Hauptspülgangs in den Innenraum einer Geschirrspülmaschine eindosiert bzw. eingetragen. Die Eindosierung bzw. der Eintrag des Geschirrspülmittels in den Innenraum der Geschirrspülmaschine kann manuell erfolgen, vorzugsweise wird das Geschirrspülmittel jedoch mittels der Dosierkammer der Geschirrspülmaschine in den Innenraum der Geschirrspülmaschine dosiert. Im Verlauf des Reinigungsprozesses wird vorzugsweise kein zusätzlicher Wasserenthärter und kein zusätzlicher Klarspüler in den Innenraum der Geschirrspülmaschine dosiert.A further subject of the present application is a machine dishwashing process in which the dishwashing detergent is used. In the method for cleaning dishes in a dishwashing machine using the dishwashing detergent, the dishwashing detergent is preferably metered or introduced into the interior of a dishwasher during the passage of a dishwashing program, before the main wash cycle or during the main wash cycle. The dispensing or the entry of the dishwashing detergent into the interior of the dishwasher can be done manually, but preferably the dishwashing detergent is metered into the interior of the dishwasher by means of the metering chamber of the dishwasher. In the course of the cleaning process preferably no additional water softener and no additional rinse aid is metered into the interior of the dishwasher.

Eine bevorzugte Ausführungsform ist ein maschinelles Geschirrspülverfahren unter Einsatz des bevorzugt festen Geschirrspülmittels, insbesondere in Gestalt eines zuvor genannten Formkörpers, insbesondere zur verbesserten Trocknung von Plastikspülgut.A preferred embodiment is a machine dishwashing process using the preferably solid dishwashing agent, in particular in the form of a previously mentioned shaped body, in particular for the improved drying of plastic dishwashing product.

Das Geschirrspülverfahren wird aus ökonomischen und ökologischen Gründen vorzugsweise bei einer Flottentemperatur unterhalb von 60°C, bevorzugt nicht oberhalb von 50°C, vorzugsweise bei 35 bis 45°C durchgeführt. In einer bevorzugten Ausführungsform dauert das Geschirrspülverfahren 5 bis 90 Minuten, insbesondere 10 bis 75 Minuten, besonders bevorzugt 20 bis 60 Minuten. In alternativ besonders bevorzugten Ausführungsformen dauert das Geschirrspülverfahren maximal 50, 40 oder 30 Minuten.For economic and ecological reasons, the dishwashing process is preferably carried out at a liquor temperature below 60 ° C., preferably not above 50 ° C., preferably at 35 to 45 ° C. In a preferred embodiment, the dishwashing process takes 5 to 90 minutes, in particular 10 to 75 minutes, particularly preferably 20 to 60 minutes. In alternatively preferred embodiments, the dishwashing process takes a maximum of 50, 40 or 30 minutes.

Wie eingangs beschrieben, zeichnet sich das Geschirrspülmittel gegenüber herkömmlichen Geschirrspülmitteln durch eine verbesserte Trockenleistung aus. Ein weiterer Gegenstand der vorliegenden Anmeldung ist daher die Verwendung eines speziellen Geschirrspülmittels zur Verbesserung der Trocknung von Plastikspülgut beim maschinellen Geschirrspülen.As described at the outset, the dishwashing detergent is distinguished from conventional dishwashing detergents by improved drying performance. Another object of the present application is therefore the use of a special dishwashing detergent to improve the drying of Plastikspülgut in automatic dishwashing.

BeispieleExamples Beispiel 1: RezepturenExample 1: Recipes

Tab. 1: Beispielhafte Rezepturen für die speziellen maschinellen Geschirrspülmitteltabletten. Rezepturen E1 und E2 entsprechen einem erfindungsgemäßen Geschirrspülmittel, die Rezepturen V1 bis V3 stellen Vergleichsbeispiele dar.Tab. 1: Exemplary formulations for the special automatic dishwashing detergent tablets. Formulations E1 and E2 correspond to a dishwasher detergent according to the invention, the formulations V1 to V3 are comparative examples. Inhaltsstoffingredient Rezeptur E1 [Gew.-%]Recipe E1 [wt .-%] Rezeptur E2 [Gew.-%]Recipe E2 [% by weight] Rezeptur V1 [Gew.-%]Recipe V1 [% by weight] Rezeptur V2 [Gew.-%]Recipe V2 [% by weight] Rezeptur V3 [Gew.-%]Recipe V3 [% by weight] Tripolyphosphattripolyphosphate 3232 3232 3232 3232 3232 (Hydrogen-)Carbonat(Hydrogen) carbonate 1515 1515 1515 1515 1515 Enzym (Amylase, Protease)Enzyme (amylase, protease) 55 55 55 55 55 Niotensid ANonionic surfactant A 22 22 1,991.99 2,52.5 2,032.03 Niotensid BNonionic surfactant B 22 22 2,432.43 33 4,24.2 Niotensid CNonionic surfactant C 22 22 1,681.68 1,51.5 --- Niotensid DNonionic surfactant D 22 11 --- --- --- Zusatzstoffeadditives auf 100on 100 auf 100on 100 auf 100on 100 auf 100on 100 auf 100on 100

Beispiel 2: TrocknungsleistungExample 2: Drying Performance

Die Trocknungsleistung wurde in einer Bosch SMS 86M12DE Spülmaschine bei Verwendung des Eco50 Variospeed Programms bestimmt. Die Wasserhärte betrug 21 °dH und es wurden 50 g Ballastschmutz eingesetzt. Es wurden sechs Spülzyklen durchgeführt, von denen der vierte bis sechste zur Bewertung herangezogen wurden, die dann auf einer Skala von 0 bis 6 bewertet wurden. Dabei bedeutet 0, dass sich kein Tropfen auf dem Geschirr befand, 1 bedeutet einen Tropfen auf dem Geschirr und 6 bedeutet sechs oder mehr Tropfen auf dem Geschirr. Ein signifikanter Unterschied ist ab 0,5 Noten zu erkennen. Tab. 2: Vergleich der Trocknung von Plastikspülgut bei Anwendung der in Tab. 1 gezeigten Rezepturen in einer automatischen Spülmaschine (Bosch SMS 86M12DE). Plastik Tensidmenge [Gew.-%] Rezeptur E1 1,1 8 Rezeptur E2 1,7 7 Rezeptur V1 2,4 6 Rezeptur V2 2,7 7 Rezeptur V3 2,4 6 The drying performance was determined in a Bosch SMS 86M12DE dishwasher using the Eco50 Variospeed program. The water hardness was 21 ° dH and 50 g ballast dirt were used. Six rinse cycles were performed, of which the fourth to sixth were used for evaluation, which were then scored on a 0-6 scale. Where 0 means no drop on the dishes, 1 means one drop on the dishes, and 6 means six or more drops on the dishes. A significant difference can be seen from 0.5 notes. Tab. 2: Comparison of the drying of plastic detergent when using the recipes shown in Tab. 1 in an automatic dishwasher (Bosch SMS 86M12DE). plastic Amount of surfactant [% by weight] Recipe E1 1.1 8th Recipe E2 1.7 7 Recipe V1 2.4 6 Recipe V2 2.7 7 Recipe V3 2.4 6

Nur durch die Kombination der vier speziellen nichtionischen Tenside, wie in den Rezepturen E1 und E2, lässt sich eine signifikante Verbesserung der Trocknung auf Plastik erzielen. Die Vergleichsrezepturen V1 bis V3 dagegen zeigen keine verbesserte Trocknungsleistung auf Plastikspülgut. Wie der Vergleich der Rezepturen V1 und V2 zeigt, führt die bloße Erhöhung der Tensidmenge zu einer Verschlechterung der Trocknung. Auch eine Kombination aus lediglich zwei nichtionischen Tensiden, nämlich den Tensiden A und B, bei identischer Menge an nichtionischem Tensid, führt nicht zu einer Verbesserung der Trocknungsleistung, wie durch die Versuche mit den Rezepturen V1 und V3 gezeigt werden konnte. Die Trocknungsleistung konnte zusätzlich auch für Glas-, Porzellan- und Stahlspülgut verbessert werden.Only by combining the four special nonionic surfactants, as in formulas E1 and E2, can a significant improvement in drying on plastic be achieved. The comparative formulations V1 to V3, however, show no improved drying performance on Plastikspülgut. As the comparison of the formulations V1 and V2 shows, the mere increase in the amount of surfactant leads to a deterioration of the drying. A combination of only two nonionic surfactants, namely the surfactants A and B, with identical amount of nonionic surfactant, does not lead to an improvement of the drying performance, as could be shown by the experiments with the formulations V1 and V3. The drying performance could also be improved for glass, porcelain and steel washing.

Claims (9)

  1. A dishwasher detergent, characterized in that it contains at least four non-ionic surfactants A, B, C and D, in which
    I. surfactant A is described by the general formula

            R1O(AlkO)xM(OAlk)yOR2,

    in which
    - R1 and R2 represent, independently of one another, a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl functional group having 4 to 22 carbon atoms,
    - Alk represents a branched or unbranched alkyl functional group having 2 to 4 carbon atoms,
    - x and y represent, independently of one another, values of between 1 and 70 and
    - M represents an alkyl functional group from the group of CH2, CHR3, CR3R4, CH2CHR3 and CHR3CHR4, in which R3 and R4 represent, independently of one another, a branched or unbranched, saturated or unsaturated, cyclic or acyclic alkyl or alkenyl functional group having 1 to 18 carbon atoms;
    II. surfactants B and C, which are different, are both described by the general formula

            R1O[CH2CH(CH3)O]x[CH2CH2O]y[CH2CH(CH3)O]zCH2CH(OH)R2,

    in which
    - R1 represents a linear or branched aliphatic hydrocarbon functional group having 4 to 22 carbon atoms,
    - R2 represents a linear or branched hydrocarbon functional group having 2 to 26 carbon atoms,
    - x and z represent values between 0 and 40 and
    - y represents a value of at least 15; and
    III. surfactant D is described by the general formula

            R1O[CH2CH(R3)O]x[CH2CHO]y[CH2CH(R4)O]zC(O)R2,

    in which
    - R1 represents a branched or unbranched alkyl functional group having 8 to 16 carbon atoms,
    - R3 and R4 represent, independently of one other, hydrogen or a branched or unbranched alkyl functional group having 1 to 5 carbon atoms,
    - R2 represents an unbranched alkyl functional group having 5 to 17 carbon atoms,
    - x and z represent, independently of one another, a value of between 1 and 5 and
    - y represents a value of from 13 to 35.
  2. The dishwasher detergent according to claim 1, characterized in that contains, as a non-ionic surfactant A, a surfactant of the general formula

            R1-CH(OH)CH2-O(CH2CH2O)xCH2CHR(OCH2CH2)yO-CH2CH(OH)-R2,

    in which
    - R1 and R2 represent, independently of one another, an alkyl functional group or alkenyl functional group having 6 to 16 carbon atoms and
    - R represents a linear, saturated alkyl functional group having 2 to 12 carbon atoms, preferably 4 to 10 carbon atoms and
    - x and y have, independently of one another, values of between 5 and 20.
  3. The dishwasher detergent according to either claim 1 or claim 2, characterized in that the non-ionic surfactants B and C have the general formula

            R1O[CH2CH2O]yCH2CH(OH)R2,

    in which
    - R1 represents a linear or branched aliphatic hydrocarbon functional group having 4 to 22 carbon atoms,
    - R2 represents a linear or branched hydrocarbon functional group having 2 to 26 carbon atoms and
    - y represents a value of between 15 and 120, preferably 20 to 100 and in particular 20 to 80.
  4. The dishwasher detergent according to one of claims 1 to 3, characterized in that the non-ionic surfactants B and C are selected from the group of hydroxy mixed ethers of the general formula C4-22-CH(OH)CH2O-(EO)20-120-C2-26, for example C8-12 fatty alcohol-(EO)22-2-hydroxydecylether and C4-22 fatty alcohol-(EO)40-80-2-hydroxyalkylether.
  5. The dishwasher detergent according to one of claims 1 to 4, characterized in that,
    as the non-ionic surfactant D, a surfactant of the general formula

            R1O[CH2CH(R3)O]x[CH2CHO]y[CH2CH(R4)O]zC(O)R2

    is used, in which
    - R1 represents a branched or unbranched alkyl functional group having 10 to 15 carbon atoms,
    - R3 and R4 represent, independently of one another, hydrogen or a branched or unbranched alkyl functional group having 2 or 3 carbon atoms,
    - R2 represents an unbranched alkyl functional group having 8 to 16 carbon atoms,
    - x and z, independently of one another, represent a value of between 1 and 5 and
    - y represents a value of between 20 and 30.
  6. The dishwasher detergent according to one of claims 1 to 5, containing 0.1 to 10 wt.%, preferably 0.5 to 7 wt.% and particularly preferably 1 to 5 wt.% of surfactant A, 0.1 to 10 wt.%, preferably 0.5 to 7 wt.% and particularly preferably 1 to 5 wt.% of surfactant B, 0.1 to 10 wt.%, preferably 0.5 to 7 wt.% and particularly preferably 1 to 5 wt.% of surfactant C and 0.1 to 10 wt.%, preferably 0.5 to 7 wt.% and particularly preferably 1 to 5 wt.% of surfactant D.
  7. A method for cleaning dishes in a dishwasher using a dishwasher detergent according to one of the claims 1 to 6.
  8. The method according to claim 7, characterized in that the dishwashing process is carried out at a solution temperature of less than 60°C, preferably no higher than 50°C.
  9. The use of a dishwasher detergent according to one of claims 1 to 6 for improving the drying of plastics washware during automatic dishwashing.
EP13802967.3A 2012-12-17 2013-12-10 Surfactant combination for improved drying Not-in-force EP2931859B1 (en)

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DE102012223339.3A DE102012223339A1 (en) 2012-12-17 2012-12-17 Surfactant combination for improved drying
PCT/EP2013/076119 WO2014095498A1 (en) 2012-12-17 2013-12-10 Surfactant combination for improved drying

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EP (1) EP2931859B1 (en)
KR (1) KR20150097638A (en)
DE (1) DE102012223339A1 (en)
ES (1) ES2624404T3 (en)
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EP3257923B1 (en) 2016-06-17 2020-04-08 The Procter and Gamble Company Automatic dishwashing detergent composition

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US5536438A (en) * 1992-11-26 1996-07-16 The Procter & Gamble Company Multi-purpose liquid cleaning composition comprising nonionic surfactants of different HLB values
DE19851453A1 (en) 1998-11-09 2000-05-11 Cognis Deutschland Gmbh Rinse aid for automatic dishwashing
WO2009027456A2 (en) * 2007-08-29 2009-03-05 Basf Se Esterified alkyl alkoxylates as solid low-foam wetting agents
DE102008009366A1 (en) 2008-02-14 2009-08-20 Cognis Ip Management Gmbh Use of surface-active substances in cleaning agents
DE102008060471A1 (en) 2008-12-05 2010-06-10 Henkel Ag & Co. Kgaa Machine dishwashing detergent
TWI501998B (en) 2010-03-15 2015-10-01 Nissan Chemical Ind Ltd A liquid crystal aligning agent containing a polyamic acid ester, and a liquid crystal alignment film
DE102010029625A1 (en) 2010-06-02 2011-12-08 Henkel Ag & Co. Kgaa Geschirrspülmittelkompaktate

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EP2931859A1 (en) 2015-10-21
PL2931859T3 (en) 2017-08-31
DE102012223339A1 (en) 2014-06-18
US9234161B2 (en) 2016-01-12
US20150275137A1 (en) 2015-10-01
ES2624404T3 (en) 2017-07-14
KR20150097638A (en) 2015-08-26
HUE034187T2 (en) 2018-01-29

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