EP1321511A2 - Mixtures of gemini surfactants and fatty alcoholalkoxylates in rinse aids - Google Patents

Mixtures of gemini surfactants and fatty alcoholalkoxylates in rinse aids Download PDF

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Publication number
EP1321511A2
EP1321511A2 EP02027460A EP02027460A EP1321511A2 EP 1321511 A2 EP1321511 A2 EP 1321511A2 EP 02027460 A EP02027460 A EP 02027460A EP 02027460 A EP02027460 A EP 02027460A EP 1321511 A2 EP1321511 A2 EP 1321511A2
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EP
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Prior art keywords
formula
gemini surfactants
rinse aid
surfactants
linear
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EP02027460A
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German (de)
French (fr)
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EP1321511A3 (en
Inventor
Ditmar Kischkel
Manfred Dr. Weuthen
Michael Elsner
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Cognis IP Management GmbH
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Cognis Deutschland GmbH and Co KG
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Publication of EP1321511A2 publication Critical patent/EP1321511A2/en
Publication of EP1321511A3 publication Critical patent/EP1321511A3/en
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • 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
    • 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
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • the invention relates to rinse aid containing mixtures of gemini surfactants and Fatty alcohol alkoxylates, optionally in combination with ingredients customary in rinse aid, and the use of these mixtures to improve the wetting behavior in rinse aid.
  • Rinse aid is therefore used to ensure that dishes are clear and spotless.
  • liquid or solid rinse aid which can be added separately or is already available in ready-to-use form with the cleaning agent and / or regeneration salt ("2 in 1", "3 in 1", eg in the form of tabs and powders) that the water runs off the dishes as completely as possible, so that the different surfaces are residue-free and shiny at the end of the wash program.
  • Commercial rinse aids are mixtures of, for example, nonionic surfactants, solubilizers, organic acids and solvents, water and, if appropriate, preservatives and fragrances.
  • the rinse aid must also have a foam-suppressing effect, be temperature-stable with a strong temperature gradient of 85-35 ° C and also be sufficiently stable against alkali and active chlorine.
  • the task was accomplished through the use of a selected combination of gemini surfactants and Fatty alcohol alkoxylates dissolved.
  • Gemini surfactants are generally prepared by reacting 1,2-epoxyalkanes (CH 2 CHO-R), where R is a linear or branched, saturated or unsaturated alkyl and / or alkenyl radical, with polyols.
  • Gemini surfactants of the formula (I) are particularly preferably present, where x is from 10 to 45, preferably from 12 to 35. Gemini surfactants of the formula (I) are very particularly preferably present, where R is a linear or branched alkyl radical having 8 to 12 carbon atoms. Gemini surfactants of the formula (I) are furthermore preferably present, where R represents a linear alkyl radical having 8 to 12 carbon atoms, in particular having 10 carbon atoms.
  • rinse aids are also claimed which contain the gemini surfactants according to the invention and further ingredients customary in rinse aids.
  • these customary ingredients can be alkyl and / or alkenyl oligoglycosides, further nonionic surfactants, anionic surfactants and further auxiliaries and additives.
  • the gemini surfactants of the formula (I) and fatty alcohol alkoxylates are particularly preferred of the formula (II) in the ratio a: b from 1.5: 1 to 3: 1.
  • the rinse aids according to the invention can contain further nonionic surfactants.
  • Typical examples of nonionic surfactants are alkyl and / or alkenyl, terminally capped alkoxylates of alkanols with no free OH groups, alkoxylated fatty acid alkyl esters, amine oxides, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers and mixed formals, fatty acid-N-alkyl, Protein hydrolysates (especially vegetable products based on wheat), polyol fatty acid esters, sugar esters, sorbitan esters and polysorbates. If the nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
  • the anionic surfactants are preferably selected from the group consisting of alkyl and / or alkenyl sulfates, alkyl ether sulfates, alkyl benzene sulfonates, monoglyceride (ether) sulfates and alkane sulfonates, in particular fatty alcohol sulfates, fatty alcohol ether sulfates, secondary alkane sulfonates and linear alkyl benzene sulfonates.
  • the rinse aids according to the invention can be used as customary ingredient substances or auxiliaries and additives, for example solubilizers such as cumene sulfonate, ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, butyl glycol, diethylene glycol, propylene glycol monobutyl ether, polyethylene or polypropylene glycol ether with molecular weights from 600 to 1,500,000, preferably with a molecular weight from 400,000 to 800,000, or in particular butyl diglycol.
  • Organic acids such as mono- and / or polyvalent carboxylic acids, preferably citric acid, and preservatives and fragrances can also be used.
  • the rinse aid contains at least 50% by weight of water. based on the mean.
  • Another object of the invention is the use of gemini surfactants of the formula (I) and Fatty alcohol alkoxylates of the formula (II) in the ratio according to the invention for improving the Wetting behavior in rinse aid, preferably on hard surfaces, especially in combined Products from machine dishwashing detergents and rinse aid.
  • the combination according to the invention of gemini surfactants and selected fatty alcohol alkoxylates in the ratio according to the invention is not only characterized by its foam-suppressing action and high compatibility, but especially by plastic, but also by its higher melting points. This makes them particularly suitable for the simplified production of solid formulations.
  • the mixtures of gemini surfactants and fatty alcohol alkoxylates according to the invention are solid in a ratio of 1: 1 to 4: 1.
  • mixtures in a ratio of 1: 4 are liquid at room temperature.
  • the solid surfactant mixtures are easy to handle and work particularly well into solid combination preparations made up of detergent and rinse aid for automatic dishwashing.
  • the mixtures according to the invention due to their higher melting points, later dissolve in the cleaning liquor and develop with a time delay and in higher concentration.
  • the rinse aids can be used both as aqueous solutions and in solid form e.g. in wax poured in or present as a gel.
  • plastic test specimens measuring 20 x 5 cm are first cleaned with 1% NaOH and then with isopropanol.
  • the test specimens pretreated in this way are then immersed in the solution to be tested and immediately removed again.
  • the evaluation is carried out visually by drawing up a ranking list or on a scale from 1-5. 5 means that spontaneous tearing of the liquid film occurs and the wetting is completely eliminated. Grade 5 is obtained when water is used.
  • the grade 1 means complete wetting of the plastic surface with an even flow of the liquid film (test substance: Maranil A55® COGNIS).
  • PP polypropylene
  • PE polyethylene
  • PC polycarbonate

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

A clear rinse liquid comprises a 'gemini' surfactant (I) and alkoxylated fatty alcohol (II) at ratio 1:1 to 4:1, and optionally other standard ingredients. A clear rinse liquid comprises a 'gemini' surfactant of formula (I) and alkoxylated fatty alcohol of formula (II) at ratio 1:1 to 4:1, and optionally other standard ingredients. R-CHOH-CH2-(OCH2CH2)x-OCH2-CHOH-R (I) R1-O-(CH2(CH3)CHO)q(CH2CH2O)r-H (II) R, R1 = 4-22C linear or branched alkyl and/or alkenyl; x = 5-90; q = 0-10; and r = 1-50.

Description

Gebiet der ErfindungField of the Invention

Die Erfindung betrifft Klarspülmittel enthaltend Mischungen aus Geminitensiden und Fettalkoholalkoxylaten, gegebenenfalls in Verbindung mit in Klarspülmittel üblichen Inhaltsstoffen, sowie die Verwendung dieser Mischungen zur Verbesserung des Netzverhaltens in Klarspülmitteln.The invention relates to rinse aid containing mixtures of gemini surfactants and Fatty alcohol alkoxylates, optionally in combination with ingredients customary in rinse aid, and the use of these mixtures to improve the wetting behavior in rinse aid.

Stand der TechnikState of the art

Mittel für das Spülen und Reinigen harter, nichttextiler Oberflächen, die im Haushalt und Gewerbesektor vorkommen sollen, die meist bei Anwendung ein geringfügiges Schaumvolumen entwickeln, das sich innerhalb von wenigen Minuten signifikant weiter verringert. Mittel dieser Art sind seit langem bekannt und im Markt etabliert. Es handelt sich dabei im wesentlichen um wässrige Tensidlösungen unterschiedlicher Art mit oder ohne Zusatz von Buildern, Lösungsvermittlem (Hydrotropen) oder Lösungsmitteln. Zum Nachweis der Wirksamkeit bei Beginn der Reinigungsarbeit wird vom Verbraucher zwar ein gewisses Schäumen der Anwendungslösung gewünscht, der Schaum soll jedoch rasch zusammenfallen, damit einmal gereinigte Flächen nicht nachgewischt werden müssen. Zu diesem Zweck werden Mittel der genannten Art üblicherweise mit schwach schäumenden nichtionischen Tensiden versetzt.
Besonders an maschinell gespültes Geschirr werden heute höhere Anforderungen gestellt als an manuell gespültes Geschirr. So wird auch ein von Speiseresten völlig gereinigtes Geschirr dann als nicht einwandfrei bewertet, wenn es nach dem maschinellen Geschirrspülen noch weißliche, auf Wasserhärte oder anderen mineralischen Salzen beruhende Flecken aufweist, die mangels Netzmittel aus eingetrockneten Wassertropfen stammen.
Um glanzklares und fleckenloses Geschirr zu erhalten, setzt man daher Klarspüler ein. Der Zusatz von flüssigem oder festem Klarspüler, der separat zugegeben werden kann oder bereits in gebrauchsfertiger Darreichungsform mit dem Reinigungsmittel und/oder Regeneriersalz zusammen ("2 in 1", "3 in 1", z.B. in Form von Tabs und Pulvern) vorliegt sorgt dafür, dass das Wasser möglichst vollständig vom Spülgut abläuft, so dass die unterschiedlichen Oberflächen am Ende des Spülprogramms rückstandsfrei und glänzend sind.
Marktübliche Klarspülmittel stellen Gemische z.B. aus nichtionischen Tensiden, Lösungsvermittlern, organischen Säuren und Lösungsmitteln, Wasser sowie ggf. Konservierungsmittel und Duftstoffe dar. Means for rinsing and cleaning hard, non-textile surfaces, which should occur in the household and commercial sector, which usually develop a small volume of foam when used, which significantly reduces within a few minutes. Means of this kind have been known for a long time and are established on the market. These are essentially aqueous surfactant solutions of various types with or without the addition of builders, solubilizers (hydrotropes) or solvents. To prove the effectiveness at the beginning of the cleaning work, the consumer wants a certain amount of foam in the application solution, but the foam should collapse quickly so that once cleaned surfaces do not have to be wiped off. For this purpose, agents of the type mentioned are usually mixed with low-foaming nonionic surfactants.
Today, more requirements are placed on machine-washed dishes than on manually washed dishes. For example, dishes that have been completely cleaned of food residues are not considered to be perfect if, after machine dishwashing, they still have whitish stains due to water hardness or other mineral salts, which, due to the lack of wetting agents, come from dried water drops.
Rinse aid is therefore used to ensure that dishes are clear and spotless. The addition of liquid or solid rinse aid, which can be added separately or is already available in ready-to-use form with the cleaning agent and / or regeneration salt ("2 in 1", "3 in 1", eg in the form of tabs and powders) that the water runs off the dishes as completely as possible, so that the different surfaces are residue-free and shiny at the end of the wash program.
Commercial rinse aids are mixtures of, for example, nonionic surfactants, solubilizers, organic acids and solvents, water and, if appropriate, preservatives and fragrances.

Die Aufgabe der Tenside in diesen Mitteln besteht darin, die Grenzflächenspannung des Wassers so zu beeinflussen, dass es in einem möglichst dünnen, zusammenhängenden Film vom Spülgut ablaufen kann, so dass beim anschließenden Trocknungsvorgang keine Wassertropfen, Streifen oder Filme zurückbleiben (sogenannte Netzwirkung).
Deswegen müssen Tenside in Klarspülem auch den durch Speisereste auftretenden Schaum in der Geschirrspülmaschine dämpfen. Da die Klarspüler meist Säuren für eine Verbesserung des Klartrockeneffekts enthalten, müssen die eingesetzten Tenside zusätzlich relativ hydrolyseunempfindlich gegenüber Säuren sein.
Klarspüler werden sowohl im Haushalt als auch in gewerblichen Bereichen eingesetzt. In Haushaltsgeschirrspülern wird der Klarspüler meist nach dem Vorspül- und Reinigungsgang bei knapp 40°C-65°C zudosiert. Die gewerblichen Geschirrspülmaschinen arbeiten mit nur einer Reinigungsflotte, die lediglich durch Zugabe der Klarspüllösung aus dem vorhergehenden Spülvorgang erneuert wird. Es findet also während des gesamten Spülprogramms kein vollständiger Wasseraustausch statt. Daher muss der Klarspüler auch schaumdämpfend wirken, temperaturstabil sein bei einem starken Temperaturgefälle von 85-35°C und außerdem ausreichend stabil gegen Alkali und Aktivchlor sein.The task of the surfactants in these agents is to influence the interfacial tension of the water so that it can run off the wash ware in a thin, coherent film, so that no water drops, streaks or films remain during the subsequent drying process (so-called wetting effect).
For this reason, surfactants in rinse aid also have to dampen the foam that arises from food residues in the dishwasher. Since the rinse aids mostly contain acids to improve the clear dry effect, the surfactants used must also be relatively insensitive to hydrolysis against acids.
Rinse aids are used both in the home and in commercial areas. In household dishwashers, the rinse aid is usually added after the pre-rinse and cleaning cycle at just under 40 ° C-65 ° C. Commercial dishwashers work with only one cleaning liquor, which is only renewed by adding the rinse aid solution from the previous washing process. There is therefore no complete water exchange during the entire washing program. Therefore, the rinse aid must also have a foam-suppressing effect, be temperature-stable with a strong temperature gradient of 85-35 ° C and also be sufficiently stable against alkali and active chlorine.

Aufgabe der vorliegenden Erfindung war Klarspülmittel bereitzustellen, die gleichzeitig ein gutes Schaum- und Reinigungsverhalten, insbesondere jedoch ein sehr gutes Ablaufverhalten, d.h. eine Verbesserung des Netzverhaltens an Kunststorfoberflächen zeigen. It was an object of the present invention to provide rinse aid which at the same time has good foam and cleaning behavior, but in particular very good drainage behavior, ie an improvement in the wetting behavior on artificial peat surfaces.

Die Aufgabe wurde durch den Einsatz einer ausgewählten Kombination aus Geminitensiden und Fettalkoholalkoxylaten gelöst.The task was accomplished through the use of a selected combination of gemini surfactants and Fatty alcohol alkoxylates dissolved.

Beschreibung der ErfindungDescription of the invention

Gegenstand der Erfindung sind Klarspülmittel enthaltend,

  • a. Geminitenside gemäß Formel (I) R-CHOH-CH2-[OCH2CH2]x-O-CH2-CHOH-R   (I) in der R für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen und x für 5 bis 90 steht und
  • b. Fettalkoholalkoxylate der Formel (II) R1O[CH2(CH3)CHO]q(CH2CH2O)rH   (II) in der R1 für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen und q für 0 bzw. für Zahlen von 1 bis 10 und r für Zahlen von 1 bis 50 steht,
    •    und gegebenenfalls weitere in Klarspülmitteln übliche Inhaltsstorfe,
       dadurch gekennzeichnet, dass die Komponenten a : b im Verhältnis 1:1 bis 4:1 enthalten sind.The invention relates to rinse aid containing
  • a. Gemini surfactants according to formula (I) R-CHOH-CH 2 - [OCH 2 CH 2 ] xO-CH 2 -CHOH-R (I) in which R is a linear or branched alkyl and / or alkenyl radical having 4 to 22 carbon atoms and x is 5 to 90 and
  • b. Fatty alcohol alkoxylates of the formula (II) R 1 O [CH 2 (CH 3 ) CHO] q (CH 2 CH 2 O) r H (II) in which R1 represents a linear or branched alkyl and / or alkenyl radical with 4 to 22 carbon atoms and q for 0 or for numbers from 1 to 10 and r for numbers from 1 to 50,
    • and, if necessary, other peat contents common in rinse aid,
    characterized in that the components a: b are contained in a ratio of 1: 1 to 4: 1.

    Geminitensidegemini

    Allgemein werden Geminitenside durch Umsetzung von 1,2-Epoxyalkanen (CH2CHO-R), wobei R für einen linearen oder verzweigten, gesättigten oder ungesättigten Alkyl- und/oder Alkenylrest steht, mit Polyolen hergestellt.Gemini surfactants are generally prepared by reacting 1,2-epoxyalkanes (CH 2 CHO-R), where R is a linear or branched, saturated or unsaturated alkyl and / or alkenyl radical, with polyols.

    Hierbei ist Polyol als die Sammelbezeichnung für mehrwertige Alkohole bzw. Polyalkylenglycole, d. h. als eine organische Verbindung, die mindestens zwei Hydroxy-Gruppen im Mol enthält, zu betrachten.
    Unter den Polyalkylenglycolen sind auch Umsetzungsprodukte von mehrwertigen Alkoholen mit Alkoxylierungsreagenzien wie Ethylenoxid und Propylenoxid zu verstehen.    Here, polyol is to be regarded as the collective name for polyhydric alcohols or polyalkylene glycols, ie as an organic compound which contains at least two hydroxyl groups in the mole.
    The polyalkylene glycols are also to be understood as reaction products of polyhydric alcohols with alkoxylation reagents such as ethylene oxide and propylene oxide.

    Im Sinne der Erfindung wird Polyethylenglycol H-[OCH2CH2]x-OH als Polyol eingesetzt.For the purposes of the invention, polyethylene glycol H- [OCH 2 CH 2 ] x-OH is used as the polyol.

    Besonders bevorzugt sind Geminitenside der Formel (I) enthalten, wobei x für 10 bis 45, vorzugsweise für 12 bis 35 steht.
    Ganz besonders bevorzugt sind Geminitenside der Formel (I) enthalten, wobei R für einen linearen oder verzweigten Alkylrest mit 8 bis 12 Kohlenstoffatomen steht.
    Weiterhin bevorzugt sind Geminitenside der Formel (I) enthalten, wobei R für einen linearen Alkylrest mit 8 bis 12 Kohlenstoffatomen, insbesondere mit 10 Kohlenstoffatomen, steht.    Gemini surfactants of the formula (I) are particularly preferably present, where x is from 10 to 45, preferably from 12 to 35.
    Gemini surfactants of the formula (I) are very particularly preferably present, where R is a linear or branched alkyl radical having 8 to 12 carbon atoms.
    Gemini surfactants of the formula (I) are furthermore preferably present, where R represents a linear alkyl radical having 8 to 12 carbon atoms, in particular having 10 carbon atoms.

    In einer weiteren Ausführungsform sind Klarspüler bevorzugt, die Geminitenside der Formel (I) enthalten, die dadurch gekennzeichnet sind, dass sie mindestens 80 Gew.%, vorzugsweise 85 bis 100 Gew.%, insbesondere 95 bis 100 Gew.% Geminitenside enthalten, bei denen alle freien Hydroxygruppen des Polyethylenglycols mit 1,2-Epoxyalkan-Einheiten verschlossen sind. In a further embodiment, rinse aids are preferred, the gemini surfactants of the formula (I) Contain, which are characterized in that they have at least 80% by weight, preferably 85 to 100 % By weight, in particular 95 to 100% by weight of gemini surfactants, all of which contain free Hydroxy groups of the polyethylene glycol are closed with 1,2-epoxyalkane units.

    Weiterhin werden in einer weiteren Ausführungsform Klarspülmittel beansprucht, die die erfindungsgemäßen Geminitenside sowie weitere, in Klarspülmittel übliche Inhaltsstoffe enthalten.
    Diese üblichen Inhaltsstoffe können, wie nachfolgend beschrieben, Alkyl- und/oder Alkenyloligoglycoside, weitere nichtionische Tenside, anionische Tenside und weitere Hilfs- und Zusatzstoffe sein.    In a further embodiment, rinse aids are also claimed which contain the gemini surfactants according to the invention and further ingredients customary in rinse aids.
    As described below, these customary ingredients can be alkyl and / or alkenyl oligoglycosides, further nonionic surfactants, anionic surfactants and further auxiliaries and additives.

    Besonders bevorzugt sind Klarspülmittel, die die Geminitenside der Formel (I) und Fettalkoholalkoxylate der Formel (II) im Verhältnis a:b von 1.5:1 bis 3:1 enthalten.Rinse aids, the gemini surfactants of the formula (I) and fatty alcohol alkoxylates are particularly preferred of the formula (II) in the ratio a: b from 1.5: 1 to 3: 1.

    Nichtionische TensideNonionic surfactants

    Die erfindungsgemäßen Klarspülmittel können weitere nichtionische Tenside enthalten. Typische Beispiele für nichtionische Tenside sind Alkyl- und/oder Alkenyloligoglykoside, endgruppenverschlossene Alkoxylate von Alkanolen ohne freie OH-Gruppen, alkoxylierte Fettsäureniedrigalkylester, Aminoxide, Alkylphenolpolyglycolether, Fettsäurepolyglycolester, Fettsäureamidpolyglycolether, Fettaminpolyglycolether, alkoxylierte Triglyceride, Mischether bzw. Mischformale, Fettsäure-N-alkylglucamide, Proteinhydrolysate (insbesondere pflanzliche Produkte auf Weizenbasis), Polyolfettsäureester, Zuckerester, Sorbitanester und Polysorbate. Sofern die nichtionischen Tenside Polyglycoletherketten enthalten, können diese eine konventionelle, vorzugsweise jedoch eine eingeengte Homologenverteilung aufweisen.The rinse aids according to the invention can contain further nonionic surfactants. Typical examples of nonionic surfactants are alkyl and / or alkenyl, terminally capped alkoxylates of alkanols with no free OH groups, alkoxylated fatty acid alkyl esters, amine oxides, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers and mixed formals, fatty acid-N-alkyl, Protein hydrolysates (especially vegetable products based on wheat), polyol fatty acid esters, sugar esters, sorbitan esters and polysorbates. If the nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.

    Gemäß der vorliegenden Erfindung können die erfindungsgemäßen Klarspülmittel anionische Tenside enthalten.According to the present invention, the rinse aid according to the invention can be anionic surfactants contain.

    Anionische TensideAnionic surfactants

    Typische Beispiele für anionische Tenside sind Seifen, Alkylbenzolsulfonate, sekundäre Alkansulfonate, Olefinsulfonate, Alkylethersulfonate, Glycerinethersulfonate, α-Methylestersulfonate, Sulfofettsäuren, Alkyl- und/oder Alkenylsulfate, Alkylethersulfate, Glycerinethersulfate, Hydroxymischethersulfate, Monoglycerid(ether)sulfate, Fettsäureamid(ether)sulfate, Mono- und Dialkylsulfosuccinate, Mono- und Dialkylsulfosuccinamate, Sulfotriglyceride, Amidseifen, Ethercarbonsäuren und deren Salze, Fettsäureisethionate, Fettsäuresarcosinate, Fettsäuretauride, N-Acylaminosäuren wie beispielsweise Acyllactylate, Acyltartrate, Acylglutamate und Acylaspartate, Alkyloligoglucosidsulfate, Proteinfettsäurekondensate (insbesondere pflanzliche Produkte auf Weizenbasis) und Alkyl(ether)phosphate. Sofem die anionischen Tenside Polyglycoletherketten enthalten, können diese eine konventionelle, vorzugsweise jedoch eine eingeengte Homologenverteilung aufweisen.Typical examples of anionic surfactants are soaps, alkyl benzene sulfonates, secondary alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerin ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl and / or alkenyl sulfates, alkyl ether sulfates, glycerin ether sulfates, mono- ether sulfate sulfates , hydroxymischogether sulfate, fatty acid ether sulfate sulfates, Mono- and dialkylsulfosuccinates, mono- and dialkylsulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acylamino acids such as acyllactylates, in particular acylolate glucosate acids, acylolate glucosate fatty acids, acylolate glucosate fatty acids, acylolate glucosate fatty acids, acylolate glucosate fatty acids, acylolate glucosate fatty acids, acylolate glucosate fatty acids, and acylolate glucosate fatty acids based on acylolate glucosate fatty acids (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.

    Vorzugsweise sind die anionischen Tenside ausgewählt aus der Gruppe, die gebildet wird von Alkylund/oder Alkenylsulfate, Alkylethersulfate, Alkylbenzolsulfonate, Monoglycerid(ether)sulfate und Alkansulfonate, insbesondere Fettalkoholsulfate, Fettalkoholethersulfate, sekundäre Alkansulfonate und lineare Alkylbenzolsulfonate.The anionic surfactants are preferably selected from the group consisting of alkyl and / or alkenyl sulfates, alkyl ether sulfates, alkyl benzene sulfonates, monoglyceride (ether) sulfates and alkane sulfonates, in particular fatty alcohol sulfates, fatty alcohol ether sulfates, secondary alkane sulfonates and linear alkyl benzene sulfonates.

    Hilfs- und ZusatzstoffeAuxiliaries and additives

    Die erfindungsgemäßen Klarspülmittel können als übliche Inhaltstosstoffe bzw. Hilfs- und Zusatzstoffe beispielsweise Lösungsvermittler wie Cumolsulfonat, Ethanol, Isopropylalkohol, Ethylenglycol, Propylenglycol, Butylglycol, Diethylenglycol, Propylenglycolmonobutylether, Polyethylen- bzw. Polypropylenglycolether mit Molmassen von 600 bis 1 500 000, vorzugsweise mit einer Molmasse von 400 000 bis 800 000, oder insbesondere Butyldiglycol enthalten. Weiterhin können organische Säuren, wie ein- und/ oder mehrwertige Carbonsäuren, bevorzugt Citronensäure, sowie Konservierungsmittel und Duftstoffe eingesetzt werden.The rinse aids according to the invention can be used as customary ingredient substances or auxiliaries and additives, for example solubilizers such as cumene sulfonate, ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, butyl glycol, diethylene glycol, propylene glycol monobutyl ether, polyethylene or polypropylene glycol ether with molecular weights from 600 to 1,500,000, preferably with a molecular weight from 400,000 to 800,000, or in particular butyl diglycol. Organic acids, such as mono- and / or polyvalent carboxylic acids, preferably citric acid, and preservatives and fragrances can also be used.

    In einer bevorzugten Ausführungsform enthalten die Klarspülmittel mindestens 50 Gew.% Wasser - bezogen auf das Mittel.In a preferred embodiment, the rinse aid contains at least 50% by weight of water. based on the mean.

    Gewerbliche AnwendungCommercial application

    Ein weiterer Gegenstand der Erfindung ist die Verwendung von Geminitensiden der Formel (I) und Fettalkoholalkoxylaten der Formel (II) im erfindungsgemäßen Verhältnis zur Verbesserung des Netzverhaltens in Klarspülmitteln, vorzugsweise auf harten Oberflächen, insbesondere in kombinierten Produkten aus maschinellen Geschirr-Reinigern und Klarspüler.Another object of the invention is the use of gemini surfactants of the formula (I) and Fatty alcohol alkoxylates of the formula (II) in the ratio according to the invention for improving the Wetting behavior in rinse aid, preferably on hard surfaces, especially in combined Products from machine dishwashing detergents and rinse aid.

    Im Gegensatz zu den bisher bekannten Hydroxymischethern zeichnet sich die erfindungsgemäße Kombination aus Geminitensiden und ausgewählten Fettalkoholalkoxylaten im erfindungsgemäßen Verhältnis, neben ihrer schaumdämpfenden Wirkung und der hohen Verträglichkeit, insbesondere gegenüber Kunststoff, durch ihre höheren Schmelzpunkte aus. Dadurch sind sie besonders zur vereinfachten Herstellung von festen Formulierungen geeignet. Die erfindungsgemäßen Mischungen aus Geminitensiden und Fettalkoholalkoxylaten sind im Verhältnis 1:1 bis 4:1 fest. Beispielsweise sind Mischungen im Verhältnis 1:4 bei Raumtemperatur flüssig. Die festen Tensidmischungen lassen sich problemlos handhaben und besonders gut in feste Kombinationspräparate aus Reiniger und Klarspüler für das maschinelle Geschirrspülen einarbeiten.
    Ebenso lösen sich die erfindungsgemäßen Mischungen, durch ihre höheren Schmelzpunkte, später in der Reinigungsflotte auf und entfalten zeitversetzt, und in höherer Konzentration ihre Wirkung.    In contrast to the previously known hydroxy mixed ethers, the combination according to the invention of gemini surfactants and selected fatty alcohol alkoxylates in the ratio according to the invention is not only characterized by its foam-suppressing action and high compatibility, but especially by plastic, but also by its higher melting points. This makes them particularly suitable for the simplified production of solid formulations. The mixtures of gemini surfactants and fatty alcohol alkoxylates according to the invention are solid in a ratio of 1: 1 to 4: 1. For example, mixtures in a ratio of 1: 4 are liquid at room temperature. The solid surfactant mixtures are easy to handle and work particularly well into solid combination preparations made up of detergent and rinse aid for automatic dishwashing.
    Likewise, the mixtures according to the invention, due to their higher melting points, later dissolve in the cleaning liquor and develop with a time delay and in higher concentration.

    Die Klarspülmittel können sowohl als wässrige Lösungen, als auch in fester Form z.B. in Wachs eingegossen oder als Gel vorliegen. The rinse aids can be used both as aqueous solutions and in solid form e.g. in wax poured in or present as a gel.

    BeispieleExamples Screening - Methode zur Bewertung der Benetzungseigenschaften von Tensid - Lösungen gegenüber KunststoffmaterialienScreening method for evaluating the wetting properties of surfactant solutions towards plastic materials

    Die Benetzungseigenschaften von Tensidlösungen gegenüber Kunststoffen wurden in einem vereinfachten Screening in Anlehnung an die Bedingungen / Testparameter in einer handelsüblichen Geschirrspülmaschine, jedoch ohne die Verwendung einer solchen, bestimmt.The wetting properties of surfactant solutions against plastics were combined in one simplified screening based on the conditions / test parameters in a commercially available Dishwasher, but without the use of such.

    Zur Bewertung der Benetzungseigenschaften werden Kunststoff - Prüfkörper der Abmessung 20 x 5 cm zuerst mit 1%iger NaOH und dann mit iso-Propanol gereinigt. Die so vorbehandelten Prüfkörper werden dann in die zu prüfende Lösung getaucht und direkt wieder entfernt. Die Bewertung erfolgt visuell durch Aufstellung einer Rangliste bzw. nach einer Notenscala von 1 - 5. Dabei bedeutet 5, daß spontanes Aufreißen des Flüssigkeitsfilms auftritt und die Benetzung vollständig aufgehoben wird. Note 5 wird bei Verwendung von Wasser erhalten. Die Note 1 bedeutet vollständige Benetzung der Kunststoffoberfläche bei einem gleichmäßigem Ablauf des Flüssigkeitsfilms (Testsubstanz: Maranil A55® COGNIS). Testparameter: Wasserhärte 2°d Salzfracht 700ppm Temperatur 60°C Tensidkonzentration 0,1% To evaluate the wetting properties, plastic test specimens measuring 20 x 5 cm are first cleaned with 1% NaOH and then with isopropanol. The test specimens pretreated in this way are then immersed in the solution to be tested and immediately removed again. The evaluation is carried out visually by drawing up a ranking list or on a scale from 1-5. 5 means that spontaneous tearing of the liquid film occurs and the wetting is completely eliminated. Grade 5 is obtained when water is used. The grade 1 means complete wetting of the plastic surface with an even flow of the liquid film (test substance: Maranil A55® COGNIS). Test parameters: water hardness 2 ° d salt load 700 ppm temperature 60 ° C surfactant 0.1%

    Prüfkörper:Test specimens:

    PP (Polypropylen); PE (Polyethylen); PC (Polycarbonat);
    In Tabelle 1 sind die Versuchsergebnisse dargestellt, wobei V1, V2, V3, V4, V5 und V6 Vergleichsversuche und I, II, III und IV die erfindungsgemäßen Beispiele wiedergeben.

    Figure 00080001
    PP (polypropylene); PE (polyethylene); PC (polycarbonate);
    The test results are shown in Table 1, with V1, V2, V3, V4, V5 and V6 comparative tests and I, II, III and IV representing the examples according to the invention.
    Figure 00080001

    KlarspülvermögenKlarspülvermögen

    Die Beurteilung des Klarspülvermögens erfolgt visuell durch Testpersonen. Dabei werden Gläser, Besteck, Kunststoff- sowie Porzellanteller unter definierten Bedingungen in einer Haushaltsgeschirrspülmaschine gespült. Danach wird das Spülgut unter definierten Lichtverhältnissen beurteilt (Beurteilung von Flecken und Belägen). Die Angabe der Ergebnisse erfolgt als "deutlich besser / besser / gleich / schlechter als Standard". Der Standard wird für jede Testreihe neu definiert. In Tabelle 2 sind die Versuchsergebnisse dargestellt, wobei V1, V2 und V3 Vergleichsversuche (=Standard) und I bis IV die erfindungsgemäßen Beispiele wiedergeben.

    Figure 00090001
    The rinse aid capacity is assessed visually by test subjects. Glasses, cutlery, plastic and porcelain plates are washed in a household dishwasher under defined conditions. The items to be washed are then assessed under defined lighting conditions (assessment of stains and deposits). The results are given as "significantly better / better / equal / worse than standard". The standard is redefined for each test series. The test results are shown in Table 2, with V1, V2 and V3 comparative tests (= standard) and I to IV representing the examples according to the invention.
    Figure 00090001

    Claims (7)

    Klarspülmittel enthaltend, a. Geminitenside gemäß Formel (I) R-CHOH-CH2-[OCH2CH2]x-O-CH2-CHOH-R   (I) in der R für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen und x für 5 bis 90 steht und b. Fettalkoholalkoxylate der Formel (II) R1O[CH2(CH3)CHO]q(CH2CH2O)rH   (II) in der R1 für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen und q für 0 bzw. für Zahlen von 1 bis 10 und r für Zahlen von 1 bis 50 steht, und gegebenenfalls weitere in Klarspülmitteln übliche Inhaltsstoffe,
    dadurch gekennzeichnet, dass die Komponenten a: b im Verhältnis 1:1 bis 4:1 enthalten sind.    Containing rinse aid, a. Gemini surfactants according to formula (I) R-CHOH-CH 2 - [OCH 2 CH 2 ] xO-CH 2 -CHOH-R (I) in which R is a linear or branched alkyl and / or alkenyl radical having 4 to 22 carbon atoms and x is 5 to 90 and b. Fatty alcohol alkoxylates of the formula (II) R 1 O [CH 2 (CH 3 ) CHO] q (CH 2 CH 2 O) r H (II) in which R1 represents a linear or branched alkyl and / or alkenyl radical with 4 to 22 carbon atoms and q for 0 or for numbers from 1 to 10 and r for numbers from 1 to 50, and, if appropriate, further ingredients customary in rinse aid,
    characterized in that the components a: b are contained in a ratio of 1: 1 to 4: 1.         Mittel nach Anspruch 1, dadurch gekennzeichnet, dass Geminitenside der Formel (I) enthalten sind, wobei x für 10 bis 45, vorzugsweise 12 bis 35 steht.Agent according to Claim 1, characterized in that gemini surfactants of the formula (I) are present, where x stands for 10 to 45, preferably 12 to 35. Mittel nach Anspruch 1 und/oder 2, dadurch gekennzeichnet, dass Geminitenside der Formel (I) enthalten sind, wobei R für einen linearen oder verzweigten Alkylrest mit 8 bis 12 Kohlenstoffatomen steht.Agent according to Claim 1 and / or 2, characterized in that gemini surfactants of the formula (I) are present, where R represents a linear or branched alkyl radical having 8 to 12 carbon atoms. Mittel nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass Geminitenside der Formel (I) enthalten sind, wobei R für einen linearen Alkylrest mit 8 bis 12 Kohlenstoffatomen steht.Agent according to one of claims 1 to 3, characterized in that gemini surfactants of the formula (I) are present, where R represents a linear alkyl radical having 8 to 12 carbon atoms. Mittel nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass Geminitenside der Formel (I) enthalten sind, die mindestens 80 Gew.% Geminitenside enthalten, bei denen alle freien Hydroxygruppen des Polyethylenglycols mit 1,2-Epoxyalkanen verschlossen sind. Agent according to one of claims 1 to 4, characterized in that it contains gemini surfactants of the formula (I) which contain at least 80% by weight gemini surfactants in which all free hydroxy groups of the polyethylene glycol are sealed with 1,2-epoxyalkanes. Wässrige Klarspülmittel nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass sie mindestens 50 Gew.% - bezogen auf das Mittel - Wasser enthalten.Aqueous rinse aid according to one of claims 1 to 5, characterized in that it contains at least 50% by weight, based on the detergent, of water. Verwendung von Geminitensiden gemäß Formel (I) und Fettalkoholalkoxylaten der Formel (II) gemäß Anspruch 1, zur Verbesserung des Netzverhaltens in Klarspülmitteln.Use of gemini surfactants according to formula (I) and fatty alcohol alkoxylates of formula (II) according to claim 1, to improve the wetting behavior in rinse aid.
    EP02027460A 2001-12-18 2002-12-10 Mixtures of gemini surfactants and fatty alcoholalkoxylates in rinse aids Withdrawn EP1321511A3 (en)

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