EP0054894B1 - Surfactant-containing mixture for cleaning hard surfaces - Google Patents

Surfactant-containing mixture for cleaning hard surfaces Download PDF

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Publication number
EP0054894B1
EP0054894B1 EP81110471A EP81110471A EP0054894B1 EP 0054894 B1 EP0054894 B1 EP 0054894B1 EP 81110471 A EP81110471 A EP 81110471A EP 81110471 A EP81110471 A EP 81110471A EP 0054894 B1 EP0054894 B1 EP 0054894B1
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Prior art keywords
weight
cleaning
atoms
surfactant
alkyl radical
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EP81110471A
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German (de)
French (fr)
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EP0054894A1 (en
Inventor
Wolfgang Klinger
Eckhard Milewski
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Hoechst AG
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Hoechst AG
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/24—Organic compounds containing halogen
    • C11D3/245—Organic compounds containing halogen containing fluorine
    • 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
    • C11D1/835—Mixtures of non-ionic with cationic compounds
    • 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
    • C11D1/835—Mixtures of non-ionic with cationic compounds
    • C11D1/8355—Mixtures of non-ionic with cationic compounds containing a combination of non-ionic compounds differently alcoxylised or with different 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
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • 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
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • the invention relates to a surfactant-containing mixture for the mechanical cleaning of hard surfaces, in particular bottles and dishes, in the alkaline to highly alkaline range of the cleaning liquor.
  • the system must also be as little or as little foam as possible, since excessive foam formation can lead to malfunctions in the operating behavior of the system, for example if the dirt that accumulates in the foam layer cannot be discharged sufficiently. Additional tendencies towards foam formation are caused by the impurities carried into the fleet by the items to be cleaned, in particular by protein-containing residues on the items to be cleaned. In the case of bottle cleaning, this also applies in particular to the labels to be removed, which are introduced into the cleaning liquor through the glue residues and residues of printing inks, including the surfactant auxiliaries contained in the latter.
  • non-ionic surfactants with a low-foaming characteristic as cleaning agents for hard surfaces in alkaline baths.
  • These are, in particular, addition products of ethylene oxide and / or propylene oxide onto amines, longer-chain fatty alcohols or alkylphenols, polyglycol ether formals or acetals or block copolymers of ethylene and propylene oxide.
  • Such surfactant systems can be adjusted, in particular, by suitable variation of the ethylene oxide and propylene oxide proportions to the lowest possible foam tendency and increased cleaning action, an excess weight of the propylene oxide favoring the former property and an excess weight of the ethylene oxide promoting the latter property.
  • the ratio of the ethylene oxide to propylene oxide units should preferably be in the range from 0.8 to 2.
  • a 3 also a polyalkylene glycol dialkyl ether of the formula be, which contains ethylene oxide and optionally propylene oxide units, which can be arranged randomly or in blocks.
  • R 1 is an alkyl radical with 6 to 22 carbon atoms, preferably with 8 to 18 carbon atoms
  • R 3 is an alkyl radical with 1 to 4 carbon atoms, preferably the tert-butyl radical
  • c is a statistical mean in the range from 5 to 20, preferably from 6 to 14
  • d has a statistical mean in the range from 0 to 3, preferably 0.
  • non-ionic surfactants can also be present as mixtures within groups A 1 ), A 2 ) or A 3 ) or else between groups A 1 ), A 2 ) and / or A 3 ).
  • the non-ionic surfactants of group A 1 ) are preferred.
  • the surfactant mixture contains a quaternary ammonium compound B of the formula as a cationic component in which R 4 and R 5 , identical or different, are an alkyl radical with 1 to 12 C atoms, preferably with 4 to 8 C atoms, in particular with 4 to 6 C atoms, R 6 is an alkyl radical with 1 to 8 C atoms Atoms, preferably 1 to 6 carbon atoms, and R 7 is an alkyl radical with 1 to 4 carbon atoms or a benzyl radical.
  • A is an anion, preferably a chloride or bromide anion or one of the formula CH 3 0S0 3 -.
  • Rf is a CF 3 - or (CF 3 ) 2 -CF radical
  • R 8 is a lower alkyl radical
  • R 9 is hydrogen or a lower alkyl radical (with a lower alkyl radical here being one with 1 to 3 carbon atoms, preferably a methyl - or ethyl radical should be understood)
  • e is an integer from 5 to
  • f is an integer from 0 to 4
  • these fluorinated alcohols are advantageously introduced in a mixture with a solubilizer in which they have been predissolved. This is especially true when very small amounts of the fluorinated alcohol are to be used.
  • a suitable solubilizer must be completely or at least largely homogeneously miscible with the surfactant mixture A + B or its single components.
  • the fluorinated alcohol C) should be largely or entirely soluble in this solubilizer.
  • An effective amount of such a solubilizer is preferably 1 to 1,000 parts by weight per 1 part by weight of the fluorinated alcohol; however, this effective amount should not exceed 20% by weight of the total weight of components A + B.
  • solubilizers are aliphatic ketones, such as dimethyl and diethyl ketone.
  • Carboxylic acid esters of aliphatic alcohols and diols such as ethyl acetate, isobutyl ester, ethylene glycol acetate, 2-ethylhexyl-2-ethylhexanoic acid ester, acid amides of longer-chain carboxylic acids, such as, for example, N- (2-ethylhexyl) -isononanoic acid amide, polypropylene glycols with molar weights of> 600 and mixed units of molecular weights> 600 and propylene oxide, ethylene and propylene glycol monoethers and the corresponding polyglycol ethers, such as methyl, ethyl and butyl monoethers of di, tri and tetraethylene glycol.
  • Alkanols with 1 to 9 carbon atoms in a straight or branched chain should
  • the surfactant-containing mixtures according to the invention can be used as a mixture of components A + B + C., optionally including the solubilizer, in undiluted, liquid form. However, they can also be used in the form of aqueous concentrates, for example for better meterability, if appropriate also with the addition of an organic solvent. that is not a solution broker in the above sense.
  • components A and B can also first be added individually or together to the aqueous cleaning liquor and the fluorinated alcohol C can be metered in, in which case a solubilizer must be present.
  • component C can also be introduced premixed with one of the two components A or B, the other being subsequently metered in.
  • the application concentration is advantageously 0.05 to 10 g of the surfactant mixture A + B (without inclusion of C) per liter of cleaning liquor, preferably 0.1 to 2 g per liter.
  • Such application concentrations are non-critical statements, since the amount depends to a certain extent on the type of surface to be cleaned and on the type and extent of the contaminants.
  • the surfactant mixtures according to the invention can optionally be used in the preparation commercially available formulations further additives and auxiliaries are added. These include dyes, fragrances, corrosion inhibitors and disinfectants.
  • auxiliaries include dyes, fragrances, corrosion inhibitors and disinfectants.
  • the known builders which are optionally also complexing agents, should also be mentioned here.
  • the condensed phosphates such as tripolyphosphates and in particular pentasodium triphosphate, come into consideration.
  • these are complex-forming aminopolycarboxylic acids and their salts, such as, in particular, alkali metal salts of nitrilotriacetic acid and ethylenediaminetetraacetic acid, and also also complex-forming hydroxycarboxylic acids and polymeric carboxylic acids, such as citric acid, tartaric acid and the like.
  • Another class of complexing builders are polyphosphonic salts, such as the alkali salts of aminophosphonic acid.
  • builders, such as silicates, for example sodium metasilicate, carbonates, bicarbonates, borates and citrates can also be added. With the aid of such additives, the mixtures according to the invention can optionally be converted into powder form and can also be used in this form.
  • the surfactant-containing mixtures according to the invention are suitable for the mechanical cleaning of hard surfaces in alkaline liquors. This applies to cleaning in household dishwashers and so-called commercial cleaning systems.
  • the mixtures are particularly suitable for industrial cleaning systems for hard surfaces, for example dishwashing and bottle washing systems, which operate under high mechanical liquor movements in continuous operation and in highly alkaline liquors at pH values of 2-t 10, preferably 2-e 12.
  • the necessary alkaline additives preferably sodium or potassium hydroxide for the highly alkaline pH range of the liquor, can be dissolved in the aqueous cleaning liquor before the surfactant-containing mixture according to the invention is introduced. However, they can also be added directly to the mixture and metered together with it.
  • the alkaline agent is expediently added in the form of powder, flakes or cookies.
  • the mixtures according to the invention have an extremely low tendency towards foaming which is indispensable for industrial cleaning systems. It is essential that the fluorinated alcohol C used as an anti-foaming agent is absolutely stable in the highly alkaline range. By adding it it is achieved that even with extremely high mechanical liquor movements, such as occur, for example, in the bottle cleaning systems of breweries, there is practically no foam formation. The tendency towards foaming is also reduced to a minimum, even with heavily to extremely foam-promoting soiling, such as protein, milk, beer, lemonade, glue and surfactant components from labels.
  • the surfactant-containing mixtures have this extraordinarily low tendency to foam formation not only at the working temperatures of such cleaning systems, that is above about 40 ° C, but also at low temperatures, so that when refilled with cold water and heating, no disruptive foam is formed, which then leads to Overflowing or disturbing the circulation of the system.
  • the surfactant mixtures according to the invention as cleaning agents for the mechanical cleaning of hard surfaces, in particular with regard to the high demands placed on industrial cleaning systems, also have the following significant advantages: the mixtures are not only resistant to alkali, but also long-term storage stability with alkali.
  • the excellent dirt absorption capacity allows long service life in the system until it is refilled without impairing the cleaning effect.
  • Good wetting capacity and drainage behavior enable dirt to be removed quickly and thus a high throughput of items to be cleaned. The freedom from stains and streaks as well as high gloss of the cleaned goods is also guaranteed.
  • the dirt absorption limit by checking the foaming capacity with increasing dirt load is determined by gradually adding a test foamer to the cleaning liquor.
  • a whisked egg is used as the test frother, which is added in portions of 0.2 g / l of liquor.
  • the dirt absorption limit is recognizable by a sudden foam increase in the cleaning liquor. 30 ml (at 65 ° C) is selected as the upper foam limit.
  • Clean 0.5 liter beer bottles are filled with 100 ml of the cleaning liquor and, after being closed, shaken vigorously five times in a cork stopper. After a short period of action (approx. 1 minute), the shaking process is repeated again for five and the detergent-containing cleaning liquor is then poured out. This is followed by rinsing four to five times in succession with 100 ml of distilled water until pH 7 is reached
  • Builders and auxiliaries 65% by weight sodium metasilicate, 20% by weight sodium hydroxide (powdered), 10% by weight sodium carbonate.
  • the surfactant components are mixed together and then the fluorinated alcohol is stirred in at 30 to 40 ° C.
  • the framework and auxiliary materials are placed in a mixing drum, where they are mixed well with the surfactant mixture.
  • Builders and auxiliaries 25% by weight of pentasodium triphosphate, 25% by weight of sodium metasilicate, 25% by weight of sodium carbonate and 15% by weight of sodium hydroxide (powdered).
  • the components of the surfactant-containing mixture are mixed and then intimately mixed with the framework and auxiliary substances that have already been mixed to form the powder.
  • Powdered dishwashing detergent
  • Builders and auxiliaries 41.5% by weight sodium metasilicate, 35% by weight pentasodium triphosphate. 20% by weight sodium carbonate and 1.5% by weight sodium dichloroisocyanurate (as disinfectant).
  • the surfactant-containing formulation which has been premixed with one another in the order of the components is incorporated into this mixture.
  • Liquid bottle cleaner
  • Builders and auxiliaries 35% by weight phosphoric acid (85% by weight), 20% by weight 2-phosphonobutane-1,2,4-tricarboxylic acid and 25% by weight deionized water.
  • Deionized water is initially introduced and phosphoric acid and 2-phosphonobutane-1,2,4-tricarboxylic acid are then stirred in. Now the premixed surfactant-containing mixture is homogenized.
  • Liquid dishwashing detergent
  • Pentasodium triphosphate is dissolved in deionized water, then phosphoric acid and finally the mixture containing surfactants are added.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

A detergent composition which is particularly suitable for the mechanical cleaning of hard surfaces, in particular glass, porcelain and the like, in a cleaning liquor within the alkaline range, is described. This detergent composition comprises (A) a nonionic surfactant selected from the group comprising polyalkylene glycol monoalkyl ethers containing ethylene oxide and propylene oxide units, polyglycol ether formals containing ethylene oxide units and, if appropriate, propylene oxide units, or polyalkylene glycol dialkyl ethers containing ethylene oxide units and, if appropriate, propylene oxide units, (B) a selected quaternary ammonium compound as a cationic surfactant, and (C) a fluorinated alcohol as an antifoaming agent. These compositions are particularly suitable for industrial crockery-cleaning and bottle-cleaning plants which are operated with considerable mechanical agitation of the liquor within a highly alkaline pH range.

Description

Die Erfindung betrifft ein tensidhaltiges Gemisch für die maschinelle Reinigung von harten Oberflächen, insbesondere von Flaschen und Geschirr im alkalischen bis hochalkalischen Bereich der Reinigungsflotte.The invention relates to a surfactant-containing mixture for the mechanical cleaning of hard surfaces, in particular bottles and dishes, in the alkaline to highly alkaline range of the cleaning liquor.

Für die Reinigung von Flaschen und sonstigen Gegenständen mit harten Oberflächen, wie Geschirr aus Porzellan, Keramik, Glas oder Kunststoff, ferner von anderen Glas- oder auch Metallgegenständen werden heute weitgehend maschinelle Reinigungsverfahren angewandt. Während bei Haushaltsspülmaschinen nur relativ geringe Flottenbewegungen entsprechend dem geringen Durchsatz an zu reinigendem Gut erforderlich sind, arbeiten gewerbliche und insbesondere industrielle Reinigungsanlagen bei großem Durchsatz mit sehr hohen Flottenbewegungen und Sprühintensitäten. Wegen der höheren Schmutzbelastungen werden dabei an die Qualität der eingesetzten tensidhaltigen Reinigungsmittel hinsichtlich ihres Reinigungs-, Schmutzaufnahme- und Netzvermögens hohe Anforderungen gestellt. Um die erforderliche schnelle Ablösung und Emulgierung der anhaftenden Verunreinigungen zu gewährleisten, wird in solchen gewerblichen und insbesondere in industriellen Reinigungsanlagen üblicherweise in hochalkalischen Flotten gearbeitet. Wegen der hohen mechanischen Flottenbewegungen muß das System auch möglichst schaumarm beziehungsweise schaumfrei sein, da übermäßige Schaumbildung zu Störungen im Betriebsverhalten der Anlage führen kann, beispielsweise, wenn der in der Schaumschicht sich ansammelnde Schmutz nicht ausreichend ausgetragen werden kann. Zusätzliche Tendenzen zur Schaumbildung werden durch die vom Reinigungsgut in die Flotte eingeschleppten Verunreinigungen, besonders durch proteinhaltige reste am Reinigungsgut, hervorgerufen. Im Falle der Flaschenreinigung gilt dies besonders auch für die zu entfernenden Etiketten, die durch die Leimreste und Reste von Druckfarben einschließlich der in letzteren enthaltenen Tensid-Hilfsmittel in die Reinigungsflotte eingebracht werden.For cleaning bottles and other objects with hard surfaces, such as dishes made of porcelain, ceramics, glass or plastic, as well as other glass or metal objects, mechanical cleaning processes are largely used today. While only relatively small movements of the liquor are required in accordance with the low throughput of items to be cleaned in household dishwashers, commercial and in particular industrial cleaning systems work with high throughput with very high liquor movements and spray intensities. Because of the higher contamination levels, high demands are placed on the quality of the surfactant-containing cleaning agents used with regard to their cleaning, dirt absorption and wetting properties. In order to ensure the necessary rapid detachment and emulsification of the adhering impurities, work is usually carried out in highly alkaline liquors in such commercial and in particular in industrial cleaning plants. Because of the high mechanical movements of the liquor, the system must also be as little or as little foam as possible, since excessive foam formation can lead to malfunctions in the operating behavior of the system, for example if the dirt that accumulates in the foam layer cannot be discharged sufficiently. Additional tendencies towards foam formation are caused by the impurities carried into the fleet by the items to be cleaned, in particular by protein-containing residues on the items to be cleaned. In the case of bottle cleaning, this also applies in particular to the labels to be removed, which are introduced into the cleaning liquor through the glue residues and residues of printing inks, including the surfactant auxiliaries contained in the latter.

Es ist bekannt, nicht-ionische Tenside mit schwach schäumender Charakterisitk als Reinigungsmittel für harte Oberflächen in alkalischen Bädern einzusetzen. Dies sind insbesondere Anlagerungsprodukte von Ethylenoxid und/oder Propylenoxid an Amine, längerkettige Fettalkohole oder Alkylphenole, Polyglykoletherformale oder -acetale oder Blockcopolymerisate des Ethylen- und Propylenoxids. Derartige Tensidsysteme können insbesondere durch geeignete Variation der Ethylenoxid- und Propylenoxid-Anteile auf möglichst geringe Schaumneigung und erhöhte Reinigungswirkung eingestellt werden, wobei ein Übergewicht des Propylenoxids die erstere Eigenschaft, ein Übergewicht des Ethylenoxids die letztere Eigenschaft begünstigt. Jedoch stellt eine solche Einstellung dieser Eigenschaften immer einen Kompromiß dar, und es wäre wünschenswert, mehr von der einen Eigenschaft zu erhalten, ohne auf Anteile der anderen verzichten zu müssen. Bei maschinellen Reinigungsprozessen für Flaschen, Geschirr und dergleichen im industriellen Bereich, die unter hoher mechanischer Bewegung ablaufen, ist die Schaumarmut der genannten Tensidsysteme zwar sehr erwünscht, jedoch die Schmutzablösung in der zur verfügung stehenden geringen Zeit beim Durchsatz des Reinigungsgutes und auch das Schmutzaufnahmevermögen häufig nicht ausreichend und verbesserungsbedürftig.It is known to use non-ionic surfactants with a low-foaming characteristic as cleaning agents for hard surfaces in alkaline baths. These are, in particular, addition products of ethylene oxide and / or propylene oxide onto amines, longer-chain fatty alcohols or alkylphenols, polyglycol ether formals or acetals or block copolymers of ethylene and propylene oxide. Such surfactant systems can be adjusted, in particular, by suitable variation of the ethylene oxide and propylene oxide proportions to the lowest possible foam tendency and increased cleaning action, an excess weight of the propylene oxide favoring the former property and an excess weight of the ethylene oxide promoting the latter property. However, such an adjustment of these properties is always a compromise, and it would be desirable to get more of one property without sacrificing portions of the other. In machine cleaning processes for bottles, crockery and the like in the industrial sector, which take place with high mechanical movement, the low foam of the surfactant systems mentioned is very desirable, but the detachment of dirt in the short time available for the throughput of the cleaning material and also the dirt absorption capacity are often not sufficient and in need of improvement.

Man hat bereits versucht, diesen Nachteil durch bestimmte Mischungen aus den genannten Klassen von nicht-ionischen Tensiden auszugleichen, wie in der DE-B-2723139 beschrieben wird. Solche Mischungen besitzen zwar bei der erhöhten Arbeitstemperatur der Anlage eine vorteilhaft niedrige Schaumneigung, jedoch eine zu hohe Schaumneigung bei tieferen Temperaturen, was beim Befüllen und Aufheizen der Anlage von Nachteil ist. Ein Rückgriff auf anionische Tenside, die das Reinigungs- und Netzvermögen erhöhen würden, ist kaum möglich, da dadurch die Schaumneigung zu stark vergrößert wird. Es ist auch schon versuch worden, kationische Tenside mit langen Alkylketten zum Zwecke der Desinfektion in Flaschenreinigungsmittel einzubeziehen. In der DE-A-2449354 wird dies beschrieben, wobei als kationische Tenside quaternäre Ammoniumsalze, die einen oder zwei langkettige Alkylreste oder Alkylreste im Molekül neben kurzkettigen Resten enthalten, eingesetzt werden. Da diese Art kationischer Tenside zu relativ starker Schaumbildung neigt, muß zusätzlich ein Entschäumer hinzugefügt werden, wofür dort Orthophosphorsäuremonoalkylester vorgesehen sind. Gegebenenfalls können nicht-ionische Tenside zusätzlich im Gemisch anwesend sein. Solche Formulierungen unter Einschluß kationischer, zumindest eine lange Alkylkette enthaltender quaternärer Ammoniumverbindungen haben jedoch den entscheidenden Nachteil, daß die genannten Verbindungen substantiv auf das Reinigungsgut aufziehen.Attempts have already been made to compensate for this disadvantage by using certain mixtures of the classes of nonionic surfactants mentioned, as described in DE-B-2723139. Such mixtures have an advantageously low foam tendency at the elevated working temperature of the system, but an excessive foam tendency at lower temperatures, which is disadvantageous when filling and heating the system. It is hardly possible to use anionic surfactants, which would increase the cleaning and wetting properties, as this increases the tendency to foam too much. Attempts have also been made to include cationic surfactants with long alkyl chains in bottle detergents for disinfection. This is described in DE-A-2449354, using quaternary ammonium salts which contain one or two long-chain alkyl radicals or alkyl radicals in the molecule in addition to short-chain radicals as cationic surfactants. Since this type of cationic surfactant tends to form a relatively large amount of foam, a defoamer must also be added, for which orthophosphoric acid monoalkyl esters are provided. If necessary, non-ionic surfactants can also be present in the mixture. However, such formulations, including cationic quaternary ammonium compounds containing at least one long alkyl chain, have the decisive disadvantage that the compounds mentioned absorb substantially onto the items to be cleaned.

Dadurch wird verhindert, daß die Flüssigkeit glatt abläuft, es bilden sich Tropfen, die dann beim Trocknen störende Ränder hinterlassen. Dieser Effekt, der beim Einsatz als Wäschenachbehandlungsmittel für Textilien sehr erwünscht ist, macht den Einsatz der genannten quaternären Ammoniumverbindungen in Geschirr- und Flaschenreinigungsmitteln für alkalische Flotten sehr problematisch. Auch wird, falls die genannten quaternären Ammoniumverbindungen in Abmischung mit nicht-ionischen Tensiden, wie ebenfalls in der DE-A-24 49-354 und auch in der DE-A-25 23 588 beschrieben ist, eingesetzt werden, keine nennenswerte Erhöhung des Schmutzaufnahmevermögens der nicht-ionischen Komponente erzielt.This prevents the liquid from running off smoothly, drops form, which then leave disruptive edges when drying. This effect, which is very desirable when used as a laundry aftertreatment agent for textiles, makes the use of the quaternary ammonium compounds mentioned in dishwashing detergent and bottle detergent very problematic for alkaline liquors. Also, if the quaternary ammonium compounds mentioned are used in a mixture with non-ionic surfactants, as is also described in DE-A-24 49-354 and also in DE-A-25 23 588, there is no appreciable increase in the dirt-holding capacity achieved the non-ionic component.

Es bestand somit die Aufgabe, das Schmutzaufnahmevermögen solcher Gemische zu verbessern, ohne den Nachteil der Substantivität in Kauf nehmen zu müssen, wobei eine minimale Schaumbildungstendenz auch bei extrem hohe.i Flottenbewegungen und/oder extrem schaumfördernden Verschmutzungen erreicht werden soll.It was therefore the task of improving the dirt-holding capacity of such mixtures without having to accept the disadvantage of substantivity, with minimal foaming tendency even with extremely high movements of the fleet and / or extremely foam-promoting soiling.

Gemäß der Erfindung wird dies erreicht durch ein tensidhaltiges Gemisch, das dadurch gekennzeichnet ist, daß es besteht aus

  • A) 20 bis 95 Gew.-% der gewichtssumme des Gemisches A + B eines nicht-ionischen Tensids der Formel
    Figure imgb0001
    Figure imgb0002
    Figure imgb0003
    oder eines Gemisches der Formeln A1). A2) und/oder A3), worin
    • R1 ein Alkylrest mit 6 bis 22 C-Atomen,
    • R2 ein Alkylrest mit 1 bis 6 C-Atomen,
    • R3 ein Alkylrest mit 1 bis 4 C-Atomen,
    • a ein statistischer Mittelwert im bereich von 2 bis 10,
    • b ein statistischer Mittelwert im Bereich von 1 bis 8,
    • c ein statistischer Mittelwert im Bereich von 5 bis 20, und
    • d ein statistischer Mittelwert im Bereich von 0 bis 3 ist,
      und worin die Ethylenoxid- und Propylenoxid-Einheiten von A1 in Form von Blöcken vorliegen und zumindest ein Teil des Propylenoxids nach Anlagerung des Ethylenoxids aufkondensiert ist, und die Einheiten von A2 und A3 statistisch oder in Blöcken angeordnet sind, und
  • B) 5 bis 80 Gew.-% der Gewichtssumme des Gemisches A + B eines kationischen Tensids der Formel
    Figure imgb0004
    worin
    • R4 und R5, gleich oder verschieden, Alkylreste mit 1 bis 12 C-Atomen sind, R6 ein Alkylrest mit 1 bis 8 C-Atomen und R7 ein Alkylrest mit 1 bis 4 C-Atomen oder ein Benzylrest ist, ferner
    • A ein Anion bedeutet,
      sowie zusätzlich
  • C) 0,001 bis 20 Gew.-%, bezogen auf die Gewichtssumme A + B = 100, eines fluorierten Alkohols der Formel
    Figure imgb0005
    worin
    • Rf ein Perfluormethyl- oder Perfluorisopropylrest,
    • R8 ein Alkylrest mit 1 bis 3 C-Atomen,
    • R9 ein Wasserstoff oder ein Alkylrest mit 1 bis 3 C-Atomen ist,
    • e eine ganze Zahl von 5 bis 15,
    • f eine ganze Zahl von 0 bis 4 bedeutet und
    • g für f = 4 den Wert 0 und für f = 0 den Wert 1 annimmt.
According to the invention, this is achieved by a surfactant-containing mixture, which is characterized in that it consists of
  • A) 20 to 95% by weight of the total weight of the mixture A + B of a nonionic surfactant of the formula
    Figure imgb0001
    Figure imgb0002
    Figure imgb0003
     or a mixture of the formulas A 1 ). A 2 ) and / or A 3 ), wherein
    • R 1 is an alkyl radical with 6 to 22 carbon atoms,
    • R 2 is an alkyl radical with 1 to 6 carbon atoms,
    • R 3 is an alkyl radical with 1 to 4 carbon atoms,
    • a a statistical mean in the range from 2 to 10,
    • b a statistical mean in the range from 1 to 8,
    • c is a statistical mean in the range of 5 to 20, and
    • d is a statistical mean in the range from 0 to 3,
      and wherein the ethylene oxide and propylene oxide units of A 1 are in the form of blocks and at least part of the propylene oxide is condensed after the ethylene oxide has been attached, and the units of A 2 and A 3 are arranged randomly or in blocks, and
  • B) 5 to 80% by weight of the total weight of the mixture A + B of a cationic surfactant of the formula
    Figure imgb0004
     wherein
    • R 4 and R 5 , the same or different, are alkyl radicals with 1 to 12 carbon atoms, R 6 is an alkyl radical with 1 to 8 carbon atoms and R 7 is an alkyl radical with 1 to 4 carbon atoms or a benzyl radical, furthermore
    • A means an anion
      as well as additionally
  • C) 0.001 to 20 wt .-%, based on the total weight A + B = 100, of a fluorinated alcohol of the formula
    Figure imgb0005
     wherein
    • Rf is a perfluoromethyl or perfluoroisopropyl radical,
    • R 8 is an alkyl radical with 1 to 3 carbon atoms,
    • R 9 is a hydrogen or an alkyl radical with 1 to 3 C atoms,
    • e is an integer from 5 to 15,
    • f represents an integer from 0 to 4 and
    • g assumes the value 0 for f = 4 and the value 1 for f = 0.

Die Wirksamkeit dieser Mittel für die maschinelle Reinigung von Geschirr, Flaschen und anderen Glasgegenständen oder auch von Metallen in alkalischen Flotten, insbesondere auch in den im industriellen Bereich angewandten hochalkalischen Flotten, beruht auf der überraschenden Erkenntnis, daß durch die Einbeziehung von quaternären Ammoniumverbindungen mit ausschließlich kurzen bis mittleren Ketten im Molekül als kationische Komponente das Schmutzaufnahmevermögen solcher Gemische erheblich verbessert werden kann, wobei diese kationschen Tenside im alkalischen Bereich praktisch nicht substantiv auf das .Reinigungsgut aufziehen, und daß ferner gleichzeitig solche Mittel infolge der als Antischaummittel hinzugefügten fluorierten Alkohole eine extrem niedrige Schaumneigung sowohl bei niedrigen als auch bei erhöhten Temperaturen und sowohl bei höchsten mechanischen Belastungen der Flotte als auch bei stark schaumfördernden Verschmutzungen aufweisen.The effectiveness of these agents for the mechanical cleaning of dishes, bottles and other glass objects or metals in alkaline liquors, especially in the highly alkaline liquors used in the industrial sector is based on the surprising finding that the inclusion of quaternary ammonium compounds with only short to medium chains in the molecule as the cationic component can considerably improve the dirt-holding capacity of such mixtures, these cationic surfactants being virtually non-substantive in the alkaline range the .Cleaning goods, and that at the same time such agents have an extremely low tendency to foam, both at low and at elevated temperatures and both under the highest mechanical loads on the liquor and with strongly foam-promoting soiling due to the addition of fluorinated alcohols as anti-foaming agents.

Die als Bestandteil eingesetzten nicht-ionischen Tenside A) sind bekannt. Es handelt sich dabei um

  • A1) Anlagerungsprodukte von Alkoholen mit 6 bis 22 Kohlenstoffatomen an Ethylenoxid und Propylenoxid, wobei diese Ethylenoxid- und Propylenoxid-Einheiten in Form von Blöcken vorliegen und zumindest ein Teil, vorzugsweise das gesamte Propylenoxid, nach Anlagerung des Ethylenoxids aufkondensiert wird. Derartige Kondensationsprodukte sind insbesondere aus ihrer Anwendung bei Waschmitteln für Textilien bekannt, beispielsweise aus der DE-B-11 35122. Sie entsprechen der allgemeinen Formel
    Figure imgb0006
    darin bedeuten
    • R' einen Alkylrest mit 6 bis 22 C-Atomen, vorzugsweise mit 7 bis 18 C-Atomen,
    • a einen statistischen Mittelwert im Bereich von 2 bis 10, vorzugsweise 3 bis 8,
    • b einen statistischen Mittelwert im Bereich von 1 bis 8, vorzugsweise 3 bis 5.
The non-ionic surfactants A) used as a component are known. It's about
  • A 1 ) adducts of alcohols having 6 to 22 carbon atoms with ethylene oxide and propylene oxide, these ethylene oxide and propylene oxide units being in the form of blocks and at least some, preferably all, of the propylene oxide being condensed after the ethylene oxide has been added on. Such condensation products are known in particular from their use in detergents for textiles, for example from DE-B-11 35122. They correspond to the general formula
    Figure imgb0006
     mean in it
    • R 'is an alkyl radical having 6 to 22 carbon atoms, preferably having 7 to 18 carbon atoms,
    • a a statistical mean in the range from 2 to 10, preferably 3 to 8,
    • b a statistical mean in the range from 1 to 8, preferably 3 to 5.

Ein solcher Mittelwert kann eine ganze oder eine gebrochene Zahl sein. Vorzugsweise soll das verhältnis der Ethylenoxid- zu Propylenoxid-Einheiten im Bereich von 0,8 bis 2 liegen.Such an average can be an integer or a fraction. The ratio of the ethylene oxide to propylene oxide units should preferably be in the range from 0.8 to 2.

Es handelt sich ferner um

  • A2) Polyglykoletherformale der allgemeinen Formel
    Figure imgb0007
    diese Formale enthalten Ethylenoxid-Einheiten und gegebenenfalls Propylenoxid-Einheiten, wobei beim Vorliegen beider diese statistisch verteilt oder in Blöcken eingebaut sein können. Solche Polyglykoletherformale können hergestellt werden, beispielsweise aus den entsprechenden Polyglykolethern und Formaldehyd, wie in der DE-A-25 23 588 beschrieben ist. In der genannten Formel bedeuten R1 einen Alkylrest mit 6 bis 22 C-Atomen, vorzugsweise mit 8 bis 18 C-Atomen, R2 einen Alkylrest mit 1 bis 6 C-Atomen, bevorzugt den n-Butylrest, c einen statistischen Mittelwert im Bereich von 5 bis 20, vorzugsweise von 6 bis 14, und d einen statistischen Mittelwert im Bereich von 0 bis 3, vorzugsweise 0.
It is also about
  • A 2 ) Polyglycol ether formals of the general formula
    Figure imgb0007
     these formals contain ethylene oxide units and, if appropriate, propylene oxide units, it being possible for these to be statistically distributed or incorporated in blocks if both are present. Such polyglycol ether formals can be prepared, for example from the corresponding polyglycol ethers and formaldehyde, as described in DE-A-25 23 588. In the formula mentioned, R 1 is an alkyl radical with 6 to 22 C atoms, preferably with 8 to 18 C atoms, R 2 is an alkyl radical with 1 to 6 C atoms, preferably the n-butyl radical, c is a statistical mean in the range from 5 to 20, preferably from 6 to 14, and d has a statistical mean in the range from 0 to 3, preferably 0.

Schließlich kann die nicht-ionische KomponenteFinally, the non-ionic component

A3) auch ein Polyalkylenglykoldialkylether der Formel

Figure imgb0008
sein, der Ethylenoxid- und gegebenenfalls Propylenoxid-Einheiten enthält, die statistisch oder in Blöcken angeordnet sein können. In dieser Formel bedeuten R1 einen Alkylrest mit 6 bis 22 C-Atomen, vorzugsweise mit 8 bis 18 C-Atomen, R3 einen Alkylrest mit 1 bis 4 C-Atomen, vorzugsweise den tert.-Butylrest, c einen statistischen Mittelwert im Bereich von 5 bis 20, vorzugsweise von 6 bis 14, und d einen statistischen Mittelwert im Bereich von 0 bis 3, vorzugsweise 0.A 3 ) also a polyalkylene glycol dialkyl ether of the formula
Figure imgb0008
 be, which contains ethylene oxide and optionally propylene oxide units, which can be arranged randomly or in blocks. In this formula, R 1 is an alkyl radical with 6 to 22 carbon atoms, preferably with 8 to 18 carbon atoms, R 3 is an alkyl radical with 1 to 4 carbon atoms, preferably the tert-butyl radical, c is a statistical mean in the range from 5 to 20, preferably from 6 to 14, and d has a statistical mean in the range from 0 to 3, preferably 0.

Die vorgenannten nicht-ionischen Tenside können auch als Gemische innerhalb der Gruppen A1), A2) oder A3) oder aber auch zwischen den Gruppen A1), A2) und/oder A3) vorliegen. Bevorzugt sind die nicht-ionischen Tenside der Gruppe A1).The aforementioned non-ionic surfactants can also be present as mixtures within groups A 1 ), A 2 ) or A 3 ) or else between groups A 1 ), A 2 ) and / or A 3 ). The non-ionic surfactants of group A 1 ) are preferred.

Als kationische Komponente enthält das Tensidgemisch eine quaternäre Ammoniumverbindung B der Formel

Figure imgb0009
in der R4 und R5, gleich oder verschieden, einen Alkylrest mit 1 bis 12 C-Atomen, vorzugsweise mit 4 bis 8 C-Atomen, insbesondere mit 4 bis 6 C-Atomen, R6 einen Alkylrest mit 1 bis 8 C-Atomen, vorzugsweise 1 bis 6 C-Atomen, sowie R7 einen Alkylrest mit 1 bis 4 C-Atomen oder einen Benzylrest, bedeuten. A ist ein Anion, vorzugsweise ein Chlorid- oder Bromidanion oder ein solches der Formel CH30S03-.The surfactant mixture contains a quaternary ammonium compound B of the formula as a cationic component
Figure imgb0009
 in which R 4 and R 5 , identical or different, are an alkyl radical with 1 to 12 C atoms, preferably with 4 to 8 C atoms, in particular with 4 to 6 C atoms, R 6 is an alkyl radical with 1 to 8 C atoms Atoms, preferably 1 to 6 carbon atoms, and R 7 is an alkyl radical with 1 to 4 carbon atoms or a benzyl radical. A is an anion, preferably a chloride or bromide anion or one of the formula CH 3 0S0 3 -.

Die im erfindungsgemäßen tensidhaltigen Gemisch als Antischaummittel eingesetzten fluorierten Alkohole der Formel

Figure imgb0010
worin Rf ein CF3- oder (CF3)2-CF-Rest, R8 ein niederer Alkylrest, R9 Wasserstoff oder ein niederer Alkylrest (wobei unter einem niederen Alkylrest hier ein solcher mit 1 bis 3 C-Atomen, vorzugsweise ein Methyl- oder Ethylrest verstanden werden soll), e eine ganze Zahl von 5 bis 15, f eine ganze Zahl von 0 bis 4 ist und g für f = 1 bis 4 den Wert 0 und für f = 0 den Wert 1 annimmt, sind an sich bekannte Substanzen. Ihre Herstellung kann erfolgen, wie beispielsweise beschrieben in der US-A-3 171 861. in der DE-C-20 28 459, in der DE-C-12 14660, in der FR-A-14 38 617, in der EP-A-8096 sowie in J. Chem. Soc. 1953. Seite 1748 ff. und in J. Am. Chem. Soc. 79 (1957), Seite 335 ff.The fluorinated alcohols of the formula used as anti-foaming agents in the surfactant-containing mixture according to the invention
Figure imgb0010
 wherein Rf is a CF 3 - or (CF 3 ) 2 -CF radical, R 8 is a lower alkyl radical, R 9 is hydrogen or a lower alkyl radical (with a lower alkyl radical here being one with 1 to 3 carbon atoms, preferably a methyl - or ethyl radical should be understood), e is an integer from 5 to 15, f is an integer from 0 to 4 and g assumes the value 0 for f = 1 to 4 and the value 1 for f = 0 are in themselves known substances. They can be prepared as described, for example, in US Pat. No. 3,171,861, in DE-C-20 28 459, in DE-C-12 14660, in FR-A-14 38 617, in the EP -A-8096 and in J. Chem. Soc. 1953. page 1748 ff. And in J. Am. Chem. Soc. 79 (1957), page 335 ff.

Von den im erfindungsgemäßen tensidischen Gemisch eingesetzten fluorierten Alkoholen sind bevorzugt diejenigen zu nennen, bei denen in der obengenannten Formel Rf = CF3, e = 5 bis 13 und g = 0 ist, wobei f die Werte 1 bis 4, insbesondere den Wert 2, annimmt. Von der Herstellung her sind insbesondere diejenigen fluorierten Alkohole bevorzugt, in denen Rf = CF3 ist und e ungeradzahlige Werte, also 5, 7, 9, 11 und 13 annimmt.Of the fluorinated alcohols used in the surfactant mixture according to the invention, preference should be given to those in which Rf = CF 3 , e = 5 to 13 and g = 0 in the above formula, where f is from 1 to 4, in particular from 2, assumes. From the point of view of manufacture, those fluorinated alcohols are particularly preferred in which Rf = CF 3 and e takes on odd values, ie 5, 7, 9, 11 and 13.

Die Zusammensetzung der tensidischen Gemische ist von wesentlicher Bedeutung für die vorteilhaften Eigenschaften. Um die erforderliche optimale Kombination von Schmutzaufnahmevermögen. geringstmöglicher Schaumneigung und Nicht-Substantivität zu erzielen, soll das Verhältnis der Komponenten A : B im Gemisch A + B im Bereich von 20 : 80 bis 95 : 5 Gew.-%, vorzugsweise 30 : 70 bis 70 : 30 Gew.-%. liegen. Bezogen auf die Gewichtssumme der Komponenten A + B = 100 ist zusätzlich der fluorierte Alkohol C) als Antischaummittel in einer Menge von 0,001 bis 20 Gew.-%, vorzugsweise von 0.1 bis 15Gew.-% im erfindungsgemäßen Gemisch anwesend. Solche fluorierten Alkohole stellen bei Raumtemperatur feste, wachsartige Substanzen dar. Sie können in Substanz dem Gemisch der Komponenten A + B oder dessen Einzelkomponenten zugesetzt werden, zweckmäßig unter gelindem Erwärmen und Rühren. Vorteilhafterweise werden diese fluorierten Alkohole aber im Gemisch mit einem Lösungsvermittler eingebracht, in dem sie vorgelöst worden sind. Die gilt vor allem dann, wenn sehr kleine Mengen des fluorierten Alkohols zum Einsatz gelangen sollen. Ein geeigneter Lösungsvermittler muß mit dem Tensid-Gemisch A + B oder dessen Einselkomponenten vollständig oder zumindest weitgehend homogen mischbar sein. Ebenso soll der fluorierte Alkohol C) in diesem Lösungsvermittler weitgehend oder gänzlich löslich sein. Eine effektive Menge eines solchen Lösungsvermittlers liegt vorzugsweise bei 1 bis 1 000 Gew.-Teilen pro 1 Gew.-Teil des fluorierten Alkohols ; diese effektive Menge soll jedoch 20 Gew.-% der Gewichtssumme der Komponenten A + B nicht übersteigen.The composition of the surfactant mixtures is essential for the advantageous properties. To the required optimal combination of dirt absorption capacity. To achieve the lowest possible foam tendency and non-substantivity, the ratio of components A: B in the mixture A + B should be in the range from 20:80 to 95: 5% by weight, preferably 30:70 to 70:30% by weight. lie. Based on the total weight of components A + B = 100, the fluorinated alcohol C) is additionally present as an antifoam in an amount of 0.001 to 20% by weight, preferably 0.1 to 15% by weight, in the mixture according to the invention. Such fluorinated alcohols are solid, wax-like substances at room temperature. They can be added in bulk to the mixture of components A + B or its individual components, expediently with gentle heating and stirring. However, these fluorinated alcohols are advantageously introduced in a mixture with a solubilizer in which they have been predissolved. This is especially true when very small amounts of the fluorinated alcohol are to be used. A suitable solubilizer must be completely or at least largely homogeneously miscible with the surfactant mixture A + B or its single components. Likewise, the fluorinated alcohol C) should be largely or entirely soluble in this solubilizer. An effective amount of such a solubilizer is preferably 1 to 1,000 parts by weight per 1 part by weight of the fluorinated alcohol; however, this effective amount should not exceed 20% by weight of the total weight of components A + B.

Beispiele für solche Lösungsvermittler sind aliphatische Ketone, wie Dimethyl- und Diethylketon. Carbonsäureester aliphatischer Alkohole und Diole, wie Essisäureethylester, -isobutylester, Ethylenglykolacetat, 2-Ethylhexyl-2-ethylhexansäureester, Säureamide längerkettiger Carbonsäuren, wie beispielsweise N-(2-Ethylhexyl)-isononansäureamid, Polypropylenglykole mit Molgewichten > 600 und Mischpolyglykole aus Einheiten von Ethylen- und Propylenoxid, Ethylen- und Propylenglykolmonoether sowie die entsprechenden Polyglykolether, wie Methyl-, Ethyl- und Butylmonoether des Di-, Tri- und Tetraethylenglykols. Vorzugsweise sind Alkanole mit 1 bis 9 C-Atomen in gerader oder verzweigter Kette zu nennen. Soweit miteinander mischbar, sind auch Gemische solcher Lösungsvermittler geeignet.Examples of such solubilizers are aliphatic ketones, such as dimethyl and diethyl ketone. Carboxylic acid esters of aliphatic alcohols and diols, such as ethyl acetate, isobutyl ester, ethylene glycol acetate, 2-ethylhexyl-2-ethylhexanoic acid ester, acid amides of longer-chain carboxylic acids, such as, for example, N- (2-ethylhexyl) -isononanoic acid amide, polypropylene glycols with molar weights of> 600 and mixed units of molecular weights> 600 and propylene oxide, ethylene and propylene glycol monoethers and the corresponding polyglycol ethers, such as methyl, ethyl and butyl monoethers of di, tri and tetraethylene glycol. Alkanols with 1 to 9 carbon atoms in a straight or branched chain should preferably be mentioned. As far as miscible with one another, mixtures of such solubilizers are also suitable.

Die erfindungsgemäßen tensidhaltigen Gemische können als Gemisch der Komponenten A + B + C. gegebenenfalls unter Einschluß des Lösungsvermittlers in unverdünnter, flüssiger Form eingesetzt werden. Sie Können aber auch, beispielsweise zwecks besserer Dosierbarkeit, in Form wäßriger Konzentrate Verwendung finden, gegebenenfalls auch unter Zusatz eines organischen Lösungsmittels. das kein Lösungsvermittler im obengenannten Sinne ist. Ebenso können auch zunächst die Komponenten A und B einzeln oder zusammen der wäßrigen Reinigungsflotte zugegeben und der fluorierte Alkohol C nachdosiert werden, wobei hier ein Lösungsvermittler zugegen sein muß. Es kann aber auch die Komponente C mit einer der beiden Komponenten A oder B vorgemischt eingebracht werden, wobei die jeweils andere nachdosiert wird.The surfactant-containing mixtures according to the invention can be used as a mixture of components A + B + C., optionally including the solubilizer, in undiluted, liquid form. However, they can also be used in the form of aqueous concentrates, for example for better meterability, if appropriate also with the addition of an organic solvent. that is not a solution broker in the above sense. Likewise, components A and B can also first be added individually or together to the aqueous cleaning liquor and the fluorinated alcohol C can be metered in, in which case a solubilizer must be present. However, component C can also be introduced premixed with one of the two components A or B, the other being subsequently metered in.

Die Anwendungskonzentration liegt zweckmäßigerweise bei 0,05 bis 10 g des Tensidgemisches A + B (ohne Einschluß von C) pro Liter Reinigungsflotte, vorzugsweise bei 0,1 bis 2 g pro Liter. Solche Anwendungskonzentrationen sind nicht-kritische Angaben, da sich die Menge in gewissem Ausmaß nach der Art der zu reinigenden Oberfläche und nach Art und Umfang der Verunreinigungen richtet.The application concentration is advantageously 0.05 to 10 g of the surfactant mixture A + B (without inclusion of C) per liter of cleaning liquor, preferably 0.1 to 2 g per liter. Such application concentrations are non-critical statements, since the amount depends to a certain extent on the type of surface to be cleaned and on the type and extent of the contaminants.

Der erfindungsgemäßen tensidischen Gemischen können gegebenenfalls bei der Herstellung handelsüblicher Formulierungen weitere Zusatz- und Hilfsstoffe beigegeben werden. Dies sind beispielsweise Farbstoffe, Duftstoffe, Korrosionsinhibitoren und Desinfektionsmittel. Insbesondere sind hier ferner zu nennen die bekannten Gerüststoffe, die gegebenenfalls gleichzeitig Komplexbildner sind. Hier kommen beispielsweise in Betracht die kondensierten Phosphate, wie Tripolyphosphate und insbesondere das Pentanatriumtriphosphat. Ferner sind dies komplexbildend wirkende Aminopolycarbonsäuren und deren Salze, wie vor allem Alkalisalze der Nitrilotriessigsäure und der Ethylendiamintetraessigsäure, weiterhin auch komplexbildende Hydroxycarbonsäuren und polymere Carbonsäuren, wie Zitronensäure, Weinsäure und dergleichen. Eine weitere Klasse von komplexbildenden Gerüststoffen stellen polyphosphonsaure Salze, wie beispielsweise die Alkalisalze von Aminophosphonsäure dar. Schließlich können auch Gerüststoffe, wie Silikate, beispielsweise Natriummetasilikat, Carbonate, Bicarbonate, Borate und Citrate hinzugefügt werden. Mit Hilfe solcher Zusatzstoffe können die erfindungsgemäßen Gemische gegebenenfalls in Pulverform überführt werden und in dieser Form auch zum Einsatz gelangen.The surfactant mixtures according to the invention can optionally be used in the preparation commercially available formulations further additives and auxiliaries are added. These include dyes, fragrances, corrosion inhibitors and disinfectants. In particular, the known builders, which are optionally also complexing agents, should also be mentioned here. Here, for example, the condensed phosphates, such as tripolyphosphates and in particular pentasodium triphosphate, come into consideration. Furthermore, these are complex-forming aminopolycarboxylic acids and their salts, such as, in particular, alkali metal salts of nitrilotriacetic acid and ethylenediaminetetraacetic acid, and also also complex-forming hydroxycarboxylic acids and polymeric carboxylic acids, such as citric acid, tartaric acid and the like. Another class of complexing builders are polyphosphonic salts, such as the alkali salts of aminophosphonic acid. Finally, builders, such as silicates, for example sodium metasilicate, carbonates, bicarbonates, borates and citrates, can also be added. With the aid of such additives, the mixtures according to the invention can optionally be converted into powder form and can also be used in this form.

Die erfindungsgemäßen tensidhaltigen Gemische sind geeignet zur maschinellen Reinigung harter Oberflächen in alkalischen Flotten. Dies gilt für die Reinigung in Haushaltsgeschirrspülmaschinen und sogenannten gewerblichen Reinigungsanlagen. Die Gemische sind aber besonders geeignet für industrielle Reinigungsanlagen für harte Oberflächen, beispielsweise Geschirr- und Flaschenspülanlagen, die unter hohen mechanischen Flottenbewegungen im Dauerbetrieb und in hochalkalischen Flotten bei pH-Werten von 2-t 10, vorzugsweise 2-e 12, arbeiten.The surfactant-containing mixtures according to the invention are suitable for the mechanical cleaning of hard surfaces in alkaline liquors. This applies to cleaning in household dishwashers and so-called commercial cleaning systems. However, the mixtures are particularly suitable for industrial cleaning systems for hard surfaces, for example dishwashing and bottle washing systems, which operate under high mechanical liquor movements in continuous operation and in highly alkaline liquors at pH values of 2-t 10, preferably 2-e 12.

Die erforderlichen alkalischen Zusätze, für den hochalkalischen pH-bereich der Flotte vorzugsweise Natrium- oder Kaliumhydroxid, können in der wäßrigen Reinigungsflotte vor Einbringen des erfindungsgemäßen tensidhaltigen Gemisches gelöst werden. Sie können aber auch dem Gemisch direkt zugesetzt und zusammen mit diesem dosiert werden. Zweckmäßig erfolgt der Zusatz des alkalischen Mittels in Form von Pulver, Schuppen oder Plätzchen.The necessary alkaline additives, preferably sodium or potassium hydroxide for the highly alkaline pH range of the liquor, can be dissolved in the aqueous cleaning liquor before the surfactant-containing mixture according to the invention is introduced. However, they can also be added directly to the mixture and metered together with it. The alkaline agent is expediently added in the form of powder, flakes or cookies.

Neben der hierfür erforderlichen hohen Alkalistabilität weisen die erfindungsgemäßen Gemische eine für industrielle Reinigungsanlagen unerläßliche, extrem niedrige Schaumbildungstendenz auf. Dabei ist es von wesentlicher Bedeutung, daß auch der als Antischaummittel eingesetzte fluorierte Alkohol C im hochalkalischen bereich absolut stabil ist. Durch dessen Zusatz wird erreicht, daß auch bei extrem hohen mechanischen Flottenbewegungen, wie sie beispielsweise in den Flaschenreinigungsanlagen von Brauereien auftreten, praktisch keine Schaumbildung stattfindet. Auch bei stark bis extrem schaumfördernden Verschmutzungen, wie beispielsweise bei Eiweiß, Milch, Bier, Limonade sowie Leim und tensidischen Bestandteilen aus Etiketten, wird die Schaumbildungstendenz auf ein Minimum herabgesetzt. Die tensidhaltigen Gemische besitzen diese außerordentlich niedrige Schaumbildungstendenz nicht nur bei den Arbeitstemperaturen solcher Reinigungsanlagen, das heißt oberhalb von etwa 40 °C, sondern auch bei niedrigen Temperaturen, so daß bei Neubefüllung mit kaltem Wasser und Aufheizen keine Bildung von störendem Schaum erfolgt, der dann zum Überschäumen oder zu Störungen der Zirkulation der Anlage führen kann.In addition to the high alkali stability required for this, the mixtures according to the invention have an extremely low tendency towards foaming which is indispensable for industrial cleaning systems. It is essential that the fluorinated alcohol C used as an anti-foaming agent is absolutely stable in the highly alkaline range. By adding it it is achieved that even with extremely high mechanical liquor movements, such as occur, for example, in the bottle cleaning systems of breweries, there is practically no foam formation. The tendency towards foaming is also reduced to a minimum, even with heavily to extremely foam-promoting soiling, such as protein, milk, beer, lemonade, glue and surfactant components from labels. The surfactant-containing mixtures have this extraordinarily low tendency to foam formation not only at the working temperatures of such cleaning systems, that is above about 40 ° C, but also at low temperatures, so that when refilled with cold water and heating, no disruptive foam is formed, which then leads to Overflowing or disturbing the circulation of the system.

Neben den bereits genannten Vorteilen weisen die erfindungsgemäßen tensidischen Gemische-als Reinigungsmittel für die maschinelle Reinigung harter Oberflächen, insbesondere bezüglich der hohen Anforderungen, die in industriellen Reinigungsanlagen gestellt werden, noch folgende bedeutsamen Vorteile auf : Die Gemische sind nicht nur beständig gegen Alkali, sondern auch zusammen mit Alkali über lange Zeiträume lagerstabil. Das ausgezeichnete Schmutzaufnahmevermögen gestattet lange Standzeiten in der Anlage bis zu deren Neubefüllung ohne Beeinträchtigung der Reinigungswirkung. Gutes Netzvermögen und Ablaufverhalten ermöglicht eine schnelle Schmutzablösung und somit einen hohen Durchsatz an Reinigungsgut. Ebenso ist die Freiheit von Flecken und Schlieren sowie hoher Glanz des gereinigten Gutes gewährleistet. Dies macht die erfindungsgemäßen Gemische beispielsweise außerordentlich geeignet zur Reinigung von Flaschen in Brauereien mit sehr hohem Flaschendurchsatz, wobei wegen der weitgehenden Schaumfreiheit ein problemloser Austrag der abgelösten Etiketten möglich ist und außerdem festgestellt wird, daß bei Befüllung der gereinigten Flaschen mit schäumenden Getränken keine Beeinträchtigung durch Schaumzusammenbruch eintritt.In addition to the advantages already mentioned, the surfactant mixtures according to the invention — as cleaning agents for the mechanical cleaning of hard surfaces, in particular with regard to the high demands placed on industrial cleaning systems, also have the following significant advantages: the mixtures are not only resistant to alkali, but also long-term storage stability with alkali. The excellent dirt absorption capacity allows long service life in the system until it is refilled without impairing the cleaning effect. Good wetting capacity and drainage behavior enable dirt to be removed quickly and thus a high throughput of items to be cleaned. The freedom from stains and streaks as well as high gloss of the cleaned goods is also guaranteed. This makes the mixtures according to the invention, for example, extremely suitable for cleaning bottles in breweries with a very high bottle throughput, with the detached labels being able to be easily removed because of the largely lack of foam and, moreover, it is found that when the cleaned bottles are filled with foaming drinks, there is no impairment due to foam breakdown entry.

Unter « Gegenständen mit harter Oberfläche im Sinne des Anwendungszwecks der erfindungsgemäßen tensidhaltigen Gemische sollen hier vornehmlich verstanden werden alle Arten von Geschirr und Flaschen aus Glas, Porzellan, Keramik und Kunststoff sowie auch andere Gegenstände aus den genannten Materialien oder auch aus Metallen.“Objects with a hard surface in the sense of the intended use of the surfactant-containing mixtures according to the invention are to be understood here primarily as all types of dishes and bottles made of glass, porcelain, ceramics and plastics as well as other objects made from the materials mentioned or from metals.

Die Erfindung wird durch folgende Beispiele erläutert :

  • In den in den folgenden Beispielen eingesetzten Tensidgemischen sind folgende Komponenten enthalten (C7-11 etc. bedeutet Kettenschnitt R1 im genannten Bereich) ;
    • Nicht-ionische tenside der Formel A') :
      Figure imgb0011
      Figure imgb0012
      Figure imgb0013
      Figure imgb0014
    • Nicht-ionische tenside der Formel A2) :
      Figure imgb0015
    • Nicht-ionische Tenside der Formel A3) :
      Figure imgb0016
      Figure imgb0017
    • Kationische Tenside der Formel B) :
      • h) Trimethylbenzylammoniumchlorid
      • i) Tetrabutylammoniumchlorid
      • j) Dibutyldimethylammoniumchlorid
      • k) Dihexyldimethylammoniumchlorid
      • I) Dioctyldimethylammoniumchlorid
    • Fluorierte Alkohole der Formel C) :
      Figure imgb0018
      Figure imgb0019
      Figure imgb0020
      Figure imgb0021
      Figure imgb0022
      (Mischung C―5/7/9/11=4:3:2:1)
The invention is illustrated by the following examples:
  • In those used in the following examples, surfactant mixtures containing the following components (C 7-11 means etc. chain sectional R 1 range specified);
    • Non-ionic surfactants of the formula A '):
      Figure imgb0011
      Figure imgb0012
      Figure imgb0013
      Figure imgb0014
    • Non-ionic surfactants of the formula A 2 ):
      Figure imgb0015
    • Non-ionic surfactants of formula A 3 ):
      Figure imgb0016
      Figure imgb0017
    • Cationic surfactants of formula B):
      • h) trimethylbenzylammonium chloride
      • i) Tetrabutylammonium chloride
      • j) dibutyldimethylammonium chloride
      • k) Dihexyldimethylammonium chloride
      • I) dioctyldimethylammonium chloride
    • Fluorinated alcohols of formula C):
      Figure imgb0018
      Figure imgb0019
      Figure imgb0020
      Figure imgb0021
      Figure imgb0022
       (Mixture C― 5/7/9/11 = 4: 3: 2: 1)

An den genannten Gemischen werden folgende Eigenschaften gemessen (alle Messungen wurden an Reinigungsflotten durchgeführt, die, mit Ausnahme der pulverförmigen Formulierungen, mit NaOH auf einen pH-Wert von 13 eingestellt sind) :

  • a) Schaumverhalten der Tensidmischung :
    • Gemessen wird in wäßriger Lösung nach DIN-Norm 53902 bei 25 °C und 65 °C.
  • β) Schaumverhalten mit 10 Gew.-% Belastung durch Bier :
    • Gemessen wird in einer wäßrigen Reinigungsflotte, die 10 Gew.-% Weizenbier enthält (Export-Weizen der Klosterbrauerei Raitenhaslach-Burghausen) bei 65 °C nach DIN-Norm 53 902.
  • γ) Ermittlung der Schumtzaufnahmegrenze :
The following properties are measured on the mixtures mentioned (all measurements were carried out on cleaning liquors which, with the exception of the powdery formulations, are adjusted to a pH of 13 with NaOH):
  • a) Foaming behavior of the surfactant mixture:
    • Measurements are carried out in aqueous solution according to DIN standard 53902 at 25 ° C and 65 ° C.
  • β) Foam behavior with 10% by weight of beer:
    • Measurements are taken in an aqueous cleaning liquor containing 10% by weight of wheat beer (export wheat from the Raitenhaslach-Burghausen monastery brewery) at 65 ° C according to DIN standard 53 902.
  • γ) Determination of the Schumtz absorption limit:

Die Schmutzaufnahmegrenze durch Prüfung des Schaumvermögens bei steigender Schmutzbelastung wird ermittelt, indem die Reinigungsflotte stufenweise mit einem Testschäumer versetzt wird. Als Testschäumer wird ein verquirltes Ei verwendet, das in Portionen von 0,2 g/I Flotte zugegeben wird. Bei der Schaumprüfung nach DIN-Norm 53902 ist die Schmutzaufnahmegrenze erkennbar an einem plötzlichen Schaumanstieg der Reinigungsflotte. Als Schaumobergrenze wird 30 ml (bei 65 °C) gewählt.The dirt absorption limit by checking the foaming capacity with increasing dirt load is determined by gradually adding a test foamer to the cleaning liquor. A whisked egg is used as the test frother, which is added in portions of 0.2 g / l of liquor. In the foam test according to DIN standard 53902, the dirt absorption limit is recognizable by a sudden foam increase in the cleaning liquor. 30 ml (at 65 ° C) is selected as the upper foam limit.

δ) Prüfung des Ablaufverhaltens in gereinigten Flaschenδ) Checking the drainage behavior in cleaned bottles

Saubere 0.5 I-Bierflaschen werden mit 100 ml der Reinigungsflotte gefüllt und nach Verschließen n einem Korkstopfen fünfmal kräftig geschüttelt. Nach kurzer Wirkzeit (ca. 1 Minute) wird erneut fünfrr der Schüttelvorgang wiederholt und dann die tensidhaltige Reinigungsflotte ausgegossen. Es folgt vie bis fünfmal hintereinander Nachspülung mit jeweils 100 ml destilliertem Wasser, bis pH 7 erreicht isClean 0.5 liter beer bottles are filled with 100 ml of the cleaning liquor and, after being closed, shaken vigorously five times in a cork stopper. After a short period of action (approx. 1 minute), the shaking process is repeated again for five and the detergent-containing cleaning liquor is then poured out. This is followed by rinsing four to five times in succession with 100 ml of distilled water until pH 7 is reached

Visuelle Beobachtung des Ablaufverhaltens an der Flascheninnenwandung :

  • Tropfenbildung deutet auf Substantivität an den Flaschenwandungen hin.
Visual observation of the drainage behavior on the inside of the bottle:
  • Drop formation indicates substantivity on the bottle walls.

Beispiele 1 bis 3Examples 1 to 3

Ermittlung des Schaumvolumens in ml nach DIN-Norm 53 902 bei verschiedenen Zusätzen fluorierten Alkoholen (Komponenten m bis q) in Gew.-% (bezogen auf die Summe nichtioniscl + kationische Bestandteile A + B = 100 %).Determination of the foam volume in ml according to DIN standard 53 902 with various additions of fluorinated alcohols (components m to q) in% by weight (based on the sum of non-ionic + cationic components A + B = 100%).

Beispiel 1example 1

Mischung aus 50 Gew.-% Komponente f und 50 Gew.-% Komponente k ; 1,5 g/I wäßrige Flotte

Figure imgb0023
Mixture of 50 wt .-% component f and 50 wt .-% component k; 1.5 g / l aqueous liquor
Figure imgb0023

Beispiel 2Example 2

Mischung aus 30 Gew.-% Komponente d und 70 Gew.-% Komponente j ; 1,5 g/l wäßrige Flotte.

Figure imgb0024
Mixture of 30% by weight of component d and 70% by weight of component j; 1.5 g / l aqueous liquor.
Figure imgb0024

Beispiel 3Example 3

Mischung aus 60 Gew.-% Komponente e und 40 Gew.-% Komponente 1 ; 1,5 g/l wäßrige Flotte.

Figure imgb0025
Figure imgb0026
 Mixture of 60% by weight of component e and 40% by weight of component 1; 1.5 g / l aqueous liquor.
Figure imgb0025
Figure imgb0026

Beispiel 4Example 4

Pulverförmiger Spritzreiniger :

  • 5 Gew.-% tensidhaltiges Gemisch aus 34 Gew.-Teilen Komponente g, 66 Gew.-Teilen Komponente k und 1 Gew.-Teil Komponente n ;
Powdery spray cleaner:
  • 5% by weight surfactant-containing mixture of 34 parts by weight of component g, 66 parts by weight of component k and 1 part by weight of component n;

Gerüst- und Hilfsstoffe : 65 Gew.-% Natriummetasilikat, 20 Gew.-% Natriumhydroxid (pulverisiert), 10 Gew.-% Natriumcarbonat.Builders and auxiliaries: 65% by weight sodium metasilicate, 20% by weight sodium hydroxide (powdered), 10% by weight sodium carbonate.

Zunächst werden die Tensid-Komponenten miteinander vermischt und dann der fluorierte Alkohol bei 30 bis 40 °C eingerührt. Die Gerüst- und Hilfsstoffe werden in eine Mischtrommel gegeben und dort mit der Tensid-Mischung gut vermischt.First the surfactant components are mixed together and then the fluorinated alcohol is stirred in at 30 to 40 ° C. The framework and auxiliary materials are placed in a mixing drum, where they are mixed well with the surfactant mixture.

Gemessen wird an einer Reinigungsflotte mit 20 g/I der Gesamtformulierung (= 1 g/l Tensidgemisch A + B) in vollentsalztem Wasser, pH 12,8.

  • Eigenschaum bei 25 °C (nach DIN-Norm 53902): 10 ml
  • Eigenschaum bei 65 °C (nach DIN-Norm 53 902) : 0 ml
  • Ablaufverhalten nach dem Klarspülen mit Wasser : keine Tropfenbildung.
Measurement is carried out on a cleaning liquor with 20 g / l of the total formulation (= 1 g / l of surfactant mixture A + B) in demineralized water, pH 12.8.
  • Own foam at 25 ° C (according to DIN standard 53902): 10 ml
  • Own foam at 65 ° C (according to DIN standard 53 902): 0 ml
  • Drainage behavior after rinsing with water: no drop formation.

Beispiel 5Example 5 Pulverförmiger FlaschenreinigerPowdered bottle cleaner

10 Gew: % tensidhaltiges Gemisch aus 78 Gew.-Teilen Komponente a, 22 Gew.-Teilen Komponente i und 11 Gew.- Teilen Komponente q ;10 wt:% surfactant-containing mixture of 78 parts by weight of component a, 22 parts by weight of component i and 11 parts by weight of component q;

Gerüst- und Hilfsstoffe : 25 Gew.-% Pentanatriumtriphosphat, 25 Gew.-% Natriummetasilikat, 25 Gew.- % Natriumcarbonat und 15 Gew: % Natriumhydroxid (pulverisiert).Builders and auxiliaries: 25% by weight of pentasodium triphosphate, 25% by weight of sodium metasilicate, 25% by weight of sodium carbonate and 15% by weight of sodium hydroxide (powdered).

Zunächst werden die Komponenten des tensidhaltigen Gemisches gemischt und anschließend mit den bereits vermengten Gerüst- und Hilfsstoffen innig zum Pulver vermischt.First, the components of the surfactant-containing mixture are mixed and then intimately mixed with the framework and auxiliary substances that have already been mixed to form the powder.

Gemessen wird an einer Reinigungsflotte mit 5 g/I der Gesamtformulierung (=0,45 g/I Tensidgemisch A + B) in vollentsalztem Wasser, pH 12,4.

  • Eigenschaum bei 25 °C (Nach DIN-Norm 53 902) : 20 ml
  • Eigenschaum bei 65 °C (nach DIN-Norm 53 902) : 0 ml
  • Schaum bei 65 °C (Nach DIN-Norm 53 902) mit Belastung durch 10 Gew.-% Bier: 0 ml
  • Maximale Eiweißbelastung (bis 30 ml Schaum) : 7,2 g/I Ablaufverhalten nach dem Klarspülen mit Wasser : keine Tropfenbildung.
Measurement is carried out on a cleaning liquor with 5 g / l of the total formulation (= 0.45 g / l of surfactant mixture A + B) in demineralized water, pH 12.4.
  • Own foam at 25 ° C (according to DIN standard 53 902): 20 ml
  • Own foam at 65 ° C (according to DIN standard 53 902): 0 ml
  • Foam at 65 ° C (according to DIN standard 53 902) with a load of 10% by weight beer: 0 ml
  • Maximum protein load (up to 30 ml foam): 7.2 g / I drainage behavior after rinsing with water: no drop formation.

Beispiel 6Example 6 Pulverförmiger Geschirr-Reiniger:Powdered dishwashing detergent:

2 Gew.-% tensidhaltiges Gemisch aus 68 Gew.-Teilen Komponente b, 32 Gew :Teilen Komponente j und 5 Gew: Teilen Komponente p ;2% by weight surfactant-containing mixture of 68 parts by weight of component b, 32 parts by weight of component j and 5 parts by weight of component p;

Gerüst- und Hilfsstoffe : 41,5 Gew.-% Natriummetasilikat, 35 Gew.-% Pentanatriumtriphosphat. 20 Gew.-% Natriumcarbonat und 1,5 Gew.-% Natriumdichlorisocyanurat (als Desinfektionsmittel).Builders and auxiliaries: 41.5% by weight sodium metasilicate, 35% by weight pentasodium triphosphate. 20% by weight sodium carbonate and 1.5% by weight sodium dichloroisocyanurate (as disinfectant).

Zuerst werden die pulverförmigen Komponenten vermischt. In dieses Gemisch wird die tensidhaltige Formulierung eingearbeitet, welche zuvor miteinander in der Reihenfolge der Komponenten vorgemischt worden ist.First the powdery components are mixed. The surfactant-containing formulation which has been premixed with one another in the order of the components is incorporated into this mixture.

Gemessen wird an einer Reinigungsflotte mit 50 g/I Gesamtformulierung ( = 0,95 g/I Tensidgemisch A + B) in vollentsalzten Wasser, pH 12,8.

  • Eigenschaum bei 25 °C (nach DIN-Norm 53 902) : 10 ml
  • Eigenschaum bei 65 °C (nach DIN-Norm 53 902) : 0 ml
  • Maximale Eiweißbelastung (bis 30 ml Schaum) : 17,5 g/I Ablaufverhalten nach dem Klarspülen mit Wasser : keine Tropfenbildung.
Measurement is carried out on a cleaning liquor with 50 g / l total formulation (= 0.95 g / l surfactant mixture A + B) in demineralized water, pH 12.8.
  • Own foam at 25 ° C (according to DIN standard 53 902): 10 ml
  • Own foam at 65 ° C (according to DIN standard 53 902): 0 ml
  • Maximum protein load (up to 30 ml foam): 17.5 g / I drainage behavior after rinsing with water: no drop formation.

Beispiel 7Example 7 Flüssiger Flaschen-Reiniger :Liquid bottle cleaner:

20 Gew.-% tensidhaltiges Gemisch aus 76 Gew.-Teilen Komponente c, 24 Gew.-Teilen Komponente k, 8 Gew.-Teilen Polypropylenglykol (MG 3 000) und 0,05 Gew.-Teilen Komponente o ;20% by weight surfactant-containing mixture of 76 parts by weight of component c, 24 parts by weight of component k, 8 parts by weight of polypropylene glycol (MW 3,000) and 0.05 parts by weight of component o;

Gerüst- und Hilfsstoffe : 35 Gew.-% Phosphorsäure (85 gew.-%ig), 20 Gew.-% 2-Phosphonobutan-1,2,4-tricarbonsäure und 25 Gew.-% vollentsalztes Wasser.Builders and auxiliaries: 35% by weight phosphoric acid (85% by weight), 20% by weight 2-phosphonobutane-1,2,4-tricarboxylic acid and 25% by weight deionized water.

Bei der Herstellung wird vollentsalztes Wasser vorgelegt und anschließend Phosphorsäure und 2-Phosphonobutan-1,2,4-tricarbonsäure eingerührt. Nun wird die bereits vorgemischte tensidhaltige Mischung einhomogenisiert.Deionized water is initially introduced and phosphoric acid and 2-phosphonobutane-1,2,4-tricarboxylic acid are then stirred in. Now the premixed surfactant-containing mixture is homogenized.

Gemessen wird an einer Reinigungsflotte mit 10 g/I Gesamtformulierung ( = 1,85 g/I Tensidgemisch A + B) in NaOH, pH 13.

  • Eigenschaum bei 25 °C (nach DIN-Norm 53 902) : 10 ml
  • Eigenschaum bei 65 °C (Nach DIN-Norm 53 902) : 0 ml
  • Schaum bei 65 °C (nach DIN-Norm 53 902) mit Belastung durch 10 Gew.-% Bier: 0 ml.
Measurements are taken on a cleaning liquor with 10 g / l total formulation (= 1.85 g / l surfactant mixture A + B) in NaOH, pH 13.
  • Own foam at 25 ° C (according to DIN standard 53 902): 10 ml
  • Own foam at 65 ° C (according to DIN standard 53 902): 0 ml
  • Foam at 65 ° C (according to DIN standard 53 902) with a load of 10% by weight beer: 0 ml.

Ablaufverhalten nach dem Klarspülen mit Wasser : keine Tropfenbildung.Drainage behavior after rinsing with water: no drop formation.

Beispiel 8Example 8 Flüssiger Geschirr-Reiniger:Liquid dishwashing detergent:

5 Gew.-% tensidhaltiges Gemisch aus 50 Gew.-Teilen Komponente e, 25 Gew.-Teilen Komponente 1,25 Gew.-Teilen Komponente h und 2 Gew.-Teilen Komponente m ; Gerüst- und Hilfsstoffe : 10 Gew.-% Phosphorsäure (85 gew.-%ig), 5 Gew.-% Pentanatriumtriphosphat und 80 Gew.-% vollentsalztes Wasser.5% by weight surfactant-containing mixture of 50 parts by weight of component e, 25 parts by weight of component 1.25 parts by weight of component h and 2 parts by weight of component m; Builders and auxiliaries: 10% by weight phosphoric acid (85% by weight), 5% by weight pentasodium triphosphate and 80% by weight deionized water.

Pentanatriumtriphosphat wird in vollentsalztem Wasser gelöst, anschließend werden Phosphorsäure und zum Schluß das tensidhaltige Gemisch zugegeben.Pentasodium triphosphate is dissolved in deionized water, then phosphoric acid and finally the mixture containing surfactants are added.

Gemessen wird an einer Reinigungsflotte mit 10 g/I Gesamtformulierung ( = 0,5 g/I Tensidgemisch A + B) in NaOH, pH 13.

  • Eigenschaum bei 25 °C (nach DIN-Norm 53 902) : 10 ml
  • Eigenschaum bei 65 °C (nach DIN-Norm 53902) : 0 ml
  • Maximale Eiweißbelastung (bis 30 ml Schaum) : 9,0 g/I Ablaufverhalten nach dem Klarspülen mit Wasser : keine Tropfenbildung.
Measurement is carried out on a cleaning liquor with 10 g / l total formulation (= 0.5 g / l surfactant mixture A + B) in NaOH, pH 13.
  • Own foam at 25 ° C (according to DIN standard 53 902): 10 ml
  • Own foam at 65 ° C (according to DIN standard 53902): 0 ml
  • Maximum protein load (up to 30 ml foam): 9.0 g / I drainage behavior after rinsing with water: no drop formation.

Claims (4)

1. A detergent composition for the mechanical cleaning of hard surfaces in alkaline liquors, characterised by
A) 20 to 95 % by weight, of the total weight of the mixture A + B, of a non-ionic surfactant of the formula
Figure imgb0032
Figure imgb0033
or
Figure imgb0034
or a mixture of the formulae A), Az), and/or A3), in which
R1 is an alkyl radical having 6 to 22 C atoms,
R2 is an alkyl radical having 1 to 6 C atoms,
R3 is an alkyl radical having 1 to 4 C atoms,
a is a statistical average value within the range from 2 to 10,
b is a statistical average value within the range from 1 to 8,
c is a statistical average value within the range from 5 to 20 and
d is a statistical average value within the range from 0 to 3,
and in which the ethylene oxide and propylene oxide units are present in the form of blocks and at least part of the propylene oxide has been condensed after adding the ethylene oxide, and in which the units of A2) and A3) are distributed statistically or in the form of blocks, and
B) 5 to 80 % by weight, of the total weight of the mixture A + B, of a cationic surfactant of the formula
Figure imgb0035
in which
R4 and R5 are identical or different alkyl radicals having 1 to 12 C atoms, R6 is an alkyl radical having 1 to 8 C atoms and R7 is an alkyl radical having 1 to 4 C atoms or a benzyl radical, and
A denotes an anion,
and additionally,
C) 0.001 to 20 % by weight, relative to the total weight A + B = 100, of a fluorinated alcohol of the formula
Figure imgb0036
in which
Rf is a perfluoromethyl or perfluoroisopropyl radical,
R8 is an alkyl radical having 1 to 3 C atoms,
R9 is hydrogen or an alkyl radical having 1 to 3 C atoms,
e denotes an integer from 5 to 15, f denotes an integer from 0 to 4 and
g assumes the value 0 in the case of f = 1 to 4, and assumes the value 1 in the case of f = 0.
2. A detergent composition as claimed in claim 1, characterised in that 30 to 70 % by weight of the non-ionic surfactant A) and 70 to 30 % by weight of the cationic surfactant B) are present.
3. A detergent composition as claimed in claims 1 or 2, characterised by the addition of an effective amount of an organic solubilizer to the fluorinated alcohol.
4. Use of the detergent composition as claimed in any of claims 1 to 3 in aqueous alkaline cleaning liquors having a pH value of s 10 for the mechanical cleaning of hard surfaces, particularly of bottles.
EP81110471A 1980-12-23 1981-12-16 Surfactant-containing mixture for cleaning hard surfaces Expired EP0054894B1 (en)

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DE3048641A1 (en) 1982-07-15
ATE8658T1 (en) 1984-08-15
JPH0225960B2 (en) 1990-06-06
DE3165128D1 (en) 1984-08-30
JPS58109599A (en) 1983-06-29
CA1160535A (en) 1984-01-17
EP0054894A1 (en) 1982-06-30
US4443364A (en) 1984-04-17

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