DE69837478T2 - Method for cleaning enamel surfaces - Google Patents

Description

The The present invention relates to a method of cleaning enamel surfaces with a liquid acidic composition.

BACKGROUND OF THE INVENTION

compositions for cleaning enamel surfaces correspond to the state of the art.

Liquid compositions with an acidic pH for cleaning enamel surfaces in the field in detail described, especially in the application of cleaners for hard surfaces (eg bathroom cleaners).

Actually the use of acidic compositions for cleaning enamel surfaces, because such formulations perform well in the elimination of lather and limescale. Soap foam and Limescale is a contaminant that often occurs on enamel surfaces. especially on enamel surfaces in the bathroom, in the kitchen and the same.

however There are some limitations in terms of the expediency acidic compositions used as enamel surface cleaners. In particular, it is known that enamel surfaces are sensitive to acids and through acidic compositions used to clean these surfaces be seriously damaged can be.

Therefore It is an object of the present invention to provide a method of cleaning of enamel surfaces with to provide an acidic composition which is safe for enamel surfaces is while it with different pollutants a good cleaning performance having.

Now it was found out that the aforementioned goal through a process for cleaning an enamel surface with a liquid acidic composition, which is an enamel safe buffer system includes, meets becomes.

Conveniently, The process can be used to clean enamel surfaces different enamel surfaces be used. enamel surfaces can be found in many places, eg. B. in the home: in the kitchen (sink and the like), in the bathroom (baths, washbasins, bathroom tiles, bathing accessories and the like), for washing machines and dishes.

One Another advantage of the above method is that the Cleaning enamel surfaces used compositions a good stain / Schmutzentfernungsleistung exhibit.

More accurate show the liquid acidic compositions have a good stain / soil removal performance on different types of stains / contaminants, in particular at: Grease dirt, z. As greasy soap scum or greasy contaminants in the kitchen; calcium deposits; Mould; mold; and other stubborn stains on enamel surfaces.

STATE OF THE ART

EP-B-580 838 and EP-A-647706 disclose compositions for cleaning hard Surfaces that a surfactant and optionally ammonium hydroxide as a buffer. However, these applications do not disclose a method of cleaning of enamel surfaces with a liquid acidic composition as described herein.

US 4,501,680 discloses acidic liquid detergent compositions comprising organic acid mixtures, an ether of diethylene glycol, and a surfactant.

SUMMARY OF THE INVENTION

The present invention comprises a method of cleaning an enamel surface with a liquid acid composition comprising an acid source and an enamel-safe buffer system, wherein the buffer system comprises a salt containing: an anion selected from the group consisting of hydroxide and carbonate; and a cation having an ionic radius of over 115 pm; with the In that no ethers of diethylene glycol are present in the composition.

In a preferred embodiment For example, the cation with an ionic radius of over 115 pm is selected from the group consisting of a potassium ion, an ammonium ion, a cesium, a barium ion and a quaternary ammonium ion.

In a further preferred embodiment For example, the composition used herein further comprises a surfactant.

The The present invention further includes the use of an enamel safe buffer system in a liquid acidic composition, the one source of acidity for cleaning an enamel surface wherein the buffer system comprises a salt comprising includes: An anion selected from the group consisting of hydroxide and carbonate; and a cation, that has an ionic radius of over 115 pm; whereby the composition is safe for enamel; with the proviso that no ethers of diethylene glycol are present in the composition are.

DETAILED DESCRIPTION OF THE INVENTION

The method of treating a hard surface

The The present invention includes a method for treating a enamel surface with a liquid acidic composition, which is an enamel safe buffer system as described here. In a preferred embodiment comes the sour liquid Composition in contact with the enamel surface.

With "enamel surface" here is any Kind of surface referred to, which was made of enamel or coated with it.

"Enamel" turns white titanium or zirconium enamel or white Titanium or zirconium powder enamel referred to as a coating for metal surfaces (e.g. Steel), preferably to prevent corrosion the metal surfaces.

Enamel surfaces are common to find in the house, z. B. in the bathroom or in the kitchen: z. In tiling, rinsing, showering, Shower trays, toilets, baths, sinks, fittings and connections and the like. Further, cookware, dishes and the like may have an enamel surface. enamel surfaces are also on home appliances find that coated with enamel on the inside and / or outside surfaces could be, including, but not limited on, boilers, washing machines, dryers, refrigerators, freezers, cookers, Microwave ovens, Dishwasher and so on. Furthermore, enamel surfaces are used in industry, in the Architecture and similar To find application areas. Examples of enamel surfaces that found in these applications include enamel surfaces or in tanks, piping, reaction vessels, pumps, chemical processing equipment, mechanical Devices, heat exchangers, Hot water tanks, signs, Silos or building panels.

The liquid Acid composition of the present invention can be used with the treating surface in undiluted Shape or in diluted Shape come into contact.

By "diluted form" is meant here that the liquid Composition is diluted by the user, usually with water. The Composition is reduced to a usual dilution grade before use from 10 to 400 times, preferably from 10 to 200, and more preferably diluted from 10 to 100 times their weight in water. A normally recommended one degree of dilution is a 1.2% dilution of the Composition in water.

"In your undiluted Form "means that the liquid Compositions directly, without prior dilution, to be treated enamel surface be applied, d. H. that the liquid compositions, such as described here, are applied to the hard surfaces.

One preferred method for cleaning an enamel surface according to the invention consists on behalf of the composition in diluted form without rinsing the hard surface after application, to a good contaminant / stain removal performance to achieve.

One another preferred method of treating an enamel surface is in applying the composition described by the present invention, either in undiluted or more dilute Shape, the action on the surface, the optional wiping the surface with a suitable tool, for. As a sponge, and the preferred rinse the surface with water.

The to be treated enamel surfaces can be polluted by a variety of contaminants, z. B. greasy Contaminants (eg greasy soap scum, body fat, kitchen grease or burned / sticky food residues, the common in a kitchen occur, and the like) or so-called "lime deposit-containing stains." With "lime deposit-containing Stains "are all pure lime deposit patches meant, d. h., any stains that are mainly from Mineral deposits, as well as limescale deposits, d. h., stains that are not just mineral deposits like calcium and / or Containing magnesium carbonate but also lather (eg calcium stearate) and other fat (eg body fat).

Cleaning performance test method

The Cleaning performance of the diluted Composition can be determined by the following test procedure Enamel tiles are prepared by adding a typical artificial Fat / Partikelschmutzstoff applied to them and this then aged becomes. The test compositions and the comparative composition are diluted (eg composition: water 1:50 or 1: 100), applied to a sponge and used to clean the tiles with a Sheen scrub tester. The number of trains, the for A 100% clean cleaning is required. There can be a minimum of 6 repetitions, with each result in terms of every soiled tile is duplicated.

The Test method for evaluating the cleaning performance of the undiluted composition is identical to the above, except that the test compositions and the comparative compositions are used undiluted and that after cleaning a rinse cycle with clear water.

Test method for cleaning performance at greasy soap foam

In this test procedure, white enamel tiles (typically 24 cm x 4 cm) are covered with typical greasy soap scum contaminants based primarily on calcium stearate and commercially available artificial body contaminants (eg, 0.3 gram with a sprayer). The soiled tiles are then dried in an oven at a temperature of 140 ° C for 20 minutes and then aged overnight at room temperature (about 20 ° C-25 ° C). Then the soiled tiles are cleaned using 3 ml of the liquid composition is applied directly onto a Spontex ^® sponge of the present invention. The ability of the composition to remove greasy soap scum is measured by the number of strokes required to perfectly clean the surface. The lower the number of puffs, the higher the ability of the composition to remove greasy soap scum.

The liquid acidic composition

The liquid acidic compositions used in a method according to the invention are preferably aqueous compositions. Therefore can from 70% by weight to 99% by weight, preferably from 75% by weight to 95% by weight and more preferably from 85% to 95% by weight of the total composition to include water.

The used according to the invention liquid Compositions are acidic and therefore preferably have one pH below 7, preferably from 1 to 6.5, more preferably from 1 to 5, more preferably from 2 to 5, and most preferred from 2 to 4 on.

The in a method according to the invention used compositions are suitably chemically stable, d. h., there are virtually no chemical reactions between the different components of the compositions, and physically stable, d. h., it occurs when stored in a rapid aging test (RAT), d. h., at ten-day Storage at 50 ° C, no phase separation.

A proviso of the present invention is that the compositions do not contain an ether of diethylene glycol. By "ether of diethylene glycol" is meant any mono-lower alkyl ether or phenyl ether of diethylene glycol as well as benzyl ether of diethylene glycol and mixtures thereof Cyl ether of diethylene glycol "is meant the C _2-6 alkyl ether of diethylene glycol.

buffer system

When an essential constituent include those in a process according to the invention used a buffer system.

The Buffer system comprises a salt containing: a Anion selected from the group consisting of hydroxide and carbonate; and a cation, that has an ionic radius of over 115 pm.

Usually can the compositions of the invention from 0.1% to 5% by weight of the total composition, a buffer system comprise, preferably from 0.1 wt .-% to 4 wt .-% and more preferably from 0.1% to 3% by weight.

Preferably is the salt of one whose cation has an ionic radius of at least 125 pm, more preferably at least 130 pm, even more preferably at least 135 pm, and most preferably at least 140 pm.

Examples of suitable cations in the salt are potassium ions (the ionic radius of K ⁺ is 133 pm), ammonium ions (the ionic radius of NH ₄ ⁺ is 143 pm), cesium ions (the ionic radius of Cs ⁺ is 167 pm), barium ions (the ionic radius of Ba ²⁺ is 134 pm) or quaternary ammonium ions.

Other suitable cations having an ionic radius above 115 pm include Ac ³⁺ , Ag ⁺ , Ar ⁺ , Au ⁺ , Ba ⁺ , Ca ⁺ , Ce ⁺ , Fr ⁺ , Hg ⁺ , La ⁺ , Pb ²⁺ , Ra ^{2 +} , Rb ⁺ and T1 ⁺ .

sodium has an ionic radius of 97 pm and is therefore a cation in the buffer component not suitable.

Preferably is the cation in the salt selected from the group consisting from a potassium ion, an ammonium ion, a cesium ion, a barium ion and a quaternary Ammonium ion. More preferably, the cation in the salt is a potassium ion or an ammonium ion.

The anion in the salt is a hydroxide or a carbonate. By "hydroxide" is meant an OH ^- ion, by "carbonate" is meant an HCO ₃ or CO ₃ ² ion.

Examples of suitable salts to be part of the buffer system are selected from the group consisting of potassium hydroxide (KOH), potassium carbonate (K ₂ CO ₃ ), potassium bicarbonate (KHCO ₃ ), ammonium hydroxide (NH ₄ OH), ammonium carbonate ((NH ₄ ) ₂ CO ₃ ), ammonium bicarbonate (NH ₄ HCO ₃ ), cesium hydroxide (CsOH), barium hydroxide (Ba (OH) ₂ ), barium carbonate (BaCO ₃ ) and mixtures thereof.

Preferably, the salt is selected from the group consisting of potassium hydroxide (KOH), potassium carbonate (K ₂ CO ₃ ), potassium bicarbonate (KHCO ₃ ), ammonium hydroxide (NH ₄ OH), ammonium carbonate ((NH ₄ ) ₂ CO ₃ ), ammonium bicarbonate (NH ₄ HCO ₃ ), cesium hydroxide (CsOH), barium hydroxide (Ba (OH) ₂ ), barium carbonate (BaCO ₃ ) and mixtures thereof. More preferably, the salt is selected from the group consisting of potassium hydroxide, ammonium hydroxide and mixtures thereof.

Preferably the buffer system consists of one or more salts as above described.

The The present invention is based on the finding that a method for cleaning enamel with a liquid acidic composition, the one for Enamel safe buffer system as described here, safe for enamel surfaces is.

One Another aspect of the present invention is in the Using a for Enamel safe buffer system in a liquid acidic composition, the one source of acidity for cleaning an enamel surface wherein the buffer system comprises a salt comprising includes: An anion selected from the group consisting of hydroxide and carbonate; and a cation, that has an ionic radius of over 115 pm; causing the composition to become enamel that's for sure; with the proviso that in the composition no ethers of diethylene glycol available.

With "sure for enamel surfaces "is meant here that the acidic compositions as described herein do not have enamel surfaces damage, as other acidic compounds could potentially do.

Damage to enamel surfaces can be caused by small cations, d. h., Cations with an ionic radius of 115 pm or less, the are present in acidic compositions which are for cleaning the enamel surfaces be used. The small cation can enter the upper class of the Crystal lattice of enamel penetrate and spread in it. The little cations can after all Replace cations that originally present in the upper layers of the crystal lattice of enamel and / or otherwise modify the top layers of the crystal lattice of enamel. As a result, the enamel surface loses its smoothness and therefore their splendor. The loss of shine is perceived as damage to the enamel surface.

Without To be bound by theory, it is believed that the relatively large cations, in the buffer system according to the invention be used and a cationic ionic radius of over 115 pm, not in the top layer of the crystal lattice of enamel invade and spread in it. Therefore, those are in one Method of cleaning an enamel surface as used herein Compositions for sure the enamel surfaces.

Of the Degree of damage to the enamel can be determined by the following enamel damage test procedure.

Enamel damage test method

Some a few drops of the composition according to the invention are placed on an enamel surface (For example, an enamel tile) and then the surface with covered by a watch glass. After 15 minutes, the watch glass is removed, the enamel surface rinsed with water (either demineralized or tap water) and then dry wiped. By optical inspection (optical Classification) or gloss measurements of the surface can be determined whether the product for Enamel is safe (no difference in gloss compared to untreated enamel surface) or for enamel not sure (difference in gloss compared to untreated Enamel surface).

of acidity

The Compositions of the invention are formulated as acidic compositions. Therefore, the include Compositions an acid source.

typically, can the sources of acidity for this purpose Use any organic or inorganic acid, which is well known to those skilled in the art, or a mixture thereof.

suitable organic acids for this purpose Uses are those of the group consisting of citric acid, maleic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and adipic acid and mixtures thereof selected.

A mixture of suitable acids for use herein is commercially available under the trade name Sokalan ^® DCS commercially available from BASF. A preferred organic acid for use herein is citric acid.

Preferably, the inorganic acids have a pK _a of less than 3 for use herein. Suitable inorganic acids for use herein are those selected from the group consisting of sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid and mixtures thereof. A preferred inorganic acid for use herein is sulfuric acid.

The in a method according to the invention used compositions comprise an acidity source from between 0.5% by weight and 10% by weight, preferably between 1% by weight and 8 wt%, and most preferably between 2 wt% and 6 wt% the overall composition.

Optional surfactant

The liquid compositions used in a method of the invention may preferably comprise a surfactant. Surfactants may be desirable here as they continue to be purified performance of the compositions of the present invention.

surfactants for this purpose Close use nonionic surfactants, cationic surfactants, anionic surfactants, zwitterionic surfactants, amphoteric surfactants and mixtures thereof one.

Accordingly, the in a method according to the invention used compositions up to 15 wt .-%, more preferably from From 0.5% to 8% by weight, more preferably from 0.5% to 8% by weight and most preferably 0.5% to 8% by weight of the total composition include a surfactant.

• (i) Die Polyethylenoxidkondensate von Alkylphenolen, z. B. den Kondensationsprodukten von Alkylphenolen mit einer Alkylgruppe, die von 6 bis 20 Kohlenstoffatome entweder in einer geraden Kettenkonfiguration oder in einer verzweigten Kettenkonfiguration, vorzugsweise von 8 bis 14, und mehr bevorzugt von 8 bis 12 Kohlenstoffatomen, mit Ethylenoxid enthalten. Das Ethylenoxid liegt üblicherweise in Anteilen von 3 bis 25, vorzugsweise von 10 bis 25 Mol Ethylenoxid pro Mol Alkylphenol vor. Der Alkylsubstituent in solchen Verbindungen kann von polymerisiertem Propylen, Diisobutylen, Octan und Nonan abgeleitet werden; Beispiele dieser Art nichtionischer Tenside schließen Triton N-57^®, ein Nonylphenolethoxylat (5EO) von Rohm & Haas, und Imbentin O200^®, ein Octylphenolethoxylat (20EO) von KOLB, ein.
• (ii) Solche, die durch die Kondensation von Ethylenoxid mit dem Produkt, das aus der Reaktion von Propylenoxid und Ethylendiaminprodukten entsteht, gewonnen werden, die in der Zusammensetzung entsprechend dem gewünschtem Gleichgewicht zwischen den hydrophoben und hydrophilen Elementen variiert werden können. Beispiele hierfür sind Verbindungen, die von 40 Gew.-% bis 80 Gew.-% Polyoxyethylen enthalten und ein Molekulargewicht von 5.000 bis 11.000 aufweisen, resultierend aus der Reaktion von Ethylenoxidgruppen mit einer hydrophoben Base, die aus dem Reaktionsprodukt von Ethylendiamin und überschüssigem Propylenoxid besteht, wobei die Base ein Molekulargewicht in der Größenordnung von 2.500 bis 3.000 aufweist; Beispiele dieser Art nichtionischer Tenside schließen bestimmte der im Handel erhältlichen Tetronic^TM-Verbindungen, die von BASF vermarktet werden, ein.
• (iii) Das Kondensationsprodukt von aliphatischen Alkoholen mit von 2 bis 24 Kohlenstoffatomen, entweder in einer geraden Kettenkonfiguration oder in einer verzweigten Kettenkonfiguration, vorzugsweise von 6 bis 22, mehr bevorzugt von 6 bis 28 und noch mehr bevorzugt 8 bis 18 Kohlenstoffatomen, mit von 2 bis 35, vorzugsweise von 4 bis 25, mehr bevorzugt von 5 bis 18, und noch mehr bevorzugt 3 bis 15 Mol Ethylenoxid. Ein Beispiel für diese Art von Material ist Kokosnussalkohol-Ethylenoxid-Kondensat mit 5 bis 18 Mol Ethylenoxid pro Mol Kokosnussalkohol, wobei die Kokosnussalkohol-Fraktion 9 bis 14 Kohlenstoffatome aufweist. Zu weiteren Beispielen dieser Art von nichtionischem Tensid gehören bestimmte der im Handel erhältlichen Dobanol^®, Neodol^®, die von Shell oder Lutensol^® von BASF vermarktet werden. Zum Beispiel Dobanol^® 23,5 (C12-C13 EO5), Dobanol^® 91.5 (C9-C11 EO5), Dobanol^® 91,8 (C9-C11 EO8) und Lutensol^® AO30 (C12-C14 EO30).
• (iv) Trialkylaminoxide und Trialkylphosphinoxide, worin eine Alkylgruppe von 10 bis 18 Kohlenstoffatome aufweist, und zwei Alkylgruppen von 1 bis 3 Kohlenstoffatome besitzen; die Alkylgruppen können Hydroxysubstituenten enthalten; spezifische Beispiele sind Dodecyldi(2-hydroxyethyl)aminoxid und Tetradecyldimethylphosphinoxid.
• (v) Das Kondensationsprodukt von Ethylenoxid mit einer hydrophoben Base, die durch Kondensation von Propylenoxid mit Propylenglycol gebildet wird. Der hydrophobe Teil dieser Verbindungen weist vorzugsweise ein Molekulargewicht von 1.500 bis 1.800 auf und zeigt Wasserunlöslichkeit. Bei Zugabe von Polyoxyethylengruppen zu diesem hydrophoben Teil besteht die Tendenz zu einem Anstieg der Wasserlöslichkeit des Moleküls als Ganzem und die flüssige Eigenschaft des Produkts wird beibehalten bis zu dem Punkt, an dem der Polyoxyethylengehalt 50 % des Gesamtgewichts des Kondensationsprodukts beträgt, was einer Kondensation mit bis zu 40 Mol Ethylenoxid entspricht. Beispiele für Verbindungen dieses Typs umfassen bestimmte im Handel erhältliche Pluronic^TM-Tenside, vertrieben von BASF.

Suitable nonionic surfactants for use herein include a class of compounds that can broadly be defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound that is branched or linear aliphatic (e.g., Guerbet or secondary alcohol) or alkylaromatic nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with a particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements. Accordingly, suitable nonionic synthetic detergents include the following:

• (i) The polyethylene oxide condensates of alkylphenols, e.g. The condensation products of alkylphenols having an alkyl group containing from 6 to 20 carbon atoms in either a straight chain configuration or in a branched chain configuration, preferably from 8 to 14, and more preferably from 8 to 12 carbon atoms, with ethylene oxide. The ethylene oxide is usually present in proportions of from 3 to 25, preferably from 10 to 25, moles of ethylene oxide per mole of alkylphenol. The alkyl substituent in such compounds can be derived from polymerized propylene, diisobutylene, octane and nonane; Examples of this type of nonionic surfactants include Triton N-57 ^®, a nonyl phenol ethoxylate (5EO) from Rohm & Haas and Imbentin O200 ^®, an octyl phenol ethoxylate (20EO) from KOLB, a.
• (ii) those obtained by the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine products, which can be varied in composition according to the desired balance between the hydrophobic and hydrophilic elements. Examples thereof are compounds containing from 40% to 80% by weight of polyoxyethylene and having a molecular weight of from 5,000 to 11,000, resulting from the reaction of ethylene oxide groups with a hydrophobic base consisting of the reaction product of ethylenediamine and excess propylene oxide wherein the base has a molecular weight of the order of 2,500 to 3,000; Examples of this type of nonionic surfactants include certain of the commercially available Tetronic ^™ compounds marketed by BASF.
• (iii) The condensation product of aliphatic alcohols having from 2 to 24 carbon atoms, either in a straight chain configuration or in a branched chain configuration, preferably from 6 to 22, more preferably from 6 to 28 and even more preferably 8 to 18 carbon atoms, with from 2 to 35, preferably from 4 to 25, more preferably from 5 to 18, and even more preferably from 3 to 15 moles of ethylene oxide. An example of this type of material is coconut alcohol-ethylene oxide condensate with 5 to 18 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having 9 to 14 carbon atoms. Among other examples of this type of nonionic surfactant include certain of the commercially available Dobanol ^®, Neodol ^®, marketed by Shell or Lutensol ^® from BASF. For example Dobanol ^® 23.5 (C12-C13 EO5), Dobanol ^® 91.5 (C9-C11 EO5), Dobanol ^® 91.8 (C9-C11 EO8) and Lutensol AO30 ^® (C12-C14 EO30).
• (iv) trialkylamine oxides and trialkylphosphine oxides wherein one alkyl group has from 10 to 18 carbon atoms and two alkyl groups of from 1 to 3 carbon atoms; the alkyl groups may contain hydroxy substituents; specific examples are dodecyldi (2-hydroxyethyl) amine oxide and tetradecyldimethylphosphine oxide.
• (v) The condensation product of ethylene oxide with a hydrophobic base formed by condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds preferably has a molecular weight of 1,500 to 1,800 and exhibits water insolubility. Addition of polyoxyethylene groups to this hydrophobic moiety tends to increase the water solubility of the molecule as a whole, and the liquid property of the product is maintained to the point where the polyoxyethylene content is 50% of the total weight of the condensation product, causing condensation with bis corresponds to 40 moles of ethylene oxide. Examples of compounds of this type include certain commercially available Pluronic ^™ surfactants, marketed by BASF.

Also useful as a nonionic surfactant are the alkyl polysaccharides disclosed in U.S. Patent No. 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing 6 to 30 Carbon atoms, preferably 10 to 16 carbon atoms, and a hydrophilic polysaccharide, e.g. A polyglycoside group containing from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms may be used, e.g. For example, glucosyl groups can be substituted by glucose, galactose and galactosyl groups. (Optionally, the hydrophobic group is attached to the 2-, 3-, 4-position, etc., thus yielding a glucose or galactose, as opposed to a glucoside or galactoside.) The intersaccharide bonds may be e.g. Between position 1 of the additional saccharide units and positions 2, 3, 4 and / or 6 of the previous saccharide units.

Optionally, and less desirable a polyalkylene oxide chain may be present which is the hydrophobic Unit and the polysaccharide unit connects. The preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched with 8 to 18, preferably 10 to 16 Carbon atoms. Preferably, the alkyl group can have up to 3 hydroxy groups and / or the polyalkylene oxide chain can be up to 10, preferably contain less than 5, alkylene oxide groups. Suitable alkyl polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, Pentadecyl, hexadecyl, heptadecyl, and octadecyl, -di-, -tri-, tetra-, penta- and hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructoses and / or galactoses. Suitable mixtures include coconut alkyl, di-, tri-, tetra- and pentaglucosides and tallow alkyltetra-, penta- and -hexaglucosides.

The preferred alkylpolyglycosides have the formula: R ² O (C _n H _2n O) _t (glucosyl) _x wherein R ^{2 is} selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to 10, preferably 0, and x is from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is first formed and then chemically reacted with glucose or a source of glucose to form the glucoside (bond at position 1). The additional glycosyl units can then be attached between their position 1 and the previous glycosyl units at positions 2, 3, 4 and / or 6, preferably above all at position 2.

worin: R¹ für H, C₁-C₄-Hydrocarbyl, 2-Hydroxyethyl, 2-Hydroxypropyl oder eine Mischung davon steht, vorzugsweise für C₁-C₄-Alkyl, stärker bevorzugt für C₁- oder C₂-Alkyl, am stärksten bevorzugt für C₁-Alkyl(d. h. Methyl); und R² für ein C₅-C₃₁-Hydrocarbyl, vorzugsweise ein geradkettiges C₇-C₁₉-Alkyl oder Alkenyl, stärker bevorzugt ein geradkettiges C₉-C₁₇-Alkyl oder Alkenyl, am stärksten bevorzugt ein geradkettiges C₁₁-C₁₇-Alkyl oder Alkenyl oder deren Mischungen steht; und Z ein Polyhydroxyhydrocarbyl mit einer linearen Hydrocarbylkette mit mindestens 3 Hydroxylen, die direkt mit der Kette verbunden sind, oder ein alkoxyliertes Derivat (vorzugsweise ethoxyliert oder propoxyliert) davon ist. Z wird vorzugsweise in einer reduktiven Aminierungsreaktion von einem reduzierenden Zucker abgeleitet; mehr bevorzugt ist Z ein Glycidyl. Geeignete reduzierende Zucker schließen Glucose, Fructose, Maltose, Lactose, Galactose, Mannose und Xylose ein. Als Ausgangsmaterialien kann dextrosereicher Maissirup verwendet werden sowie die oben genannten einzelnen Zucker. Diese Maissirupe können eine Mischung von Zuckerbestandteilen für Z ergeben. Es wird darauf hingewiesen, dass keinesfalls beabsichtigt ist, andere geeignete Ausgangsmaterialien auszuschließen. Z ist vorzugsweise ausgewählt aus der Gruppe bestehend aus -CH₂-(CHOH)_n-CH₂OH, -CH(CH₂OH)-(CHOH)_n-1-CH₂OH, -CH₂-(CHOH)₂-(CHOR')(CHOH)-CH₂OH, worin n eine ganze Zahl von 3 bis einschließlich 5 ist und R' H oder ein cyclisches oder aliphatisches Monosaccharid und alkoxylierte Derivate davon ist. Am meisten bevorzugt sind Glycidyle, in denen n 4 ist, besonders -CH₂-(CHOH)₄-CH₂OH.Other suitable nonionic surfactants for use herein include polyhydroxy fatty acid amides of the following structural formula:

in which: R ^{1 is} H, C ₁ -C ₄ -hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, preferably C ₁ -C ₄ -alkyl, more preferably C ₁ - or C ₂ -alkyl, most preferably C ₁ alkyl (ie, methyl); and R ^{2 is} a C ₅ -C ₃₁ hydrocarbyl, preferably a straight chain C ₇ -C ₁₉ alkyl or alkenyl, more preferably a straight chain C ₉ -C ₁₇ alkyl or alkenyl, most preferably a straight chain C ₁₁ -C ₁₇ Alkyl or alkenyl or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly attached to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z is preferably derived from a reducing sugar in a reductive amination reaction; more preferably, Z is a glycidyl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose. As starting materials, dextrose-rich corn syrup can be used as well as the individual sugars mentioned above. These corn syrups may yield a mixture of sugar ingredients for Z. It should be noted that it is by no means intended to exclude other suitable starting materials. Z is preferably selected from the group consisting of -CH ₂ - (CHOH) _n -CH ₂ OH, -CH (CH ₂ OH) - (CHOH) _n-1 -CH ₂ OH, -CH ₂ - (CHOH) ₂ - (CHOR ') (CHOH) -CH ₂ OH, wherein n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosaccharide and alkoxylated derivatives thereof. Most preferred are glycidyls in which n is 4, especially -CH ₂ - (CHOH) ₄ -CH ₂ OH.

In formula (I), R ^{1 'may be,} for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl or N-2-hydroxypropyl.

For example, R ² -CO-N <may be cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.

Z may 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl, etc.

Other suitable nonionic surfactants for use herein include the amine oxides having the formula: RR'R''N → O wherein R is a primary alkyl group containing from 6 to 24 carbons, preferably from 10 to 18 carbons, and wherein R 'and R "are each independently an alkyl group containing from 1 to 6 carbon atoms. The arrow in the formula is the conventional representation of a semipolar bond. The preferred amine oxides are those in which the primary alkyl group in at least most of the molecules has a straight chain, generally at least 70%, preferably at least 90% of the molecules, and the amine oxides which are particularly preferred are in which R contains from 10 to 18 carbons and R 'and R "are both methyl. Examples of the preferred amine oxides are N-hexyldimethylamine oxide, N-octyldimethylamine oxide, N-decyldimethylamine oxide, N-dodecyldimethylamine oxide, N-tetradecyldimethylamine oxide, N-hexadecyldimethylamine oxide, N-octadecyldimethylamine oxide, N-eicosyldimethylamine oxide, N -docosyldimethylamine oxide, N-tetracosyldimethylamine oxide, the corresponding amine oxides in which one or both of the methyl groups are replaced by ethyl or 2-hydroxyethyl groups, and mixtures thereof. A highly preferred amine oxide for use herein is N-decyldimethyl amine oxide.

Other suitable nonionic surfactants for the purpose of the present invention are the phosphine or sulfoxide surfactants of the formula: RR'R''A → O wherein A is a phosphorus or sulfur atom, R is a primary alkyl group of 6-24 carbons, preferably 10-18 carbons, and wherein R 'and R "are each independently selected from methyl, ethyl and 2-hydroxyethyl. The arrow in the formula is the conventional representation of a semipolar bond.

In a preferred embodiment, suitable nonionic surfactants to be used herein are polyethylene oxide condensates of alkylphenols, polyethylene oxide condensates of alkyl alcohols, alkyl polysaccharides, or mixtures thereof. Highly preferred are C ₆ -C ₂₀ -, preferably C ₈ -C ₁₂ -alkylphenol ethoxylates having from 3 to 25, preferably 10 to 25 ethoxy groups and C ₂ -C ₂₄ -, preferably C ₈ -C ₁₈ -alcohol ethoxylates having from 2 to 35 , preferably from 4 to 25, more preferably from 5 to 18 and most preferably from 3 to 15 ethylene oxide units, and mixtures thereof.

suitable zwitterionic surfactants for use herein both basic and acidic groups that form an internal salt, this includes both cationic and anionic hydrophilic groups the same molecule in a relatively wide pH range provides. The typical cationic group is one quaternary Ammonium group, although other positively charged groups such as phosphonium, Imidazolium and sulfonium groups can be used. The typical anionic hydrophilic groups are carboxylates and sulfonates, although other groups such as sulfates, phosphonates and the like, can be used.

A generic formula for preferred zwitterionic surfactants for use herein (ie, betaine and / or sulfobetaine) is: R ₁ -N ⁺ (R ₂ ) (R ₃ ) R ₄ X ^- wherein R _{1 is} a hydrophobic group, R _{2 is} hydrogen, a C ₁ -C ₆ alkyl, hydroxyalkyl or other substituted C ₁ -C ₆ alkyl group; R _{3 is} a C ₁ -C ₆ alkyl, hydroxyalkyl or another substituted C ₁ -C ₆ alkyl group which may also be linked to R ₂ to form ring structures with N, or a C ₁ -C ₆ - Carboxylic acid group or a C ₁ -C ₆ sulfonate group; R _{4 is} a moiety linking the cationic nitrogen atom to the hydrophilic group and is usually an alkylene, hydroxyalkylene or polyalkoxy group of 1 to 10 carbon atoms and X is the hydrophilic group which is a carboxylate or sulfonate group, preferably a sulfonate group.

Preferred hydrophobic groups R ₁ are aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chains which may contain linking groups such as amido groups and ester groups. More preferably, R _{1 is} an alkyl group containing from 1 to 24, preferably from 8 to 18, and more preferably from 10 to 16, carbon atoms. These simple alkyl groups are preferred for cost and stability reasons. However, the hydrophobic group R _{1 may} also be an amido radical of the formula R _a -C (O) -NR _b - (C (R _c ) ₂ ) _m wherein R _{a is} an aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chain which contains from 8 up to 20 carbon atoms, preferably an alkyl group containing from 8 up to 20, preferably up to 18, more preferably up to 16 carbon atoms, R _b is either hydrogen, a short chain alkyl or substituted alkyl derived from Contains from 1 to 4 carbon atoms, preferably a group selected from the group consisting of methyl, ethyl, propyl, hydroxy-substituted ethyl or propyl and mixtures thereof, more preferably methyl or hydrogen, R _c is selected from the group consisting of hydrogen and hydroxy groups, and m is from 1 to 4, preferably from 2 to 3, more preferably 3, with no more than one hydroxy group in any (C (R _c ) ₂ ) unit.

Preferably, R _{2 is} hydrogen or an alkyl or substituted alkyl containing from 1 to 4 carbon atoms, preferably a group selected from the group consisting of methyl, ethyl, propyl, hydroxy-substituted ethyl or propyl, and mixtures thereof, more preferably methyl. Preferably, R _{3 is} a C ₁ -C ₄ carboxylic acid group, a C ₁ -C ₄ sulfonate group, or an alkyl or substituted alkyl containing from 1 to 4 carbon atoms, preferably a group selected from the group consisting of methyl, ethyl, Propyl, hydroxy substituted ethyl or propyl, and mixtures thereof, more preferably methyl. Preferred R ₄ is (CH ₂ ) _n , wherein n is an integer from 1 to 10, preferably from 1 to 6, more preferably from 1 to 3.

Some common examples for betaine / sulfobetaine are described in U.S. Pat. Pat.-No. 2,082,275, 2,702,279 and 2,255,082.

Examples of particularly suitable alkyl dimethyl betaines include coconut dimethyl betaine, lauryl dimethyl betaine, decyl dimethyl betaine, 2- (N-decyl-N, N-dimethyl ammonium) acetate, 2- (N-coconut N, N-dimethyl ammonium) acetate, myristyl dimethyl betaine, palmityldimethyl betaine, cetyl dimethyl betaine, stearyl dimethyl betaine. For example, coconut-is commercially available from Seppic under the trade name Amonyl265 ^®. Lauryl betaine is commercially available from Albright & Wilson under the trade name Empigen BB / L ^®.

A further example of betaine is Lauryl commercially available from Rhone-Poulenc under the trade name Mirataine H2C-HA ^®.

Especially preferred zwitterionic surfactants for use in the compositions In the present invention, the sulfobetaine surfactants are provide optimal benefits in fat removal.

Examples of particularly suitable surfactants include tallow bis sulfobetainer (hydroxyethyl) sulphobetaine, Cocoamidopropylhydroxy-sulfobetaines which are commercially available from Rhone Poulenc and Witco, respectively under the trade name Mirataine CBS ^® and Rewoteric AM CAS 15 ^®.

Further examples of amido betaines / amido sulfobetaines include cocoamidoethyl betaine, cocoamidopropyl betaine or C ₁₀ -C ₁₄ fatty acylamidopropylene (hydropropylene) sulfobetaine. C ₁₀ -C ₁₄ fatty acylamidopropylene (hydropropylene) sulfobetaine is commercially available, for example from Sherex Company under the trade name "Varion CAS ^® sulfobetaine".

suitable Amines to the relevant Use correspond to the following formula RR'R''N, wherein R is a saturated or unsaturated, substituted or unsubstituted, linear or branched Alkyl group is from 1 to 30 carbon atoms and preferably contains from 1 to 20 carbon atoms and wherein R 'and R "independently of one another saturated or unsaturated, substituted or unsubstituted, linear or branched Alkyl groups are from 1 to 30 carbon atoms or hydrogen contain. Particularly preferred amines to be used according to the invention are Amines of the following formula RR'R''N, where R is a saturated or unsaturated, is a linear or branched alkyl group containing from 1 to 30 carbon atoms, preferably from 8 to 20, more preferably from 6 to 16, most preferably contains from 8 to 14 carbon atoms and wherein R 'and R "independently substituted or unsubstituted, linear or branched alkyl groups, those from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms and more preferably methyl groups or mixtures thereof are.

Suitable amines for use herein are, for example, C ₁₂ dimethylamine, coco dimethylamine, C ₁₂ -C ₁₆ dimethylamine. The amines may be available under the trade name Radiamine ^® commercially available from Hoechst under the trade name Genamin ^®, AKZO under the trade name Aromox ^® or Fina.

Suitable quaternary ammonium surfactants for use herein correspond to the formula R ₁ R ₂ R ₃ R ₄ N ⁺ X ^- wherein X is a counter anion such as halogen, methyl sulfate, methyl sulfonate or hydroxide. R ₁ is a saturated or unsaturated, substituted or unsubstituted, linear or branched alkyl group containing from 1 to 30 carbon atoms, preferably from 12 to 20, more preferably from 8 to 20 carbon atoms and R ₂ , R ₃ and R ₄ are independently hydrogen or saturated or unsaturated, substituted or unsubstituted, linear or branched alkyl groups corresponding to from 1 to 4 carbon atoms preferably, from 1 to 3 and more preferably methyl. In highly preferred quaternary ammonium surfactants, R _{1 is} a C ₁₀ -C ₁₈ hydrocarbon chain, most preferably C ₁₂ , C ₁₄ , or C ₁₆ , and R ₂ , R ₃ and R ₄ are all three methyl and X is halogen, preferably bromide or chloride, most preferably bromide.

Examples of quaternary ammonium surfactants are myristyltrimethylammonium methylsulfate, cetyltrimethylammonium methylsulfate, lauryltrimethylammonium bromide, stearyltrimethylammonium bromide (STAB), cetyltrimethylammonium bromide (CTAB) and myristyltrimethylammonium bromide (MTAB). Here, lauryltrimethylammonium salts are highly preferred. Such trimethyl quaternary ammonium may be commercially available from Hoechst, or from Albright & Wilson under the trade name Empigen CM ^®.

Cationic surfactants suitable for use in the compositions of the present invention are those having a long chain hydrocarbyl group. Examples of such cationic surfactants include the ammonium surfactants, such as the alkyl dimethyl ammonium halides, and those surfactants having the formula: [R ² (OR ³ ) _y ] [R ⁴ (OR ³ ) _y ] ₂ R ⁵ N ⁺ X wherein R ^{2 is} an alkyl or alkylbenzyl group having from 8 to 18 carbon atoms in the alkyl chain, each R ^{3 is} selected from the group consisting of -CH ₂ CH ₂ -, -CH ₂ CH (CH ₃ ) -, -CH ₂ CH (CH ₂ OH) -, -CH ₂ CH ₂ CH ₂ - and mixtures thereof; each R ^{4 is} selected from the group consisting of C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, benzyl ring structures formed by a compound of the two R ⁴ groups, -CH ₂ CHOH-CHOHCOR ⁶ CHOHCH ₂ OH, wherein R ^{6 is} any hexose or hexose polymer having a molecular weight of less than 1000 and hydrogen when y is not 0; R ⁵ is R ⁴ or an alkyl chain wherein the total number of carbon atoms of R ² and R ^{5 is} not more than 18; each y is from 0 to 10 and the sum of the y values is from 0 to 15 and X is any compatible anion.

Other Suitable cationic surfactants herein are also disclosed in U.S. Patent 4,228,044, Cambre, issued October 14, 1980.

amphoteric Surfactants and ampholytic detergents that are either cationic, depending on the pH of the system or anionic, are prepared by detergents such as dodecyl-betaalanine, N-alkyltaurines, such as those obtained by reaction of dodecylamine with Sodium isethionate according to the teachings from U.S. Patent No. 2,658,072, higher N-alkylaspartic acids, such as those who, according to the teachings of US Pat. No. 2,438,091, and the products, which are sold under the trade name "Miranol" and in U.S. Patent No. 2,528,378. Further synthetic detergents and listings of their commercial sources are in McCutcheon's "Detergents and Emulsifiers ", North American edition 1980, to find.

Suitable anionic surfactants for use herein are those generally known to those skilled in the art. Preferably, the anionic surfactants for use herein include alkyl sulfonates, alkylaryl sulfonates, alkyl sulfates, alkyl alkoxylated sulfates, alkyl alkoxylated linear or branched C ₆ -C ₂₀ diphenyl oxide disulfonates, or mixtures thereof.

Suitable alkyl sulfonates for use herein include water-soluble salts or acids of the formula RSO ₃ M, wherein R is a linear or branched, saturated or unsaturated C ₆ -C ₂₀ alkyl group, preferably a C ₈ -C ₁₈ alkyl group, and more preferably a C ₁₀ C ₁₆ alkyl group, and M is H or a cation, for example an alkali metal cation (eg sodium, potassium, lithium) or ammonium or substituted ammonium (eg methyl, dimethyl and trimethylammonium cations and quaternary ammonium cations, such as tetramethylammonium and dimethylpiperidinium cations, and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof).

Suitable alkylarylsulfonates for use herein include water-soluble salts or acids of the formula RSO ₃ M, wherein R is an aryl, preferably a benzyl, substituted with a linear or branched, saturated or unsaturated C ₆ -C ₂₀ alkyl group, preferably a C ₈ - C ₁₈ alkyl group, and more preferably a C ₁₀ -C ₁₆ alkyl group, and is MH or a cation, for example, an alkali metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.) or ammonium or substituted ammonium (e.g. Methyl, dimethyl and trimethylammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof and the like).

An example of a C ₁₄ -C ₁₆ alkyl sulphonate is Hostapur ^® SAS available from Hoechst. An example of a commercially available alkylaryl sulfonate is lauryl aryl sulfonate from Su. Ma. Particularly preferred alkylaryl sulfonates are alkyl benzene sulfonates, commercially available under the tradename ^Nansa® from Albright & Wilson.

Suitable alkyl carboxylate surfactants for use herein correspond to the formula R ₁ SO ₄ M, wherein R _{1 represents} a hydrocarbon group selected from the group consisting of straight or branched alkyl radicals having 6 to 20 carbon atoms and alkylphenyl radicals having 6 to 18 carbon atoms in the alkyl group. M is H or a cation, for example, an alkali metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, and the like) or ammonium or substituted ammonium (e.g., methyl, dimethyl, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl ammonium and dimethyl piperidinium cations, and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).

Particularly preferred branched alkyl sulfates for use herein are those having a total number of 10 to 14 carbon atoms such as Isalchem 123 AS ^®. Isalchem 123 AS ^®, commercially available from Enichem is a C _12-13 -Tensid, which is 94% branched. This material can be described as CH ₃ - (CH ₂ ) _m CH (CH ₂ OSO ₃ Na) - (CH ₂ ) _n -CH ₃ where n + m = 8 - 9. Also preferred alkyl sulfates are the alkyl sulfates in which the alkyl chain comprises a total of 12 carbon atoms, ie, sodium 2-butyloctyl sulfate. Such an alkyl sulfate is commercially available from Condea under the trade name Isofol ^® 12S. Particularly suitable linear alkyl sulphonates include C ₁₂ -C ₁₆ paraffin sulphonate like Hostapur ^® SAS commercially available from Hoechst.

Suitable alkyl alkoxylated sulfonate surfactants for use herein correspond to the formula RO (A) _m SO ₃ M, wherein R is an unsubstituted C ₆ -C ₂₀ alkyl, hydroxyalkyl or alkylaryl group having a C ₆ -C ₂₀ alkyl moiety, preferably a C ₁₂ C ₂₀ alkyl or hydroxyalkyl, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, A is ethoxy or propoxy or butoxy mo, m is greater than zero, usually between 0.5 and 6, more preferably between 0.5 and 3 and MH or a cation which z. A metal cation (e.g., sodium, potassium, lithium, calcium, magnesium), ammonium, or a substituted ammonium cation. Also contemplated herein are ethoxylated alkyl sulfates and propoxylated alkyl sulfates. Specific examples of substituted ammonium cations include methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium, dimethylpiperidinium and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine, mixtures thereof and the like. Exemplary surfactants are C ₁₂ -C ₁₈ -alkyl polyethoxylate (1.0) sulfate (C ₁₂ -C ₁₈ E (1.0) SM), (C ₁₂ -C ₁₈ -alkyl polyethoxylate (2.25) sulfate, (C ₁₂ -) C ₁₈ E (2.25) SM), C ₁₂ -C ₁₈ alkyl polyethoxylate (3.0) sulfate (C ₁₂ -C ₁₈ E (3.0) SM) and C ₁₂ -C ₁₈ alkyl polyethoxylate (4.0 ) sulfate (C ₁₂ -C ₁₈ E (4.0) SM), where M is conveniently selected from sodium and potassium.

worin R eine lineare oder verzweigte, gesättigte oder ungesättigte C₆-C₂₀-Alkyl-gruppe ist, vorzugsweise eine C₁₂-C₁₈-Alkylgruppe und mehr bevorzugt eine C₄-C₆-Alkylgruppe, und X+ H oder ein Kation ist, z. B. ein Alkalimetallkation (z. B. Natrium, Kalium, Lithium, Calcium, Magnesium usw.). Besonders geeignete alkylalkoxylierte lineare oder verzweigte C₆-C₂₀-Diphenyloxiddisulfonat- Tenside zum diesbezüglichen Gebrauch sind die verzweigte C12-Diphenyloxiddisulfonsäure bzw. das lineare C 16-Diphenyloxiddisulfonat-Natriumsalz, im Handel erhältlich von DOW unter den Handelsbezeichnungen Dowfax 2A1^® bzw. Dowfax 8390^®.Suitable alkylalkoxylated linear or branched C ₆ -C ₂₀ diphenyloxide disulphonate surfactants for use herein correspond to the following formula:

wherein R is a linear or branched, saturated or unsaturated C ₆ -C ₂₀ -alkyl group, preferably a C ₁₂ -C ₁₈ -alkyl group and more preferably a C ₄ -C ₆ -alkyl group, and X + is H or a cation, z. An alkali metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.). Particularly suitable alkyl alkoxylated linear or branched C ₆ -C ₂₀ -Diphenyloxiddisulfonat- surfactants for use herein are the C12 branched-Diphenyloxiddisulfonsäure or linear C 16 diphenyl oxide sodium salt, commercially available from DOW under the trade names Dowfax 2A1 ^® and Dowfax 8390 ^® .

Other anionic surfactants useful herein include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C ₈ -C ₂₄ olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed Alkaline earth metal citrate product, e.g. As described in British Patent No. 1,082,179, C ₈ -C ₂₄ alkyl polyglycol ether sulfates (containing up to 10 moles of ethylene oxide); Alkyl ester sulfonates such as C _14-16 methyl ester sulfonates; Acylglycerol sulfonates, fatty oleyl glycerol sulfates, alkylphenol ethylene oxide ether sulfates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters), diesters of sulfosuccinate (especially saturated and unsaturated C ₆ -C _14- diesters), acyl sarcosinates, sulfates of alkyl polysaccharides such as the sulfonates of alkyl polyglucoside (wherein the nonionic, unsulfated compounds are described below), alkyl polyethoxycarboxylates such as those of the formula RO (CH ₂ CH ₂ O) _k CH ₂ COO-M ⁺ , wherein R is C ₈ -C ₂₂ alkyl, k is an integer of 0 to 10 and M is a soluble, salt-forming cation. resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are given in "Surface Active Agents and Detergents" (Volumes I and II by Schwartz, Perry and Berch) A number of such surfactants are generally described in U.S. Patent No. 3,929,678 issued December 30, 1975 to Laughlin et al ., in column 23, line 58 to column 29, line 23.

Preferably are the surfactants to be used here as optional ingredients selected from the group consisting of nonionic surfactants, cationic surfactants, anionic surfactants, zwitterionic surfactants, amphoteric surfactants and mixtures thereof. More preferably, the surfactant is a nonionic Surfactant or an anionic surfactant or a mixture thereof.

Other optional ingredients

The Compositions can furthermore conventional Include components for cleaning enamel. Preferably, the liquid compositions according to the invention, depending on the desired technical advantage and the treated surface, one Include a variety of optional ingredients.

suitable Optional ingredients for use herein include Solvent, a builder, a chelating agent, a buffer, a bactericide, a hydrotrope, a coloring agent, a stabilizer, a radical scavenger, a vinylpyrrolidone homopolymer or copolymer, a polysaccharide polymer, a bleach, a bleach activator, a preservative, a suds regulator such as a fatty acid, an enzyme, a soil suspending agent, a color transfer agent, a brightener, a dust control, a dispersant, a dye transfer inhibitor, a pigment, an acid, a dye and / or a fragrance.

solvent

The used according to the invention Compositions can as a highly preferred optional ingredient solvent include.

solvent are wanted here because they improve the cleaning performance of the composition with greasy contaminants contribute.

Suitable solvents for use herein include glycols or alkoxylated glycols, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated linear C ₁ -C ₅ -alcohols, linear C ₁ -C ₅ -alcohols, C ₈ -C ₁₄ alkyl and cycloalkyl hydrocarbons and halocarbons and mixtures thereof, provided that the solvent is not an ether of diethylene glycol as described herein.

Suitable glycols for use herein are of the formula HO-CR1R2-OH wherein R1 and R2 are independently H or a saturated or unsaturated C ₂ -C ₁₀ aliphatic hydrocarbon chain and / or cyclic. Suitable glycols for use herein are dodecane glycol and / or propanediol.

suitable alkoxylated glycols for the purpose Use correspond to the formula R- (A) n -R1-OH, wherein R is H, OH, a linear saturated or unsaturated Alkyl of 1 to 20 carbon atoms, preferably 2 to 15 and more preferably from 2 to 10 carbon atoms, wherein R1 a linear saturated or unsaturated Alkyl of 3 to 20 carbon atoms, preferably from 3 to 15 and more preferably from 3 to 10 carbon atoms and A is a Alkoxy group, preferably ethoxy, methoxy and / or propoxy and n is from 1 to 5, preferably 1 to 2. Suitable alkoxylated glycols for the purpose Uses are methoxyoctadecanol and / or ethoxyethoxyethanol.

Suitable alkoxylated aromatic alcohols for use herein correspond to the formula R- (A) _n -OH wherein R is an alkyl-substituted or non-alkyl-substituted aryl group of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to 10 carbon atoms in which A is an alkoxy group, preferably butoxy, propoxy and / or ethoxy, and n is an integer from 1 to 5, preferably 1 to 2. Suitable alkoxylated aromatic alcohols are benzoxyethanol and / or benzoxypropanol.

Suitable aromatic alcohols for use herein correspond to the formula R-OH, wherein R is an alkyl-substituted or non-alkyl-substituted aryl group of 1 to 20 carbon atoms, preferably is 1 to 15 and more preferably 1 to 10 carbon atoms. A suitable aromatic alcohol for use herein is, for example, benzyl alcohol.

suitable aliphatic branched alcohols for use herein of the formula R-OH, wherein R is a branched saturated or unsaturated alkyl group from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 5 to 12 carbon atoms. Particularly suitable Aliphatic branched alcohols for use herein include 2-ethylbutanol and / or 2-methylbutanol.

Suitable alkoxylated aliphatic branched alcohols for use herein correspond to the formula R- (A) _n -OH wherein R is a branched saturated or unsaturated alkyl group of 1 to 20 carbon atoms, preferably 2 to 15 and more preferably 5 to 12 carbon atoms A is an alkoxy group, preferably butoxy, propoxy and / or ethoxy, and n is an integer from 1 to 5, preferably 1 to 2. Suitable alkoxylated aliphatic branched alcohols include 1-methylpropoxyethanol and / or 2-methylbutoxyethanol.

Suitable alkoxylated linear C ₁ -C ₅ alcohols for use herein correspond to the formula R- (A) _n -OH wherein R is a linear saturated or unsaturated alkyl group of 1 to 5 carbon atoms, preferably 2 to 4 carbon atoms wherein A is a Alkoxy group, preferably butoxy, propoxy and / or ethoxy, and n is an integer from 1 to 5, preferably 1 to 2. Suitable alkoxylated aliphatic linear C ₁ -C ₅ -alcohols are butoxypropoxypropanol (n-BPP), Butoxyethanol, butoxypropanol, ethoxyethanol or mixtures thereof. Butoxy available under the trade name n-BPP ^® from Dow Chemical.

Suitable linear C ₁ -C ₅ alcohols for use herein correspond to the formula R-OH wherein R is a linear saturated or unsaturated alkyl group of from 1 to 5 carbon atoms, preferably from 2 to 4 carbon atoms.

Suitable linear C ₁ -C ₅ -alcohols are methanol, ethanol, propanol or mixtures thereof.

Further suitable solvents include butyl triglycol ether, t-amyl alcohol and the like. Especially preferred solvents for this purpose Use are butoxypropoxypropanol, benzyl alcohol, butoxypropanol, Ethanol, methanol, isopropanol and mixtures thereof.

The preferred solvents for this purpose Use is butoxypropoxypropanol (n-BPP).

Usually include the invention used Compositions to 0.1 wt .-% to 8 wt .-%, preferably of 0.5 Wt% to 5 wt%, and more preferably from 1 wt% to 3 wt% the total composition is a solvent.

Vinylpyrrolidone homopolymer or copolymer

The Compositions used in the invention may include Vinylpyrrolidone homopolymer or copolymer.

Usually can in a process according to the invention used compositions of 0.01 wt .-% to 5 wt .-%, more preferably from 0.05% to 3% by weight and most preferably from From 0.05% to 1% by weight of the total composition of a vinylpyrrolidone homopolymer or copolymer.

worin n (Polymerisationsgrad) eine ganze Zahl von 10 bis 1.000.000, vorzugsweise von 20 bis 100.000 und mehr bevorzugt von 20 bis 10.000 ist.Suitable vinylpyrrolidone homopolymers for use herein are homopolymers of N-vinylpyrrolidone with the following basic monomer:

wherein n (degree of polymerization) is an integer of 10 to 1,000,000, preferably 20 to 100,000, and more preferably 20 to 10,000.

Accordingly, show suitable vinylpyrrolidone homopolymers ("PVP") for use herein are average Molecular weight of 1,000 to 100,000,000, preferably 2,000 to 10,000,000, more preferably from 5,000 to 1,000,000 and most preferably from 50,000 to 500,000.

Suitable vinyl pyrrolidone homopolymers are commercially available from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K- ^15® (viscosity molecular weight 10,000), PVP K- ^30® (average molecular weight 40,000), PVP K- ^60® (average molecular weight 160,000) and PVP K- ^90® (average molecular weight 360,000). Other suitable vinylpyrrolidone homopolymers which are commercially available from BASF Cooperation include Sokalan HP 165 ^®, Sokalan HP 12 ^®, Luviskol K30 ^®, Luviskol K60 ^®, Luviskol K80 ^®, Luviskol K90 ^® and other vinylpyrrolidone homopolymers include those skilled in the detergent field (see, for example, EP-A-262,897 and EP-A-256,696).

suitable Copolymers of vinylpyrrolidone for use herein include copolymers of N-vinylpyrrolidone and alkylenically unsaturated monomers or mixtures one of them.

The alkylenically unsaturated Monomers of the copolymers include unsaturated dicarboxylic acids such as maleic acid, chloromaleic acid, fumaric acid, itaconic acid, citraconic acid, phenylmaleic acid, aconitic acid, acrylic acid, N-vinylimidazole and vinyl acetate. Any of the anhydrides of the unsaturated acids can be used for example acrylate, methacrylate. Aromatic monomers such as styrene, sulfonated styrene, alpha-methylstyrene, vinyltoluene, t-butylstyrene and similar, Well-known monomers can be used.

The Molecular weight of the copolymer of vinylpyrrolidone is not particularly crucial as long as the copolymer is water-soluble, has some surface activity and from the liquid Composition that it contains on the hard surface is adsorbed in such a way that the hydrophilicity of the surface is increased. However, the preferred copolymers of N-vinylpyrrolidone and alkylenically unsaturated Monomers or mixtures thereof have a molecular weight of between 1,000 and 1,000,000, preferably between 10,000 and 500,000 and more preferably between 10,000 and 200,000.

To the For example, particularly suitable N-vinylimidazole N-vinylpyrrolidone polymers are useful herein Use an average molecular weight in the range of 5,000 to 1,000,000, preferably from 5,000 to 500,000 and more preferably from 10,000 to 200,000. The average molecular weight range was light scattered as described in Barth, H.G. and Mays, J.W., Chemical Analysis, Vol. 113, "Modern Methods of Polymer Characterization ".

Such copolymers of N-vinylpyrrolidone and alkylenically unsaturated monomers like PVP / vinyl acetate copolymers are commercially available under the trade name Luviskol ^® series from BASF.

The Copolymers of vinylpyrrolidone for use in the compositions The present invention also includes quaternized or non-quaternized vinyl pyrrolidone / dialkylaminoalkyl acrylate or Methacrylate copolymers one.

worin n zwischen 20 und 99 und vorzugsweise zwischen 40 und 90 Mol-% und m zwischen 1 und 80 und vorzugsweise zwischen 5 und 40 Mol-% beträgt; R₁ steht für H oder CH₃; y bedeutet 0 oder 1; R₂ ist -CH₂-CHOH-CH₂- oder C_xH_2x, wobei x = 2 bis 18; R₃ steht für eine Niederalkylgruppe mit 1 bis 4 Kohlenstoffatomen, vorzugsweise Methyl oder Ethyl, oder

R₄ eine Niederalkylgruppe von 1 bis 4 Kohlenstoffatomen bezeichnet, vorzugsweise Methyl oder Ethyl; X^– aus der Gruppe bestehend aus C1, Br, I, 1/2 SO₄, HSO₄ und CH₃SO₃ ausgewählt ist. Die Polymere können nach dem in den französischen Patenten mit den Nummern 2,077,143 und 2,393,573 beschriebenen Verfahren hergestellt werden.Such vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate copolymers (quaternized or not quaternized) suitable for use in the compositions of the present invention conform to the following formula:

wherein n is between 20 and 99 and preferably between 40 and 90 mol% and m between 1 and 80 and preferably between 5 and 40 mol%; R ₁ is H or CH ₃ ; y is 0 or 1; R ₂ is -CH ₂ -CHOH-CH ₂ - or C _x H _2x , where x = 2 to 18; R ₃ represents a lower alkyl group having 1 to 4 carbon atoms, preferably methyl or ethyl, or

R ₄ denotes a lower alkyl group of 1 to 4 carbon atoms, preferably methyl or ethyl; X ^{- is selected} from the group consisting of Cl, Br, I, ½ SO ₄ , HSO ₄ and CH ₃ SO ₃ . The polymers can be prepared by the method described in French Patent Nos. 2,077,143 and 2,393,573.

The preferred quaternized or non-quaternized vinyl pyrrolidone / dialkylaminoalkyl acrylate or -methacrylate copolymers for use herein Molecular weight between 1,000 and 1,000,000, preferably between 10,000 and 500,000 and more preferably between 10,000 and 100,000 on.

Such vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate copolymers are commercially available under the name Copolymer 845 ^®, Gafquat 734 ^® or Gafquat 755 ^® from ISP Corporation, New York, NY and Montreal, Canada or from BASF under the trade name Luviquat.RTM ^® available.

preferred Vinyl pyrrolidone homopolymers or copolymers for the same Use are the vinylpyrrolidone homopolymers.

Polysaccharide polymer

The used according to the invention Compositions can a polysaccharide polymer.

Usually can the compositions of the present invention to 0.01 wt .-% to 5 wt .-%, more preferably from 0.05 wt .-% to 3 wt .-% and am most preferably from 0.05% to 1% by weight of the total composition a polysaccharide polymer.

suitable Polysaccharide polymers for use herein include substituted ones Cellulosic materials, such as carboxymethylcellulose, ethylcellulose, Hydroxyethylcellulose, hydroxypropylcellulose, hydroxymethylcellulose, Succinoglycan and of course occurring polysaccharide polymers such as xanthan gum, guar gum, Locust bean gum, gum tragacanth or derivatives thereof or mixtures one of them.

Particularly preferred polysaccharide polymers for use herein are xanthan gum and derivatives thereof. Xanthan gum and derivatives thereof may be commercially available for instance from Kelco under the trade name Keltrol RD ^®, Kelzan S ^® or Kelzan T ^®. Another suitable Xanthan gum is commercially available from Rhone Poulenc under the trade name Rhodopol T ^® and Rhodigel X747 ^®. Succinoglycan for use herein is commercially available from Rhone Poulenc under the trade name Rheozan ^®.

dye

The used according to the invention liquid Compositions can colored be. Accordingly, they can include a dye. Suitable dyes for this purpose Use are stable colors. By "stable" is meant here a compound the chemically and physically in the acidic environment of the compositions of the invention are stable.

preservative

The used according to the invention Compositions can and, as an optional ingredient, a preservative include. Preservatives for use herein include all, the professionals for Compositions for cleaning hard surfaces are known.

preservatives are wanted here as they contribute to stability contribute to the compositions.

suitable Preservatives for this purpose Uses are diazolidinyl urea, triethyl citrate, propyl 4-hydroxybenzoate, sorbic acid, Na salt of p-hydroxybenzoate or gluteraldehyde or a mixture from that.

radical scavengers

The used according to the invention Compositions can a radical scavenger include.

Suitable radical scavengers for use herein include the known substituted mono- and dihydroxybenzenes and their analogs, alkyl and aryl carboxylates, and mixtures thereof. Preferred such radical scavengers for use herein include di-t-butylhydroxytoluene (BHT), hydroquinone, di-t-butylhydroquinone, mono-t-butylhydroquinone, t-butylhydroxyanisole, benzoic acid, toluic acid, catechol, t-butylcatechol, benzylamine, 1,1, 3-tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane, n-propyl gallate or mixtures thereof, and highly preferred is di-t-butyl hydroxytoluene. Such radical scavengers like N-propyl are commercially available under the trade name Nipanox S1 ^® from Nipa Laboratories.

If radical scavengers they are usually used in amounts of up to 10% by weight and preferably of 0.001% by weight to 0.5% by weight of the total composition.

The Presence of radical scavengers can contribute to chemical stability the invention used Contribute to compositions.

perfume

The used according to the invention Compositions can further comprising a fragrance.

suitable Perfumes for this purpose Close use Materials that have an aesthetic odor benefit deliver and / or mask any "chemical" odor, the product may have. The main function of a small fraction of highly volatile, low boiling (low boiling point) perfume components in these fragrances is the fragrance of the product itself to improve, instead of the subsequent smell of the purified surface to influence. Some of the less volatile, high-boiling perfume ingredients however, they lend to the surfaces a fresh and clean impression and it is desired that these ingredients are deposited on the dry surface and present are. Perfume ingredients can easily solubilized in the compositions, for example by an anionic detergent surfactant, if present. The suitable Perfume ingredients and compositions to the relevant Use are the conventional, which are used in the field. The selection of any Perfume ingredient or any proportion of perfume based solely on aesthetic considerations.

Suitable perfume compounds and compositions are found in the art including U.S. Pat. Nos. 4,145,184, Brain and Cummins, issued Mar. 20, 1979; 4,209,417, Whyte, issued June 24, 1980; 4,515,705, Moeddel, issued May 7, 1985; and 4,152,272, Young, issued May 1, 1979. In general, the degree of substantivity of a perfume is approximately proportional to the percentage of substantive perfume material used. Relatively substantive perfumes contain at least 1%, preferably at least 10% substantive fragrance materials. Substantive perfume materials are the fragrance compounds that deposit on surfaces through the cleaning process and which are perceptible by persons with normal sense of smell. Such materials typically have vapor pressures lower than average fragrance material. In addition, they usually have a molecular weight of 200 and above and can be perceived in amounts below that of the average perfume material. Fragrance ingredients useful herein, along with their fragrance character and physical and chemical properties, such as boiling point and molecular weight, are listed in Perfume and Flavor Chemicals (Aroma Chemicals), Steffen Arctander, published by the author, 1969, incorporated herein by reference.

Examples for the strongly volatile, low boiling fragrance ingredients are: anethole, benzaldehyde, benzyl acetate, Benzyl alcohol, benzyl formate, isobornyl acetate, kamphene, ciscitral (Neral), Citronellal, Citronellol, Citronellylacetat, Paracymen, Decanal, Dihydrolinalool, Dihydromyrcenol, Dimethylphenylcarbinol, Eukaliptol, geranial, geraniol, geranyl acetate, geranyl nitrile, cis-3-hexenyl acetate, Hydroxycitronellal, d-limonene, linalool, linalooloxide, linalyl acetate, Linalylpropionate, methylanthranilate, alpha-methylionone, methylnonylacetaldehyde, methylphenylcarbinylacetate, Left-menthyl acetate, Menthone, isomenthone, myrcene, myrcenyl acetate, myrcenol, nerol, neryl acetate, Nonyl acetate, phenylethyl alcohol, alpha-pinene, beta-pinene, gamma-terpinene, alpha-terpineol, beta-terpineol, terpinyl acetate and vertenex (para-tertiary butylcyclohexyl acetate). Some natural oils can also size percentages more volatile Contain fragrance ingredients. For example, lavandin contains as main ingredients: linalool; Linalylacetat; Geraniol and citronellol. Lemon oil and orange terpenes Both contain 95% D-limonene.

Examples of moderately volatile perfume ingredients are: amylcinnamaldehyde, isoamylsalicylate, beta-caryophyllene, cedrene, cinnamyl alcohol, coumarin, dimethylbenzylcarbinylacetate, ethylvanillin, eugenol, isoeugenol, fluoroacetate, heliotropin, 3-cis-hexenylsalicylate, hexylsalicylate, lilial (paratertiary butylalphamethyl-hydrocinnamaldehyde), gamma Methylionone, nerolidol, patchouli alcohol, phenylhexanol, beta-selenines, trichloromethylphenylcarbinylacetate, triethylcitrate, vanillin and veratraldehyde. Cedarwood terpenes are composed mainly of alpha-cedrene, beta-cedrene and other C ₁₅ H ₂₄ sesquiterpenes.

Examples for the less volatile, high-boiling fragrance components are: benzophenone, benzyl salicylate, Ethylene brassylate, galaxolide (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gamma-2-benzopyran), Hexyl cinnamaldehyde, lyral (4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-10-carboxaldehyde), Methylatedrylon, methyldihydrojasmonate, methyl-beta-naphthylketone, Musk indanone, musk ketone, musk musk and phenylethyl phenylacetate.

The Selection of any particular fragrance ingredient becomes primarily through aesthetic considerations specified.

The Compositions can a fragrance ingredient in proportions of up to 5.0% by weight, preferably at levels of from 0.1% to 1.5% by weight of the total composition include.

complexing

A another class of optional compounds for this purpose Close use Complexing agent.

complexing can in the compositions in proportions of up to 10.0% by weight, preferably 0.01 Wt .-% to 5.0 wt .-% of the total composition be incorporated.

Suitable phosphonate chelating agents for use herein include alkali metal ethane 1-hydroxy diphosphonates (HEDP), alkylene poly (alkylene phosphonate), and aminophosphonate compounds including amino-amino tri (methylene phosphonic acid) (ATMP), nitrilotrimethylene phosphonates (NTP), ethylenediamine tetramethylene phosphonates, and diethylene triamine pentamethylene phosphonates (U.S. DTPMP). The phosphonate compounds may be present either in their acid form or as salts of various cations on some or all of their acid functions. Preferred phosphonate chelating agents for use herein are diethylene triamine pentamethylene phosphonate (DTPMP) and ethane 1-hydroxy diphosphonate (HEDP). Such phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST ^®

Polyfunctionally-substituted aromatic chelating agents may also be useful in the present compositions. See U.S. Patent 3,812,044, issued May 21, 1974 to Connor et al. Before ferred compounds of this type in acid form are Dihydroxydisulfobenzole, such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelator for use herein is ethylenediamine-N, N'-disuccinic acid or alkali metal or alkaline earth, ammonium or substituted ammonium salts thereof or mixtures thereof. Ethylenediamine N, N'-disuccinic acids, especially the (S, S) isomer, are described in detail in U.S. Patent 4,704,233 issued November 3, 1987 to Hartman and Perkins. Ethylenediamine-N, N'-disuccinic acid is z. Example, under the trade name ssEDDS ^® from Palmer Research Laboratories are commercially available.

Suitable aminocarboxylates for use herein include ethylenediamine tetraacetates, diethylenetriamine pentaacetates, diethylenetriamine pentaacetate (DTPA), N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetrapropionates, triethylenetetraaminehexaacetates, ethanoldiglycines, propylenediaminetetraacetic acid (PDTA), and methylglycinediacetic acid (MGDA), both in their acid form and in their alkali metal form. Ammonium and substituted ammonium salts. For use particularly suitable amino carboxylates are diethylenetriaminepentaacetic acid, propylene diamine (PDTA) which is available for example under the trade name Trilon FS ^® by BASF and methyl (MGDA).

Further Carboxylate complexing agents for use herein include salicylic acid, aspartic acid, glutamic acid, glycine, malonic or mixtures thereof.

bleach

The used here liquid Compositions can also include a bleaching component. Every one of the professionals known can for this purpose Use, including any Peroxygenbleichmittels and any hypohalite bleach.

suitable Peroxy bleach for this purpose Close use Hydrogen peroxide or water-soluble Sources of it. A hydrogen peroxide source as used herein refers to any compound that is active on contact with water Oxygen generated. Suitable water-soluble sources of hydrogen peroxide for this purpose Uses include percarbonates, preformed percarboxylic acids, persilicates, Persulfates, perborates, organic and inorganic peroxides and / or Hydrogen peroxide.

suitable Hypohalite bleaches for use herein include chlorine-releasing Ingredients such. For example, alkali metal hypochlorites. Purpose moderately are the compositions of the invention stable in the presence of this bleaching component. Although alkali metal hypochlorites can be preferred other hypochlorite compounds are also used here and z. B. be selected from calcium and magnesium hypochlorite. A preferred alkali metal hypochlorite for this purpose Use is sodium hypochlorite.

Bleach activators

In a preferred embodiment, in which the compositions of the present invention are a peroxygen bleach includes, can the compositions further comprise a bleach activator.

With "bleach activator" is here a connection meant reacting with peroxide bleaches such as hydrogen peroxide, around a peracid to build. The peracid thus formed represents the activated bleach. To suitable bleach activators for this purpose Use belong those which belong to the class of esters, amides, imides or anhydrides belong.

Examples of suitable compounds of this type are in the British patent GB 1 586 769 and GB 2 143 231 and a process for its formation into a prilled form is described in published European patent application EP-A-62 523. Suitable examples of such compounds for use herein are tetraacetylethylenediamine (TAED), sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate, diperoxydodecanoic acid, as disclosed, for example, in US Pat US 4,818,425 and nonylamide from peroxyadipic acid, such as in US 4,259,201 described, and n-nonanoyloxybenzenesulfonate (NOBS). Also suitable are N-acyl caprolactams selected from the group consisting of substituted or unsubstituted benzoyl caprolactam, octanoyl caprolactam, nonanoyl caprolactam, hexanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, formyl caprolactam, acetyl caprolactam, pro panoyl caprolactam, buta noylcaprolactam, pentanoylcaprolactam or mixtures thereof. A particularly interesting family of bleach activators has been found in EP 624.154 disclosed and particularly preferred in this family is acetyl triethyl citrate (ATC). Acetyl triethyl citrate has the advantage that it is environmentally friendly as it eventually degrades to citric acid and alcohol. In addition, acetyl triethyl citrate has a good hydrolytic stability in the product upon storage and is an effective bleach activator. Finally, it gives the composition a good builder capacity.

Packaging form of the compositions

The in a method according to the invention used compositions in a variety of suitable detergent packages available to those skilled in the art are known to be packaged. The liquid compositions are preferably in conventional Detergent plastic bottles packed.

In an embodiment can the compositions used herein in manual or electrical actuated Packed spray containers which are usually made of synthetic organic polymer plastic bottles are made. Accordingly, includes the present invention also liquid cleaning compositions of the invention contained in a spray dispenser, preferably in a pump lever spray distributor or a pump spray distributor, are packed.

Actually enable it the spray dispensers, the liquid, according to the invention for use suitable cleaning compositions to a relatively large range a surface to be cleaned apply. Such spray dispensers are particularly suitable for cleaning vertical surfaces.

Suitable spray dispensers for use in a method of the invention include manually operated foam dispensers of the trigger type, e.g. From Specialty Packaging Products, Inc., or Continental Sprayers, Inc. These donor species are described, for example, in US 4,701,311 to Dunnining et al. and U.S. 4,646,973 and U.S. 4,538,745, both to Focarracci. Especially preferred for use herein are spray dispensers such as T ^8500® , commercially available from Continental Spray International, or T ^8100® , commercially available from Canyon, Northern Ireland. In such a dispenser, the liquid composition is subdivided into fine liquid droplets which give a spray which is directed to the surface to be treated. In fact, in such a spray dispenser, the composition contained in the body of this dispenser is directed out of the head of the spray dispenser by energy supplied by the user to a pumping mechanism when the user actuates the pumping mechanism. More specifically, the composition in the spray dispenser head is urged against an obstruction, e.g. As a grid or a cone or the like, which impacts are caused, which help in the atomization of the liquid composition, that help in the formation of liquid droplets.

Examples

These compositions were prepared to contain the listed ingredients in the listed proportions (wt%).

Of the pH of these examples is acidic.

Isalchem 123 AS ^® is a branched alkyl sulfate and commercially available from Enichem. Kelzan T ^® is a xanthan gum, available from Kelco.

Luviskol K60 ^® is a polyvinylpyrrolidone available from BASF.

n-BPP is butoxypropoxypropanol, commercially available from Dow Chemical.

Dobanol ^® 91-8 is an ethoxylated C ₉ -C ₁₁ alcohol, commercially available from Shell.

Lutensol® AO 30 is an ethoxylated C _12-14 alcohol, commercially available from BASF.

All of the aforementioned compositions used in a method according to the invention sure for Enamel when used to treat enamel surfaces become.

Claims (10)

Method for cleaning an enamel surface with a liquid acidic composition, a source of acidity and an enamel comprising a secure buffer system, wherein the buffer system is a salt with an anion selected from the group consisting of hydroxide and carbonate, and a cation, which has an ionic radius greater than 115 pm; With the proviso that no ethers of diethylene glycol are present in the composition. The method of claim 1, wherein the cation is selected from the group consisting of a potassium ion, an ammonium ion, a cesium ion, a barium ion and a quaternary ammonium ion. Method according to one of the preceding claims, wherein the cation has an ionic radius of at least 125 pm. A process according to any one of the preceding claims, wherein the buffering component is selected from the group consisting of potassium hydroxide (KOH), potassium carbonate (K ₂ CO ₃ ), potassium hydrogen carbonate (KHCO ₃ ), ammonium hydroxide (NH ₄ OH), ammonium carbonate ((NH ₄ ) ₂ CO ₃ ), ammonium bicarbonate (NH ₄ HCO ₃ ), cesium hydroxide (CsOH), barium hydroxide (Ba (OH) ₂ ), barium carbonate (BaCO ₃ ) and mixtures thereof. Method according to one of the preceding claims, wherein the composition of from 0.1% to 5% by weight of the total composition the buffer system comprises. Method according to one of the preceding claims, wherein the composition has a pH below 7. The method of claim 7, wherein the composition between 0.5% by weight and 10% by weight of the total composition is an acidity source includes. Method according to one of the preceding claims, wherein the composition further comprises a surfactant. The method of claim 8, wherein the composition up to 15% by weight the total composition comprises a surfactant. Use of a secure enamel buffer system in a liquid acidic composition comprising an acidity source for cleaning an enamel surface, wherein the buffer system is a salt having an anion selected from the group consisting of hydroxide and carbonate, and a cation, which has an ionic radius greater than 115 pm; in which the composition for Enamel is safe; with the proviso that no ethers of diethylene glycol are present in the composition.