DE69732777T2 - Acid liquid scale removal compositions packaged in a spray dispenser - Google Patents

Abstract

The present invention relates to liquid acidic compositions suitable for removing limescale-containing stains from a hard-surface, comprising an acid, from 0.001% to 20% by weight of the total composition of a polysaccharide polymer and from 0.001% to 20% by weight of the total composition of a vinylpyrrolidone homopolymer or copolymer, said composition being packaged in a spray type-dispenser. Such a composition provides improved shine to the surface treated while exhibiting effective limescale removal performance. The use of a polysaccharide polymer and a vinylpyrrolidone homopolymer or copolymer, in a liquid acidic composition being packaged in a spray-type dispenser, to treat a hard-surface, reduces or even prevents the formation of watermarks and even limescale deposits on said hard-surface after said hard-surface has first been treated with said composition and subsequently comes in contact with water. Also the use of a polysaccharide polymer and a vinylpyrrolidone homopolymer or copolymer, in a liquid acidic composition being packaged in a spray-type dispenser, to treat a hard-surface delivers shine/long lasting shine to the surface.

Description

TECHNICAL FIELD OF THE INVENTION

The The present invention relates to liquid acid packed in a spray dispenser Compositions for the removal of calcium deposits.

BACKGROUND THE INVENTION

tap water contains a certain amount of dissolved Ions, which in case of evaporation of water finally as salts like calcium carbonate on hard surfaces, the common come into contact with water, be deposited, resulting in an unaesthetic Appearance of the surfaces leads. This phenomenon The formation and deposition of limescale is in places with especially hard water even more acute.

On It is well known in the art that lime deposits are chemical removed with acidic solutions can be and for this purpose a wide variety of acidic compositions have been used Removal of limescale described.

Besides that is it desirable that such liquid acidic compositions in addition to the ability for effective removal of limescale present on a surface the ability own the treated surfaces to give a good shine. However, surface gloss is often impaired, since water tends to drip on contact with hard surfaces the surface to form, rather than a thin, evenly over the surface to form distributed film or to run off the surface. With water evaporation does this to that hard water soluble inorganic salts such as calcium / magnesium carbonate and / or phosphate salts with consequent formation of water residues on the surface and after all Lime deposits are deposited, resulting in an unaesthetic Appearance of the surface leads.

The European patent application EP 0 013 585 discloses a gentle liquid hand dishwashing composition comprising (a) an anionic and / or nonionic surfactant, (b) a copolymer of N-vinylpyrrolidone and dimethylaminoethyl methacrylate, and (c) an alkali metal salt of casein. The composition has characteristics for modifying draining processes which cause a quick and uniform dripping of running water from rinsed dishes and utensils without the disadvantage of staining and filming.

The European patent document EP 0 091 194 discloses a thioxotropic coating composition in the form of a paste or gel for rust removal of metal surfaces comprising (a) 2-15% of an acid, (b) 3-15% xanthan gum and (c) 10-40% polyvinylpyrrolidone.

It is thus an object of the present invention, the formation of Water residues and / or calcium deposits on a hard surface, with a liquid acidic composition has been treated to reduce and this surface to give it a better shine. It is especially a task the present invention, liquid to provide acidic compositions which provide the treated surface with a give better gloss and at the same time an excellent performance when removing limescale. Another task It is the object of the present invention to provide such liquid acidic compositions in a practical way to avoid any of it Consumers carried out operations for decalcification of hard surfaces to facilitate.

With The present invention addresses these problems by formulation of liquid overcome acidic compositions, comprising an acid, a polysaccharide polymer (0.001% -20%) and a vinylpyrrolidone homopolymer or copolymer (0.001% -20%), wherein the compositions are packaged in a spray dispenser. Actually has It has been found that by the addition of a polysaccharide polymer, preferably xanthan gum, together with a vinylpyrrolidone homopolymer or copolymer, to a liquid acidic composition the formation of lime deposits on one Surface that previously treated with such a composition is reduced or even prevented. Furthermore a lower formation of water residues on a surface is observed those previously treated with the compositions described herein and then, for example while a rinsing process, comes into contact with water, giving the surface a better gloss becomes.

Another advantage of the present invention is the fact that the gloss advantage associated with a hard surface treated with the compositions of the present invention, even after several cycles of rinsing, so as to provide long lasting protection against the formation of water residues and / or even limescale deposits on the surface and thus long-lasting glossy surfaces. In other words, the housewife has the advantage of being able to defer the next descaling process. The gloss benefits described herein are advantageously achieved at very low total concentrations of both a polysaccharide polymer and a vinylpyrrolidone homopolymer or copolymer in the acidic compositions of the present invention.

One Another advantage of the liquid acidic compositions of the invention is the fact that the treated surfaces become smoother (this becomes by touch the surfaces ) Perceived. This can also help the consumer To convey the perception of a perfectly decalcified surface.

It was surprisingly also found that by the compositions of the invention the ones mentioned here Advantages (eg reducing or preventing the formation of Water residues and / or even limescale, which is a good and even long-lasting Gloss advantage) when the compositions are used to treat a variety of of surfaces, including metal surfaces such as aluminum, chrome steel, stainless steel, synthetic materials like vinyl, linoleum, glazed or unglazed ceramic tiles and / or enamel surfaces, be used.

In a preferred embodiment of the present invention include the compositions herein maleic together with a second acid, usually Sulfamic acid. It has been found that these compositions are particularly gentle on various types of hard surfaces treated with it as well milder for the skin are.

One Another advantage of the present invention is the fact that the present compositions compared to the application a liquid Composition by direct casting on the treated surface instead of by inventive spraying, under Use a minimal amount of the composition slightly the surface to be treated can be applied. Furthermore allows spraying the composition in comparison to the surface to be treated for casting the liquid Composition on the surface to be treated the treatment of a larger area with a given amount of the product. In addition, the danger of spilling as well as the tendency of the liquid Compositions to be dirty when applied to the surface, when applied using a spray dispenser.

The liquid Acidic compositions of the present invention will be advantageous using a spray dispenser on the surfaces to be treated applied and are both for the user as well the surfaces treated with it gently. Indeed can the present acidic compositions with minimal inhalation by the user of the acidic compositions and thus under Avoidance of any potential health hazard due to Presence of an acid sprayed in the compositions on the surfaces to be treated.

STATE OF TECHNOLOGY

compositions The removal of limescale involving acids is well known in the art known. For example, EP A 666 305 discloses acidic compositions for the removal of calcium deposits, the maleic acid and a second acid such as sulfamic include. However, it does not disclose liquid acidic compositions, as described in the present invention, which is a polysaccharide polymer together with a vinylpyrrolidone homopolymer or copolymer, disclosed.

EP A 467 472 discloses a liquid Composition for hard surfaces with antistatic / dirt-repellent cationic quaternized Polymers. Cationic quaternized polymethacrylates include Beta (trialkylammonium) ethyl methacrylates / acrylates. It will be in it but no liquid acidic compositions as described in the present invention, a polysaccharide polymer together with a vinylpyrrolidone homopolymer or Copolymer.

WO 94/26858 discloses acidic compositions (pH 2-8) comprising a nonionic surfactant and an anionic polymer having an average molecular weight of less than 1,000,000, the polymer being free of quaternary nitrogen groups. There are, however, no liquid acid co compositions as described in the present invention comprising a polysaccharide polymer together with a vinylpyrrolidone homopolymer or copolymer.

SUMMARY THE INVENTION

The The present invention relates to a liquid acidic composition, the stains containing limescale deposits from a hard surface suitable, comprising an acid of a polysaccharide polymer at 0.001% to 20% by weight of the total composition and a vinylpyrrolidone homopolymer or copolymer at 0.001% by weight. to 20 wt .-% of the total composition, wherein the composition in a spray dispenser is packed.

The The present invention also includes a method of treatment hard surfaces, wherein an acidic according to the invention liquid Composition from a spray dispenser on the surfaces applied, then on the surfaces is allowed to act and then removed by rinsing.

DETAILED DESCRIPTION OF THE INVENTION

The liquid acidic compositions:

The Liquid compositions according to the invention are acidic compounds. Accordingly, the compositions of the invention typically at a pH of less than 7, preferably less than 5, more preferably below 4, more preferably at a pH between 0 and 3, even more preferably at a pH between 0.1 and 2.5, even more preferably between 0.1 and 2, and most preferably one pH formulated between 0.3 and 1.5.

The Liquid compositions according to the invention are preferably aqueous Compositions. They therefore typically comprise up to 50% by weight. up to 98% by weight of the total composition water, preferably 60% to 95%, and more preferably 70% to 90%.

The Compositions of the invention are intended for the removal of calcium deposits. Accordingly, they as the first central component of an acid or a mixture thereof. Typically, you can the acids to be used herein any inorganic or organic acid well known to those skilled in the art is known, or a mixture thereof. Suitable acids for related Uses include maleic acid, Citric acid, adipic acid, sulfamic, Phosphoric acid, Nitric acid, malic acid, sulfonic acid, sulfuric acid or their salts or mixtures thereof. Indeed, such acids can be found in their acid form or in the form of their salts (mono-, di-, trisalts) and in all their anhydrous and hydrated forms or mixtures used of it. Such acids can typically in the form of their alkali metal salts (eg, sodium salt, Potassium salt and the like) or their alkali hydrogen acid salts be used. The compositions comprise from 0.1% by weight to 70% by weight of the total composition of an acid or a mixture thereof.

Here in Preferably, the compositions according to the invention comprise at least Maleic acid. Accordingly, the compositions of the invention from 0.1% to 45% by weight of the total composition of maleic acid, preferably 1% to 25%, and more preferably 3% to 20%. This percentage will calculated on the basis of the molecular weight of the acid form, however Maleic anhydride alike Use in the compositions according to the invention suitable. Indeed is maleic anhydride generally cheaper and gets into the acid form converted when it is in an aqueous Medium is included. In one embodiment of the present invention Invention becomes maleic acid alone as the acid the acidic acid according to the invention Used compositions.

In another version In the present invention, a second acid is added to the maleic acid. It is he wishes, that the second acid Increases the performance in the removal of limescale deposits. Preferably is the first pKa of the second acids to be used herein on many surfaces are not particularly efficient at removing limescale greater than 5, more preferably not larger than 3, and most preferably not greater than 2. According to the present Invention can the acids organic or inorganic acids be. examples for inorganic acids are sulfonic acid derivatives, sulfamic (pKa = 0.1), hydrochloric acid (pKa <0), nitric acid (pKa <0), phosphoric acid (pKa = 2.1) and sulfuric acid (pKa = 0.4). An example for an organic acid is citric acid (pKa = 3.06).

Particularly suitable for use herein is sulfamic acid. Sulfamic acid can be found in the he Compositions according to the invention may be added in its acid form or as an alkali metal salt thereof. Accordingly, sulfamic acid may be added, for example, as sulfamate. Sulfamic acid is commercially available, for example, under its chemical name from Albright & Wilson or Nissan Chemicals. In fact, it has been found that the addition of sulfamic acid to maleic acid in the compositions of the invention improves the skin mildness of the compositions. In fact, when the skin comes in contact with these compositions, less skin irritation is experienced by the user compared to the same compositions but without sulfamic acid.

Other suitable second acids are sulfonic acid derivatives including alkylsulfonic and arylsulfonic acids.

suitable alkylsulfonic for this purpose Use is linear or branched C1-C6-alkyl sulfonic acids or Mixtures of which, such as methanesulfonic acid (pKa = 1.9), are commercially available For example, Aldrich, William Blythe & Co. Ltd. or Elf Atochem.

worin R₁, R₂, R₃, R₄ und R₅ jeweils H oder SO₃H oder eine lineare oder verzweigte C₁-C₄-Alkylkette oder Mischungen davon sind.Suitable arylsulfonic acids for use herein correspond to the following formula:

wherein R ₁ , R ₂ , R ₃ , R ₄ and R _{5 are} each H or SO ₃ H or a linear or branched C ₁ -C ₄ alkyl chain or mixtures thereof.

preferred arylsulfonic for this purpose Use are those that include no or only one alkyl chain. Indeed are such arylsulfonic acids especially effective at removing limescale, resulting in their longer Alkyl chain homologs is not the case. In addition, such arylsulfonic acids are special gentle on the surface treated with it. Particularly suitable arylsulfonic acids for this purpose Uses are benzenesulfonic acid (pKa = 0.7), toluenesulfonic acid and cumene sulfonic acid. Among these three we have the same percentage by weight found out that the power to remove limescale increases, the shorter the alkyl chain is and highest without alkyl chain.

preferred acids for this purpose Use whose first pKa is not greater than 5 is sulfamic acid, sulfuric acid, arylsulfonic acids, alkylsulfonic acids, citric acid, nitric acid, phosphoric acid, hydrochloric acid or Mixtures thereof, more preferred are sulfamic acid, citric acid or Mixtures thereof and especially preferred is sulfamic acid.

The Compositions of the invention from 0.1% to 25% by weight of the total composition comprises one second acid, their first pKa value is not bigger as 5, or mixtures thereof, preferably 0.1% to 20%, more preferably 0.1% to 10%, and most preferably 0.1% to 7%.

The inventive liquid acidic Compositions include as the second central component Vinylpyrrolidone homopolymer or copolymer or mixtures thereof at a level of from 0.001% to 20% by weight of the total composition. Typically, the compositions of the invention comprise 0.01% Wt .-% to 5 wt .-% of the total composition of a vinylpyrrolidone homopolymer or copolymer or a mixture thereof, more preferably 0.01% to 3% and most preferably 0.01% to 1%.

worin n (Polymerisationsgrad) eine ganze Zahl von 10 bis 1.000.000 ist, vorzugsweise von 20 bis 100.000 und mehr bevorzugt von 20 bis 10.000.Suitable vinylpyrrolidone homopolymers for use herein are homopolymers of N-vinylpyrrolidone with the following repeating 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 from 1,000 to 100,000,000, preferably from 2,000 to 10,000,000, more preferably 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® (10,000 molecular viscometry), PVP K- ^30® (average molecular weight 40,000). , PVP K- ^60® (average molecular weight of 160,000) and PVP K- ^90® (average molecular weight of 360,000). Other suitable vinylpyrrolidone homopolymers which are commercially available from BASF Corporation include Sokalan HP 165 ^®, Sokalan HP 12 ^{®, ®} Luviskol K30, Luviskol K60 ^®, Luviskol K80 ^®, Luviskol K90 ^®; Vinylpyrrolidone homopolymers are known to those skilled in the detergent art (see, for example, EP A 262 897 and EP A 256 696).

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

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

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

For example have particularly suitable N-vinylimidazole-N-vinylpyrrolidone polymers for this purpose Uses an average molecular weight of 5,000 to 1,000,000, preferably from 5,000 to 500,000 and more preferred from 10,000 to 200,000. The average molecular weight range was determined by light scattering, as in Barth H.G. and Mays J.W., Chemical Analysis, Vol. 113, "Modern Methods of Polymer Characterization " described.

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 not quaternized vinyl pyrrolidone / dialkylaminoalkyl acrylate or methacrylate copolymers.

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 bedeutet eine Niederalkylgruppe mit 1 bis 4 Kohlenstoffatomen, vorzugsweise Methyl oder Ethyl; X^– ist ausgewählt aus der Gruppe bestehend aus Cl, Br, I, 1/2SO₄, HSO₄ und CH₃SO₃. Die Polymere können mit Hilfe des Verfahrens hergestellt werden, das in den französischen Patenten Nr. 2,077,143 und 2,393,573 beschrieben ist.Such vinyl pyrrolidone / dialkylaminoalkyl acrylate or methacrylate copolymers (quaternized or non-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 represents} a lower alkyl group having 1 to 4 carbon atoms, preferably methyl or ethyl; X ^- is selected from the group consisting of Cl, Br, I, 1 / 2SO 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 second key ingredients for use herein are the vinylpyrrolidone homopolymers.

The inventive liquid acidic Compositions include as the third central component Polysaccharide polymer or a mixture thereof in a proportion of From 0.001% to 20% by weight of the total composition. typically, include the compositions of the invention from 0.01% to 10% by weight of the total composition of a polysaccharide polymer or a mixture thereof, more preferably 0.01% to 5% and most preferably 0.01% to 2%.

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 from that.

Especially polysaccharide polymers for use herein are xanthan gum and derivatives thereof. Xanthan gum and derivatives thereof are commercially available for example from Kelco under the trade name Keltrol RD ^®, Kelzan S or Kelzan T ^{® ®.} Other suitable Xanthangumini are commercially available from Rhone-Poulenc under the trade name Rhodopol T ^® and Rhodigel X747 ^®. Succinoglykangummi for use herein is commercially available from Rhone-Poulenc under the trade name Rheozan ^®.

The polysaccharide polymers herein can act as a thickener, thus the present liquid acid compositions when measured with a Carri-med rheometer CLS ^100® 5 N / m ² and 20 ° C has a viscosity of 0.001 Pa · s to 1.5 Pa · s, preferably 0.02 Pa · s to 0.8 Pa · s and more preferably 0.05 Pa · s to 0, 6 Pa · s on.

The Polysaccharide polymers, preferably xanthan gum or derivatives thereof, and vinyl pyrrolidone homopolymers or copolymers are disclosed in the acidic conditions of the present compositions are advantageous physically and chemically stable, even at a very low level pH of typically below 1.5.

The present acidic liquid Compositions are chemically stable, d. H. there are practically none chemical changes the different components due to the reaction between different Components, and physically stable, d. H. in storage in a rapid aging test (RAT) at 50 ° C over a Period of 10 days, no phase separation occurs.

It has now surprisingly that the polysaccharide polymers described herein, preferably xanthan gum or derivatives thereof, and vinyl pyrrolidone homopolymers or copolymers when added to a liquid acidic composition, in a spray dispenser is packaged, creating a better gloss and not at the same time the performance of the composition in the removal of limescale affect.

The The present invention is based on the finding that the in the compositions of the invention existing polysaccharide polymers and vinylpyrrolidone homopolymers or copolymers are able to modify the surface by they deposit themselves on the surface treated with it. Without being bound to a theory was observed to be typically hard surfaces found in a household neither strongly hydrophobic are still very hydrophilic. That means that upon contact with water with hard surfaces its distribution, which is determined by the interfacial energy (that is, the surface tension solid / liquid) is determined, is very limited. In fact, it was observed that the most stable configuration for the water is the grouping in spherical droplets and not the formation of a thin, evenly over the surface distributed film or running off the surface. at the evaporation of the water droplets then gradually increases their salt content progressively more so that finally carbonate salts are precipitated, to water residues or even cause limescale deposits. The end result is a reduction in surface gloss.

It has now been found that when adding the polysaccharide polymers, as described herein, to the liquid acidic compositions a hydrophilic layer on a hard surface treated therewith, in particular on surfaces low-energy such as stainless steel, leaving behind the hydrophilic Layer leads to that the water that is in contact with the previously so treated surface (for example, water that is used for rinsing the so treated surfaces used) evenly over the Distributed surface becomes ("foil effect") instead of droplets form. It's about it In addition, it was found that when adding the vinylpyrrolidone homopolymers or copolymers as described herein to liquid acidic compositions a hydrophobic layer on a hard surface treated therewith, in particular on surfaces with high energy such as ceramics, porcelain, glass and the like, remains, wherein the hydrophobic layer causes the water to interact with the previously treated surface comes into contact (eg, water used to rinse off the surfaces thus treated will), from the surface expires instead droplet to build. Thus, by modifying the surface features, as shown, the formation of water residues and / or lime deposits reduced or even prevented during drying. With others Words act the second and the third central part of composition according to the invention together to the benefits described here for all types of hard surfaces, of surfaces with low to surfaces with high energy, provide.

A Definition of it, what under surfaces understood with low energy up to surfaces with high energy is in is "surfactant Science and Technology ", 2nd Edition, by Drew Myers, 1992, VCH Publishers Inc., on the pages 268-272 listed.

In addition, it has surprisingly been found that the polysaccharide polymers and vinylpyrrolidone homopolymers or copolymers not only have the ability to adhere to a surface which has been treated with the liquid acidic compositions of the present invention containing these polysaccharide polymers and vinylpyrrolidone homopolymers -Copolymers and are packaged in a spray dispenser, but even after several rinse cycles (eg, when water is applied later to this surface, for example, in a sink in daily household operations) continue to adhere to the surface and thus a long-lasting protection against the formation of water residues and / or to provide limescale and hence long lasting glossy surfaces.

Without to be bound by theory, it is believed that the polysaccharide polymers and vinylpyrrolidone homopolymers or copolymers also the ability own, on the surface the skin of the user to make a film and thereby the skin's mildew properties continue to reinforce due to the presence of sulfamic acid together with maleic acid, the otherwise as stronger irritating to the skin, causing this in the preferred embodiment the present invention is true, in the actual sulfamic acid together with maleic acid is used.

One additional Advantage regarding the use of polysaccharide polymers and vinylpyrrolidone homopolymers or copolymers in the present acidic compositions the fact that when they adhere to hard surfaces, making them more hydrophilic, the surfaces themselves become smoother (this can be done by touching the surfaces be perceived) and thus contribute to the perception of a perfectly decalcified surface to convey.

These Advantages are advantageous at low levels of those described herein Polysaccharide polymers, preferably xanthan gum or derivatives thereof, and vinylpyrrolidone homopolymers or copolymers obtained, so that still another advantage of the present invention therein lies that the desired benefits be provided at low cost. The liquid acidic according to the invention Compositions typically comprise from 0.002% to 5% by weight Wt .-% of the total composition of a polysaccharide polymer or a mixture thereof together with a vinylpyrrolidone homopolymer and / or copolymer, preferably 0.005% to 2%, more preferably 0.01% to 2%, and most preferably 0.01% to 1%.

When Another essential feature are the liquid acids according to the invention Compositions in a spray dispenser packed up.

With The term "spray dispenser" is any The spray dispenser known to the person skilled in the art meant, including Trigger spray dispensers or pump spray dispensers.

Suitable spray dispensers for use in the invention include manually operated foam dispensers of the trigger type, e.g. From Specialty Packaging Products, Inc., or Continental Sprayers, Inc. These donor types are z. In U.S. 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-type dispensers such as T8500 T8900 ^® or ^®, commercially available from Continental Spray International or T8100 ^®, 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.

preferred Foam dispensers of the trigger type for use herein have one Cone as an impact zone. The two main dimensions, through the property, size and pattern distribution of the Foam are determined opening diameter and distribution channel width. By the interaction of these two factors Beyond that the flow rate and the rate of flow through the nozzle are determined.

A preferred trigger Schaumsprühspender for use herein is the known as the T8900 ^® model, which is commercially available from CSI. This foam spray dispenser has a piston pump with an impingement tube that contacts the spray cone, creating turbulence and creating foam. This foam spray dispenser originally had an opening diameter of 0.0007 m (0.7 mm) and a width of 0.00108 m (1.08 mm), based on two distribution channels. Such a commercially available atomizer may also be subjected to modifications to improve the spray pattern and reduce the spray effect. Preferred configurations are, for example, those with smaller distribution channels and larger openings leading to a foam spray with less spray formation. A more preferred configuration has a diameter orifice of 0.00076 m (0.76 mm) or 0.00081 m (0.81 mm) in width and distribution channels of 0.00108 m (1.08 mm) or 0.00076 in (0 , 76 mm) width. The am Most preferred foam spray dispensers have an 0.7676 m (0.76 mm) orifice and 0.00108 m (1.08 mm) manifolds.

The Trigger foam spray dispensers mentioned in the present invention preferably have a bayonet lock instead of a threaded closure and thereby provide a child safety device. Actually allowed the bayonet case (with two or four noses) that the spray dispenser in a safer Way is attached to the bottle, allowing easy opening through Children and uncleanliness during use can be prevented.

One Advantage of the present invention is the fact that the acidic liquid compositions with the help of a spray dispenser evenly a relatively large one Area of a surface to be treated can be applied, wherein They perform excellently in the removal of limescale deposits guarantee and at the same time very gentle on the treated surface and the user.

One Another advantage of the present invention is the fact that the liquid acids according to the invention Easily released compositions on the surfaces to be treated can be.

One another advantage according to the present Invention is the fact that the surface treatment in an economic Way executed is, d. h., it is no longer used by the product as really necessary.

optional ingredients

The Compositions of the invention can Furthermore a variety of other ingredients, including surfactants, colorants, bactericides, thickeners, dyes, Masking agents, pigments, solvents, Stabilizers, fragrances, corrosion inhibitors and the like.

surfactants

One in particular, preferred optional ingredient for use in the compositions of the invention is suitable, is a surfactant or a mixture thereof. Surfactants are desired herein since they contribute to the cleaning advantages of the compositions according to the invention contribute to the removal of calcium deposits. In fact, that promotes Presence of a surfactant, the cleaning of greasy soap scum the present compositions.

general allows the presence of a surfactant in the liquid acids according to the invention Compositions, the surface tension to reduce and the wettability of the liquid acidic with the inventive Improve compositions of treated surfaces. The presence a surfactant or a mixture thereof in the liquid acids according to the invention Compositions supported the solubilization the pollution.

Accordingly, the Compositions of the invention a surfactant or a mixture thereof. The compositions of the invention can up to 40% by weight of the total composition of a surfactant or a Mixture thereof, more preferably 0.05% to 15%, more preferably 0.1% to 10%, and most preferably 0.1% to 5%. In the present Invention can all types of surfactants are used, including non-ionic, anionic, cationic, zwitterionic or amphoteric surfactants. It is also possible, Use mixtures of such surfactants, without departing from the spirit of the present Deviate from the invention.

Especially preferred surfactants for this purpose Uses are zwitterionic surfactants. In fact, these have on addition to the acidic according to the invention Compositions the ability to Performance of the acidic system in removing limescale maintain (ie a similar one Performance in removing limescale compared to the same acidic compositions but without a surfactant) while they are simultaneously with the compositions of the invention an excellent ability for cleaning greasy soap foam.

Suitable zwitterionic surfactants for use herein contain both basic and acidic groups which form an internal salt containing both cationic and anionic hydrophilic groups pen on the same molecule in a relatively large pH range. The typical cationic group is a 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 general 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, C ₁ -C ₆ alkyl, hydroxyalkyl or another substituted C ₁ -C ₆ alkyl group; R ₃ is C ₁ -C ₆ -alkyl, hydroxyalkyl or another substituted C ₁ -C ₆ -alkyl group which may 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 unit connecting the cationic nitrogen atom to the hydrophilic group, and is usually an alkylene, hydroxyalkylene or polyalkoxy group having 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, ester groups. More preferably, R _{1 is} an alkyl group of 1 to 24 carbon atoms, preferably 8 to 18, and more preferably 10 to 16. 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 not is atoms substituted hydrocarbon chain having from 8 to 20 carbon atoms, preferably an alkyl group having 8 to 20 carbon atoms, preferably up to 18, more preferably up to 16, R _b is either a hydrogen a short chain alkyl or substituted alkyl having 1 to 4 carbon atoms, preferably a 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 1 to 4, preferably 2 to 3 , more preferably 3, and not more than one hydroxy group on each (C (R _c ) ₂ ) moiety.

Preferably, R _{2 is} hydrogen or an alkyl or substituted alkyl of 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 of 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 _{4 is} (CH 2) _n , where n is an integer from 1 to 10, preferably from 1 to 6, more preferably from 1 to 3.

Some general examples of Betaine / sulfobetaine are described in US Pat 2,255,082.

Examples of particularly suitable alkyl dimethyl betaines include coco dimethyl betaine, lauryl dimethyl betaine, decyl dimethyl betaine, 2- (N-decyl-N, N-dimethyl ammonium) acetate, 2- (N-coco-N, N-dimethyl ammonium) acetate, myristyl dimethyl betaine, palmityldimethyl betaine, cetyl dimethyl betaine, stearyl. For example, coconut dimethylbetaine is commercially available from Seppic under the trade name Amonyl 1265 ^®. Lauryl betaine is commercially available from Albright & Wilson under the trade name Empigen BB / L ^®.

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

Especially preferred zwitterionic surfactants for use in the acidic compositions of the present invention are the sulfobetaine surfactants as they provide optimal removal benefits of limescale and soap scum cleaning.

Examples of particularly suitable sulfobetaine surfactants include tallow bis (hydroxyethyl) sulfobetaine, cocoamidopropyl hydroxysulfobetaines commercially available from Rhone-Poulenc and Witco under the trade name Mirataine CBS ^® or Rewoteric AM CAS 15 ^{® are} available.

Further examples of amido betaines / amidosulfobetaine include cocoamidoethyl betaine, cocoamidopropyl betaine or C10-C14 fatty acylamidopropylene (hydropropylene) sulfobetaine. C10-C14 fatty acylamidopropylene (hydro) sulfobetaine, for example commercially available from Sherex Company under the trade name "Varion CAS ^® sulfobetaine".

Suitable amine oxides for use herein correspond to the formula R ₁ R ₂ R ₃ NO wherein R1, R2 and R3 is independently a saturated or unsaturated, substituted or unsubstituted, linear or branched alkyl group having 1 to 30 carbon atoms and preferably 1 represent up to 20 carbon atoms , Particularly preferred amine oxides for use in this invention are amine oxides of the formula R ₁ R ₂ R ₃ NO wherein R _{1 is} a saturated or unsaturated, substituted or unsubstituted, linear or branched alkyl group of 1 to 30 carbon atoms, preferably 8 to 20 carbon atoms, more preferably 6 to 16, most preferably 8 to 14 and wherein R2 and R3 are independently substituted or unsubstituted, linear or branched alkyl groups having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, and more preferably methyl groups or mixtures thereof.

Suitable amine oxides for use herein are, for example, coco-dimethylamine oxides, C12-C16 dimethylamine oxides. The amine oxides are commercially available from Hoechst, Stephan, AKZO (under the trade name Aromox ^®) or FINA (under the trade name Radiamox ^®).

suitable Amines to the relevant Use correspond to the formula RR'R ,, N, wherein R is a saturated or unsaturated, substituted or unsubstituted, linear or branched Alkyl group having 1 to 30 carbon atoms, and preferably 1 to 20 Is carbon atoms and wherein R 'and R "are independently saturated or unsaturated, substituted or unsubstituted, linear or branched Alkyl groups having 1 to 30 carbon atoms or hydrogen. Particularly preferred amines for use according to the invention are amines with of the formula RR'R ,, N, wherein R is a saturated or unsaturated, linear or branched alkyl group having 1 to 30 carbon atoms, preferably 8 to 20 carbon atoms, more preferably 6 to 16, most preferably 8 to 14 and wherein R 'and R "independently substituted or unsubstituted, linear or branched alkyl groups 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, and more preferably methyl groups or mixtures thereof.

Suitable amines for use herein are, for example, C12-dimethylamine, coco-dimethylamine, C12-C16-dimethylamine. The amines are commercially available from Hoechst under the trade name Genamin ^®, AKZO under the trade name Aromox ^® or Fina under the trade name Radiamine ^®.

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, methylsulfate, methylsulfonate or hydroxide, R _{1 is} a saturated or unsaturated, substituted or unsubstituted, linear or branched alkyl group having 1 to 30 carbon atoms, preferably 12 to 20, more preferably 8 to 20, and R ₂ , R ₃ and R _{4 are} independently hydrogen or saturated or unsaturated, substituted or unsubstituted, linear or branched alkyl groups having 1 to 4 carbon atoms, preferably 1 to 3, and more preferably are methyl. In particular, quaternary ammonium surfactants herein R ₁ is a preferred 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). Particularly preferred are lauryltrimethylammonium salts. Such quaternary Trimethylammoniumtenside are commercially available from Hoechst, or under the trade name Empigen CM ^® by Albright & Wilson.

In a preferred embodiment, the surfactant used in the acidic compositions of the present invention is a surfactant system comprising a zwitterionic surfactant with a second surfactant, e.g. An amine oxide and / or amine and / or a quaternary ammonium surfactant as described herein, having a weight ratio between the zwitterionic surfactant and the second surfactant of at least 1: 1, preferably at least 2: 1. This surfactant system imparts optimum performance to the acidic compositions of the present invention in removing scale deposits (ie, comparable to the performance of the same compositions, but without a surfactant, in the removal of limescale) also optimal performance when cleaning greasy soap scum.

suitable Nonionic surfactants for use herein are alkoxylated nonionic alcohol surfactants readily available in the art well-known condensation processes can be made. A size Variety of such alkoxylated alcohols, in particular ethoxylated and / or propoxylated alcohols, but is also convenient available in the stores. There are surfactant catalogs available, in which numerous surfactants, including nonionic surfactants, are listed.

Accordingly, preferred alkoxylated alcohols for use herein are nonionic surfactants of the formula RO (E) e (P) pH, where R is a hydrocarbon chain of 2 to 24 carbon atoms, E is ethylene oxide and P is propylene oxide, and e and p are the average ethoxylation alcohols. or Propoxylierungsgrad stand, 0 to 24 are. The hydrophobic group of the nonionic compound may be a primary or secondary, straight or branched alcohol having 8 to 24 carbon atoms. Preferred nonionic surfactants for use in the compositions of the invention are the condensation products of ethylene oxide with alcohols having a straight alkyl chain of 6 to 22 carbon atoms, the degree of ethoxylation being 1 to 15, preferably 5 to 12. Such suitable nonionic surfactants are commercially available for example from Shell under the trade name Dobanol ^® or from BASF under the trade name Lutensol ^®. These nonionic surfactants are preferred because they have been found to permit the formulation of a stable product without the need to add stabilizers or hydrotropes.

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 ₁₂ -C ₁₈ alkyl group, and more preferably a C C ₁₄ -C ₁₆ alkyl group, and M is H or a cation, for example, an alkali metal cation (e.g., sodium, potassium, lithium) or ammonium or a substituted ammonium (e.g., a methyl, dimethyl and trimethyl ammonium cation and quaternary ammonium cations such as the cations tetramethylammonium and dimethylpiperidinium, and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof).

"Secondary C6-C20-alkyl or C6-C20-alkylarylsulfonates " here, that in the formula defined above, the SO3M or aryl-SO3M group is connected to a carbon atom of the alkyl chain, between two other carbon atoms of the alkyl chain is arranged (secondary carbon atom).

An example of a C14-C16 alkyl sulfonate is HostapurTM ^® 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, which are commercially available under the tradename ^Nansa® from Albright & Wilson.

Suitable alkyl sulfate 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 groups of 6 to 20 carbon atoms and alkylphenyl groups of 6 to 15 carbon atoms in the alkyl group. M is H or a cation, for example an alkali metal cation (eg sodium, potassium, lithium, calcium, magnesium and the like) or ammonium or a substituted ammonium (eg a methyl, dimethyl and trimethylammonium cation and quaternary Ammonium cations such as the cations tetramethylammonium and dimethylpiperidinium, and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).

Suitable alkoxylated alkyl sulfate surfactants for use herein correspond to the formula RO (A) _m SO ₃ M wherein R is an unsubstituted C ₆ -C ₂₀ alkyl or hydroxyalkyl 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 an ethoxy or propoxy moiety, m is greater than zero, usually between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which may be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium, or a substituted ammonium cation. Here also ethoxylated alkyl sulfates and propoxylated alkyl sulfates are considered. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations such as tetramethyl-ammonium, dimethyl-piperidinium and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine, mixtures thereof and the like. Exemplary surfactants are polyethoxylated (1,0) C ₁₂ -C ₁₈ alkyl sulfate (C ₁₂ -C ₁₈ E (1.0) M), polyethoxylated (2.25) C ₁₂ -C ₁₈ alkyl sulfate (C ₁₂ -C ₁₈ E (2.25) M), polyethoxylated (3.0) C ₁₂ -C ₁₈ alkyl sulfate (C ₁₂ -C ₁₈ E (3.0)) and polyethoxylated (4.0) C ₁₂ -C ₁₈ alkyl sulfate ( C ₁₂ -C ₁₈ E (4.0) M), wherein M is preferably selected from the group consisting of Sodium and potassium is selected.

worin R eine lineare oder verzweigte, gesättigte oder ungesättigte C₆-C₂₀-Alkylgruppe ist, vorzugsweise eine C₁₂-C₁₈-Alkylgruppe und mehr bevorzugt eine C₁₄-C₁₆-Alkylgruppe, und X+ ist H oder ein Kation, beispielsweise ein Alkalimetall kation (z. B. Natrium, Kalium, Lithium, Calcium, Magnesium und dergleichen). Besonders geeignete alkoxylierte lineare oder verzweigte C₆-C₂₀-Alkyldiphenyloxiddisulfonattenside zur Verwendung hierin sind die verzweigte C12-Diphenyloxiddisulfonsäure und das lineare C16-Diphenyloxiddisulfonat-Natriumsalz, die im Handel von DOW unter der Handelsbezeichnung Dowfax 2A1^® bzw. Dowfax 8390^® erhältlich sind.Suitable alkoxylated linear or branched C ₆ -C ₂₀ alkyldiphenyloxide disulfonate 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 ₁₄ -C ₁₆ -alkyl group, and X + is H or a cation, for example one Alkali metal cation (eg., Sodium, potassium, lithium, calcium, magnesium and the like). Particularly suitable alkoxylated linear or branched C ₆ -C ₂₀ -Alkyldiphenyloxiddisulfonattenside for use herein are the C12 branched-Diphenyloxiddisulfonsäure and linear C16 diphenyl oxide sodium salt, the 8390 ^® are commercially available from DOW under the trade name Dowfax 2A1 ^® and Dowfax.

Other anionic surfactants useful herein include salts (including, for example, sodium, potassium, ammonium salts and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C ₈ -C ₂₄ olefin sulfonates, sulfonated polycarboxylic acids obtained by sulfonation of the pyrolyzed product of a Alkaline earth metal citrates, 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, non-sulfated compounds are described below), alkyl polyethoxycarboxylates such as those having the formula RO (CH ₂ CH ₂ O) _k CH ₂ COO-M ⁺ , wherein R is a C ₈ -C ₂₂ alkyl, k is an integer from 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 in or derived from tall oil. Other examples include "Surface Active Agents and Detergents" (Volumes I and II by Schwartz, Perry and Berch) A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678 issued December 30, 1975 to Laughlin et al. , in column 23, line 58, to column 29, line 23.

Preferred anionic surfactants herein include the C ₆ -C ₂₀ primary and secondary alkyl chlorides and the C ₆ -C ₂₀ primary and secondary alkylaryl sulfonates or a mixture thereof.

dyes

The Liquid compositions according to the invention can colored be. Accordingly, they can one Dye or a mixture thereof. Suitable dyes for this purpose Uses are acid-resistant dyes. The term "acid-resistant" is here a connection meant in the acidic environment of the present compositions is chemically and physically stable. Suitable dyes for this purpose Uses include α- or β-metal phthalocyanines and / or trimethylmethane dyes.

wobei der Substituent X eine der folgenden Gruppen sein kann: H, Cl, HSO₃, COO-M+, Br, NO₂, OCH₃ oder eine C₁- bis C₁₀-Alkylgruppe und wobei Me Kupfer, Chrom, Vanadium, Magnesium, Nickel, Platin, Aluminium, Kobalt, Blei, Barium oder Zink ist. Bevorzugte α- oder β-Metallphthalocyanin-Farbstoffe zur Verwendung hierin sind α- oder β-Kupferphthalocyanin-Farbstoffe.The α- or β-metal phthalocyanine dyes suitable for use in the compositions of the present invention are photostable organic pigments having four isoindole groups, (C ₆ H ₄ ) C ₂ N, linked by four nitrogen atoms to form a conjugated chain. They have the following general structure

where the substituent X can be one of the following groups: H, Cl, HSO ₃ , COO-M +, Br, NO ₂ , OCH ₃ or a C ₁ - to C ₁₀ -alkyl group and where Me is copper, chromium, vanadium, magnesium, Nickel, platinum, aluminum, cobalt, lead, barium or zinc. Preferred α- or β-metal phthalocyanine dyes for use herein are α- or β-copper phthalocyanine dyes.

Examples of such α copper phthalocyanine dyes to be used herein are copper phthalocyanine (X = H, blue color), the blue commercially available under the name UNISPERSE Blue BE ^® from Ciba-Geigy or Cosmenyl A2R from Hoechst, or Pigmasol blue available 6900 ^® from BASF , or chlorinated copper phthalocyanine (X = Cl, green color), the 8730 ^® is commercially available under the name Pigmasol green from BASF.

Examples of trimethyl methane dyes are commercially available from Hoechst under the name Vitasyn ^® or from BASF under the name Acid Blue ^®.

Also for use suitable dyes are polymeric liquid colors such as the liquid polymer-blue supplied by Milliken Company under the designation Liquitint ^® Blue 65, Liquitint ^® Patent Blue and Liquitint ^® Bright Blue.

typically, can the compositions of the invention up to 0.2% by weight of the total composition of a dye or a mixture thereof, preferably 0.0001% to 0.015% and more preferably 0.001% to 0.010%.

Radical scavengers:

The Compositions of the invention can a radical scavenger or a mixture thereof.

Free radical scavengers suitable 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-tert-butylhydroxytoluene (BHT), hydroquinone, di-tert-butylhydroquinone, mono-tert-butylhydroquinone, tert-butylhydroxyanisole, benzoic acid, toluene acid, catechol, tert-butylcatechol, benzylamine 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, n-propyl gallate or mixtures thereof, and particularly preferred is di-tert-butyl hydroxytoluene. Such radical scavengers like N-propyl are commercially available under the trade name Nipanox S1 ^® from Nipa Laboratories.

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

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

Method of treatment of surfaces:

The compositions of the invention are particularly suitable for the treatment of hard surfaces contaminated with limescale-containing stains. "Limescale-containing stains" here means any pure limescale deposits, ie any stains, the essenli patches containing limescale deposits typically found, for example, in a kitchen or in a bathroom, ie patches containing not only mineral deposits such as calcium and / or magnesium carbonate but also lather (eg calcium stearate). and other fat (eg body fat). In fact, when used to treat all types of surfaces contaminated by limescale-containing stains comprising not only pure limescale but also at least 10% by weight of the lime scale, the compositions of the present invention exhibit excellent limescale removal performance total stain organic deposits such as soap scum and fat, preferably more than 30%. Such surfaces can be found in bathrooms, kitchens, but also in appliances, including large appliances such as automatic dishwashers and / or washing machines.

Accordingly, includes the present invention is a method for treating hard Surfaces that Contaminated by lime deposits containing stains, where an aqueous acid according to the invention liquid Composition from a spray dispenser on the surfaces applied, then on the surfaces is allowed to act and then removed by rinsing.

Of the Term "treatment" includes removal of calcium deposits, while the treatment is gentle at the same time for the treated surfaces and, optionally, the cleaning of greasy soap scum stains, especially when surfactants are present.

Test method for determination Performance in the removal of limescale:

The ability of a composition of the present invention to remove limescale can be assessed by spraying the composition onto dried ceramic tiles prepared using the automatic dishwashing machine. Black glazed ceramic tiles (typically 20 cm x 20 cm) are placed in the automatic dishwashing machine and treated with 7 complete rinse cycles. Each cycle is carried out using 15 g of sodium carbonate (instead of the rinse) at a temperature of 80 ° C and rinse water at a temperature of 70 ° C. The resulting tiles have a homogeneous thin layer of limescale (precipitated calcium carbonate during the rinse cycle). Subsequently, two vertical dried tiles are sprayed three times (corresponding to about 5 g of the product) with a composition according to the invention and a reference composition, for example of the same composition but without the polymers described herein. The compositions are sprayed using the Schaumsprühspenders ^® T8900 (with a modified orifice diameter of 0.00076 m (0.76 mm) wide and manifold channels of 0.00108 m (1.08 mm) width). After 30 seconds, rinse the surfaces with water (until all residue of the product is removed) and then allow to dry. After the surfaces treated with the compositions of the present invention and those treated with the reference composition are dried, they are compared side by side and evaluated by visual evaluation to evaluate the difference in lime scale removal. The performance evaluation can generally be performed using the scoring unit (PSU).

Method of determination the performance of cleaning greasy soap foam:

In this test procedure, white enamel tiles (typically 24 cm x 4 cm) are covered with typical greasy soap scum stains based primarily on calcium stearate and artificial, commercially available body soil (eg, 0.3 g with a spray). Subsequently, the soiled tiles are dried in an oven at a temperature of 140 ° C for 30 minutes and then stored overnight at room temperature (about 15 ° C-20 ° C) for the purpose of aging. Then the soiled tiles are using 3 ml of the liquid acidic composition of the invention directly on a Spontex ^® sponge is cast cleaned. The ability of the greasy soap scum removal composition to be measured by the number of movements required to perfectly clean the surface. The lower the number of movements, the higher the ability of the composition to cleanse greasy soap scum.

Gloss Test method:

Obtaining a good final gloss result results from a good distribution of a liquid composition over the surface when treated with the surface, and from less formation of water residues and less precipitation of poorly water-soluble salts in the evaporation of water. The ability of a composition to cause "shine" on the surface, be draws on the ability of the composition to leave no water residue after the evaporation of water. This can be assessed by human visual judgment.

In a suitable test procedure, two rectangular areas (10 cm x 4 cm) of a sink (made of either stainless steel or ceramic) twice (corresponding to about 3 g of the product) with a composition according to the invention and a reference composition, e.g. Example of the same composition, but without the polymers described herein, sprayed. Then, each surface is wiped with a sponge Spontex ^® (10 movements). Subsequently, each treated surface is rinsed with 200 g of tap water and allowed to dry. During the drying phase, the surfaces are observed for the evaluation of the water distribution / sliding movement on the treated surface. After the surfaces treated with the compositions of the present invention and those treated with the reference composition are dried, they are side by side compared and evaluated by visual evaluation to evaluate the gloss difference. The evaluation can generally be carried out using the scoring unit (PSU). The gloss result is expressed by reporting whether the effect of water distribution / skid exists and by the final PSU rating.

In a test method for determining long-lasting gloss can the test method described above are performed, however, the Rinsing and Drying cycles repeated several times. Every time both surfaces have dried are, they are compared side by side and by visual judgment evaluated to determine the gloss difference. The rating will generally using the scoring unit (PSU) carried out.

The The present invention will be further understood by the following examples illustrated.

Examples

These Compositions were made by inclusion of the listed ingredients prepared in the stated proportions (wt .-%).

Mirataine CBS ^® and Rewoteric AM CAS ^® 15 are Cocoamidopropylhydroxysulfobetaine, which are available from Rhone-Poulenc and Witco.

Dobanol ^® 91-8 and Lutensol TO 6 ^® are ethoxylated alcohol nonionic surfactants which are available from Shell (with an alkyl chain length of C9-C11 and a degree of ethoxylation of 8) and BASF (having an alkyl chain length of C13 and a degree of ethoxylation of 3).

Aromox ^® C12-C14 is an amine oxide with an alkyl chain length of C12-C14, available from AKZO.

Kelzan T ^® and Rhodopol ^® T are xanthan gum, available from Kelco and Rhone-Poulenc.

Rheozan ^® is a Succinoglykangummi, available from Rhone-Poulenc.

PVP K60 and Luviskol K30 ^{® ®} are polyvinyl pyrrolidone homopolymers, which are available from ISP and BASF.

Gafquat ^® 755 is available from ISP, a vinylpyrrolidone / dialkylaminoalkyl methacrylate copolymer.

BHT is tert-butylhydroxytoluene.

The compositions listed above were packaged in a spray dispenser, such as the Model T8900 ^® (Continental Spray International) provided with an opening diameter of 0.00076 m (0.76 mm) wide and manifold channels of 0.00108 m (1.08 mm) Width was modified. They all show excellent immediate and long-lasting gloss benefits on the treated surface while exhibiting excellent limescale removal performance. In addition, the re-deposition of limescale deposits on a hard surface previously treated with one of the compositions exemplified above is reduced or even prevented for a prolonged period of time when the surface comes into contact with water again, and this is for the use of both pure as well as the diluted form applies.

Claims (15)

liquid Acid composition containing for the removal of calcium deposits Stains from a hard surface suitable, comprising an acid, a polysaccharide polymer at 0.001% to 20% by weight of the total composition and a vinylpyrrolidone homopolymer or copolymer at 0.001% by weight. to 20 wt .-% of the total composition, wherein the composition packed in a spray dispenser is. A composition according to claim 1, wherein the acid is a organic or inorganic acid or a mixture thereof, typically in a proportion of 0.1% to 70% by weight of the total composition. A composition according to any one of the preceding claims, wherein the acid maleic acid, alone or together with a second acid, its first pKa value not bigger than Is 5, or mixtures thereof. A composition according to claim 3, wherein the second Acid sulfamic acid, alkyl sulfonic acid, aryl sulfonic acid, citric acid, nitric acid, sulfuric acid, phosphoric acid, hydrochloric acid or a mixture thereof, and preferably sulfamic acid. A composition according to claim 3 or 4, wherein the Composition to 0.1 wt .-% to 45 wt .-% of the total composition maleic preferably 1% to 25% and more preferably 6% to 20%, and optionally from 0.1% to 25% by weight of the total composition the second acid or Mixtures thereof, preferably 0.1% to 20% and more preferably 0.1% until 10%. A composition according to any one of the preceding claims, wherein the vinylpyrrolidone homopolymer is a homopolymer of N-vinylpyrrolidone having the following repeating monomer:

wherein n is an integer of 10 to 1,000,000, preferably 20 to 100,000, and more preferably 20 to 10,000. A composition according to any one of the preceding claims, wherein the vinylpyrrolidone copolymer is a copolymer of N-vinylpyrrolidone and alkylenically unsaturated Is monomers, preferably selected from the group consisting from maleic acid, chloromaleic, fumaric acid, itaconic, citraconic, phenylmaleic, aconitic, Acrylic acid, N-vinylimidazole, vinyl acetate and anhydrides thereof, styrene, sulfonated styrene, alpha-methyl styrene, Vinyl toluene, t-butyl styrene and mixtures thereof. A composition according to any one of the preceding claims wherein the vinylpyrrolidone copolymer is a quaternized or non-quaternized vinyl pyrrolidone / dialkylaminoalkyl acrylate or methacrylate copoly in accordance with 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 -CHOR-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 represents} a lower alkyl group having 1 to 4 carbon atoms, preferably methyl or ethyl; X ^- is selected from the group consisting of Cl, Br, I, 1 / 2SO ₄ , HSO ₄ and CH ₃ SO ₃ , and preferably a quaternized copolymer of vinyl pyrrolidone and dimethylaminoethyl methacrylate. A composition according to any one of the preceding claims which from 0.01% to 5% by weight of the total composition of a vinylpyrrolidone homopolymer or copolymer or a mixture thereof, preferably 0.01% to 3%, more preferably 0.01% to 1%. A composition according to any one of the preceding claims, wherein the polysaccharide polymer is a substituted cellulosic material or a natural one occurring polysaccharide polymer or a mixture thereof, preferably carboxymethylcellulose, ethylcellulose, hydroxyethylcellulose, Hydroxypropyl cellulose, hydroxymethyl cellulose, succinoglycan, xanthan gum, Guar gum, locust bean gum, gum tragacanth or derivatives thereof or Mixtures thereof and more preferably xanthan gum or derivatives thereof or a mixture of them. A composition according to any one of the preceding claims, wherein at 0.01% to 10% by weight of the total composition of a polysaccharide polymer or a mixture thereof, preferably 0.01% to 5%, more preferably 0.01% to 2%. A composition according to any one of the preceding claims, further comprising a surfactant or a mixture thereof up to 40% by weight of the total composition, typically selected from the group consisting of anionic, nonionic, cationic, amphoteric, zwitterionic surfactants and mixtures thereof more preferably at least one zwitterionic surfactant according to the following formula: R ₁ -N ⁺ (R ₂ ) (R ₃ ) R ₄ X ^- wherein R _{1 is} an aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chain, the linked groups such as amido groups, ester groups, preferably an alkyl group having 1 to 24 carbon atoms, more preferably 8 to 18, or an amido radical having the formula R _a -C (O) -NR _b (C (R _c ) ₂ ) _m in which R _{a is} an aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chain having 8 to 20 carbon atoms, R _{b is} either hydrogen, is a short chain alkyl or substituted alkyl of 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 1 to 4, preferably 2 to 3, more before 3, and not more than one hydroxy group on each (C (R _c ) ₂ ) moiety; R _{2 is} hydrogen, C ₁ -C ₆ alkyl, hydroxyalkyl or another substituted C ₁ -C ₆ alkyl group; R _{3 is} C ₁ -C ₆ -alkyl, hydroxyalkyl or another substituted C ₁ -C ₆ -alkyl group which may 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 which links 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 or a mixture thereof. A composition according to any one of the preceding claims, wherein the composition has a pH of below 7, preferably below 4, preferably has a pH of from 0.1 to 2.5, and more preferably from 0.1 to 2. A composition according to any one of the preceding claims, wherein the spray dispenser a trigger foam spray dispenser is. Method of removing limescale from a hard surface, the stain containing limescale is soiled, being an acidic liquid Composition according to one of the preceding claims a spray dispenser on the surface applied, then on the surface is allowed to act and then removed by rinsing.