DE60038458T2 - USE OF POLYMERIC MATERIAL FOR THE TREATMENT OF HARD SURFACES - Google Patents

Description

introduction

The The present invention relates to the use of a polymeric Materials in the treatment of hard surfaces to form with scale To cope with calcium salts. Scale is an essential Pollution in bathrooms and kitchens and one that is not easy to remove. Tap water supplies contain fluctuating Levels of calcium and magnesium salts. Remaining water, that remains, d. H. from bathing, showering, dishwashing, rinsing, etc., may be evaporate, resulting in the deposition of calcium salts on the surface as Scale leads.

The formed scale deposits can be unsightly, hard and very difficult to remove. This happens especially fast in Hard water areas where the calcium content in drinking water is high is.

conventional Cleaning agent for hard surfaces can for the support the scale removal acid or abrasives. Enamel and marble surfaces are for acid damage, however very vulnerable, and all surfaces can through excessive use Scratch and unsightly from abrasive.

polymers Materials were used in water treatment to precipitate to prevent scale-forming salts from standing water. However, this requires a body of water in which the scale remain suspended salts. For hard household surfaces possibly Water drops containing calcium or magnesium salts to dryness evaporate, and the calcium salts are inevitably deposited.

It has attempted in the art to deposit polymeric material on hard surfaces, to enable that subsequently deposited Dirt like grease can be easily removed.

It However, it has not been generally accepted in the art that it is possible to a release polymer for limestone provide.

WO 99/60086 discloses acidic compositions comprising polyvinylpyrrolidone and a polysaccharide such as xanthan. The compositions provide a cleaning benefit for the next clean and are known to reduce or prevent the formation of scale. However, no data supporting this claim is provided.

EP 0 875 555 discloses acidic compositions comprising a polysaccharide such as xanthan. These compositions also provide a cleaning benefit for the next clean and are known to reduce or prevent the formation of scale, but no data supporting this claim is provided.

The The inventors concerned have recognized that where it is not possible To prevent the deposition of calcium salts, it should be possible will to control the mechanism of calcium salt deposition and thereby the binding strength between calcium salts and the hard surface.

• (a) Kristallisation in der Gesamtlösung; hier kann sich Kesselstein durch homogene Keimbildung oder durch heterogene Keimbildung auf z. B. Staubteilchen bilden, die als Kerne für die Keimbildung fungieren können. Der Großteil der heterogenen Keimbildung und der homogenen Keimbildung erfordert eine hohe Übersättigung der Kesselstein bildenden Salze und kann schnell von statten gehen. Unter diesen Bedingungen gebildeter Kesselstein ist wahrscheinlich amorph und haftet nur schlecht an dem Substrat. Kesselstein, der größtenteils mittels heterogener Keimbildung auf Staubteilchen Kristallisationskeime bildet, kann sich bei einer geringeren Übersättigung bilden und bildet sich gewöhnlich langsamer; er ist daher wahrscheinlich kristalliner, wird jedoch nur schlecht an Haushaltsoberflächen haften.
• (b) Kristallisation auf harten Oberflächen; hier können sich Kristalle durch heterogene Keimbildung bilden, wobei die Haushaltsoberfläche als Ort der Keimbildung fungiert.

Scale can deposit on household surfaces in two ways:

• (a) crystallization in the total solution; here scale can be due to homogeneous nucleation or heterogeneous nucleation on z. B. form dust particles that can act as nuclei for nucleation. The majority of heterogeneous nucleation and nucleation require high supersaturation of the scale-forming salts and can be rapid. Scale formed in these conditions is likely to be amorphous and poorly adherent to the substrate. Scale, which mostly forms nucleation sites by means of heterogeneous nucleation on dust particles, can form with less supersaturation, and usually forms slower; it is therefore likely to be more crystalline, but will adhere poorly to household surfaces.
• (b) crystallization on hard surfaces; Here, crystals can form by heterogeneous nucleation, with the household surface acting as a site of nucleation.

In this case, the scale is formed at a slight supersaturation; the process is relatively slow and results in crystalline deposits that compactly and tightly bound to the surface they are.

The The inventors concerned have recognized that a polymeric material a hard surface can be deposited to heterogeneous nucleation on the surface to inhibit. Most of the Nucleation will then take place in the overall solution, resulting in deposition Resulting in scale-forming salts, which are easy to remove. The polymer also reduces further Aggregation and solidification of new scale at already existing scale deposits.

Further it was found that such Polymers provide an anti-corrosion advantage when applied to metal surfaces become.

By preventing that from happening Scale or stick to household surfaces, the smoothness of the surface maintain and protect it from dying. This is especially true surfaces important, which are likely to come into contact with water often, such as in bathrooms, toilets, kitchens and the like. Such surfaces are often made of metal, glassy materials or hard plastics.

Summary of the invention

The The present invention accordingly provides the use of a polymeric Material for reducing the heterogeneous nucleation of calcium and magnesium salts on hard surfaces, including deposition a polymeric material which is a natural polymer that is characterized by Nitrogen-containing species has been modified, and wherein the polymeric material further has a weight average molecular weight of more than 10,000 and cationic groups or groups, which become cationic at the use pH possesses, on the hard Surface.

The The invention further provides a method for preventing scale forms or metallic, glassy or hard plastic surfaces adhering comprising applying a cleaning composition, the one cleaning active substance and a polymeric material, such as described above, comprising on the surface.

Detailed description of the invention

Polymeric material

Lots Types of polymeric material are for use in the present Invention suitable. The polymer must be one that, if it is on a hard surface deposited at a suitable level, the heterogeneous nucleation Scale scale forming salts on this surface will decrease. Preferably polymeric material achieves a reduction in nucleation rate (Number of germs per unit area per unit time) scale-forming salts on the surface. Of the The following test was done to determine if a polymeric material a reduction of the nucleation density (number of germs per unit area) achieved, which are easily converted into a nucleation rate can if the duration of the experiment is also recorded.

Of the Test covers the application of a polymer solution known concentration on a first surface sample of the hard surface, the Providing a second surface sample the hard surface without polymer on it and the flow of a supersaturated solution from scale forming salt over every surface sample the hard surface for one known period and comparing the number of cores that per unit area per time unit for the surface sample having been treated with the polymeric material with the number of scale cores per unit area per unit of time for the untreated surface sample has made an assessment with regard to the reduction of To obtain rate of heterogeneous nucleation on the hard surface.

Device for measuring the Reduction of nucleation density

The apparatus for use in the test for determining whether a polymeric material is suitable for reducing the nucleation density on a surface is described below:
The device 1 comprises means for providing two solutions which, when mixed, produce a supersaturated solution of scale-forming salt. The device for providing the two solutions comprises two syringes 2 and 3 , The syringes 2 and 3 contain the solutions A and B, respectively. To ensure that the flow rates of the solutions A and B are the same, a conventional An drive mechanism 4 provided for both syringes. The mechanism 4 is adjusted so that it provides a con stant flow of the solutions A and B. The mechanism 4 may include a dual-drive syringe pump available from CP Instruments, Model 200. A mixed cell 5 , which will be further described below, is provided for mixing solutions A and B. The mixed solutions A and B are then applied to a surface to be tested 6 in a manner described below. The expiring solution is separated.

The All hoses used in the device include PTFE tubing, for example OD 3.2 mm, ID 1.5 mm, available from Omnifit (brand). The device is coated with nitrogen, to ensure that carbon dioxide is not absorbed again.

The mixing cell 5 comprises a PTFE block with a cavity 7 which is formed in its interior. The cavity 7 has a volume of 1 mm ³ . Through the block and into the room 7 lead two capillary tubes 8th and 9 , via which the solutions A and B are supplied. The capillary tubes 8th and 9 terminate in outflow openings near the center of the cavity 7 , The solutions A and B are directed towards each other and in the middle of the cavity 7 mixed. If the block is formed of PTFE, even if in the cavity occurs 7 a supersaturated solution is formed, substantially no adhesion or precipitation of the crystalline material on the surface of the room 7 on. The resulting mixed solution leaves the cavity 7 through a pipe 10 from where it points to the experimental surface to be tested 6 is brought. The capillaries 8th and 9 have end openings with a diameter of 100 microns.

The mixed solution is passed to a surface to be tested. The surface to be tested 11 is between an exhaust port 12 from which the mixed solution from the mixing cell 5 on the surface 11 brought attached. The resulting flow pattern is a wall-nozzle flow pattern that is generally understood by one skilled in the art. The flow extends from the center of the surface to be tested 11 radially outward and is uniform.

The discharge opening 12 is a PTFE outflow opening with an inside diameter of 0.8 mm, placed 3 mm above the surface 11 , The mixed solution is supplied at a flow rate of 4 cm ³ / min. The wall nozzle device 6 is coated with nitrogen to prevent CO ₂ absorption.

All Experiments were carried out in an air-conditioned laboratory. The Temperature was measured at the beginning of each run. The Temperatures were typically 23 ° C.

The Device allows continuous refreshment of the surface with solution the known composition, whereby crystals under conditions constant supersaturation could grow.

method

The Apparatus is used to test a surface by the following method used.

A supersaturated solution is produced in a manner known to those skilled in the art by mixing two stable undersaturated solutions. The solutions are degassed prior to use using N ₂ to remove the dissolved CO ₂ .

The solution will over the surface to be treated for one feast time calmly. A suitable time is 45 minutes.

As a result of the solution flowing over the surface to be tested 11 scale-forming salt is deposited on the surface. At the end of each experiment, all crystals are sucked away at the air / water interface using a small piece of tubing connected to a water pump. The surface is then removed from the device 6 rinsed briefly with a saturated solution of scale-forming salt, purged with nitrogen and examined under a microscope.

The Characterization of the degree of crystal growth on a test to be tested surface can be generated using a digitized map of the surface be achieved by micrographic representation. This map can then using image analysis software (for example Aequitas, Dynamic Data Links Ltd.) are processed, which is automatic Measurement of crystal size, number and distribution over a selected one Area allows. this makes possible measuring the nucleation density.

The surfaces to be tested can prepared and treated in some way for so long like the surface fairly just stays. sample surfaces are prepared using 0.05 gamma alumina, available from Buehler, preferably polished to a surface finish of 1/20 microns.

To the effect of the surface to be tested 11 In order to examine deposited polymer, half of the surface was covered and half treated with a solution or dispersion of the polymeric material. A 50 microliter drop of the polymer solution was placed on the uncovered half of the sample surface and allowed to wet this portion of the surface. The drop is left there until dried and washed with 10 sprays of deionized water from a pulser spray gun. The drying time can be correspondingly from 5 minutes to 20 hours.

Preferably, the surface to be tested is located 11 in the form of a disk.

Preferably discs of the same size are used consisting of a stainless steel disc, a ceramic disc, a with enamel coated disc, a glass pane and a Plexiglas pane.

The Nucleation density on the untreated half may then be with the nucleation density on the treated half be compared.

The Experiment can be done with different types of calcium salts, for example Calcium carbonate or calcium sulfate, or with magnesium salts, such as Magnesium carbonate or magnesium sulfate.

polymers the for the use particularly suitable in the present invention reduce the nucleation density on the surface by at least 10% on at least one of the test surfaces (glass, steel, ceramics, Enamel or plexiglass) with at least one of the salts (calcium carbonate, Calcium sulfate, magnesium sulfate, magnesium carbonate). More preferred the polymer will increase the nucleation rate by at least 20%, even more stronger preferably at least 30%, and most preferably at least Reduce 50%.

The Polymer should also preferably reduce nucleation density of at least 10%, stronger preferably at least 20% with both calcium carbonate and calcium sulfate on any of the surfaces, stronger preferably both steel and glass, and most preferably reach on all of steel, glass, ceramics and enamel.

It was also found out that it a correlation between the contact angle caused by a drop of water is produced on a polymer-treated steel surface, on the one hand and easier cleaning of the steel surface of scale deposits (measured as explained below) and the reduction in nucleation density, on the other hand. Therefore It has been found that polymers, which cause a contact angle of <30 ° or> 60 °, a significant Increase in cleaning performance compared to polymers cause a contact angle within these limits. Preferred are the polymers which cause the contact angle to be <20 ° stronger preferred are those which cause it to be> 60 ° or even> 65 ° is.

Without to be bound by theory, it is believed that the contact angle a manifestation of surface energy at the interface between water and the polymer-treated surface is what in turn determines the degree to which evolving scale crystal nuclei to the surface be bound. It seems that this Bonding to the surfaces the strongest is that cause that Contact angle between 30 ° and 60 °.

The contact angle produced by a drop of water on the treated steel surface can be measured by any of the commonly known methods. For the purposes of this invention, the measurements may be made using a carriage microscope with a simple angle measuring head in which the lens is fitted with the reticule. A 20 μl drop of water was pipetted onto the horizontal treated steel surface. The reticle in the microscope lens is aligned so that the horizontal mark is in line with the steel surface (ie, along the steel / water interface). The center of the cross is aligned with the three-phase contact point (ie, the water / steel / air interface). The crosshairs are then rotated so that they line up with the edge of the water drop (ie, along the air / water interface), and the resulting win The angle is read off the scale of the protractor.

Deposition of the polymeric material

polymers for the Use in the present invention may be preferable good on hard surfaces deposit. You can be applied in any manner known in the art. Preferably they are in the form of a liquid Composition applied to the polymer in solution or Dispersion contains. Stronger preferably such compositions are aqueous liquids.

compositions the polymers for used in the present invention can be used in be applied in a variety of ways, as discussed below becomes. For example, you can she on a surface be applied and with evaporation to dryness in contact stay. In this case, the polymer should only have a thin and can form a smooth layer, suitably the arrangement of some molecular layers with a Thickness in submicrometer range. Other compositions may be on the surface be applied with the intention that the surface then dry is wiped. In such cases In addition, the polymer should preferably be reinforced tend to stick to the hard surface Adsorptive store.

Examples of compositions containing the polymers are cleaning compositions, the extra Have effect that they a polymer for inhibiting nucleation on the treatment surface deposit. Such compositions will usually be one in addition to the polymer or more detergent-active substances.

The Polymer should preferably act at the solid / liquid interface. Particularly preferably, the polymer is to adhere sufficiently strongly to the surface, that it across from Remove by rinsing is resistant. However, the polymer should not adhere too much to the surface, otherwise could the polymer on the surface resulting in negative effects, e.g. B. too bad appearance, to lead could.

Some Surfaces, the most vulnerable for scale deposits are made of steel, ceramics, glass and enamel, are known to be negative loaded. The polymer should have cationic groups or groups that become cationic at the use pH. The polymer should preferably be amine groups, in particular quaternary ammonium or tertiary amine groups, include.

The Deposition of the polymer can be further assisted if it is a relative has high molecular weight. The weight average molecular weight is bigger than 10,000, preferably larger than 50,000.

The Deposition of the polymer may be further assisted when the polymer or a complex of the polymer with a surfactant, rigid or is semi-rigid. The polymeric material can be an inflexible backbone have, for. Due to unsaturation or the presence of rings. Alternatively, it may be either permanent or temporary, in which pH of the composition have a positive charge, whereby the Conformation of the main chain due to repulsion between the charges limited is, or it may have a main chain, which is basically flexible is, in terms of molecular conformation, on the polymer structure is due z. Networking, unsaturation, Rings or voluminous Page groups, but restricted is.

is the polymer itself is not positively charged (for example, if negatively charged or neutral), the deposition of the polymer Furthermore by the use of a deposition aid such as a cationic supported polymer or surfactant.

Keimbildungsinhibierungswirkung

• 1. Hydrophobie. Das polymere Material kann hydrophobe Teile besitzen. Wie oben angegeben, wird das Polymer, um die Abscheidung des Polymers auf Oberflächen wie Stahl, Glas, usw. zu verbessern, vorzugsweise ebenso hydrophile Teile aufweisen. Demgemäß ist das Po lymer in diesem Fall besonders bevorzugt oberflächenaktiv, wobei es hydrophile und hydrophobe Teile an verschiedenen Teilen des Moleküls aufweist, beispielsweise an verschiedenen Seiten der Polymerhauptkette.

In order to provide a polymer which inhibits nucleation on a surface on which it is deposited, the polymeric material preferably has at least one of the following properties:

• 1. hydrophobicity. The polymeric material may have hydrophobic parts. As stated above, to improve the deposition of the polymer on surfaces such as steel, glass, etc., the polymer will preferably also have hydrophilic parts. Accordingly, the polymer in this case is more preferably surface-active, having hydrophilic and hydrophobic parts on different parts of the molecule, for example on different sides of the polymer backbone.

• 2. sterische Faktoren. Die Inhibierung der Keimbildung kann durch sterische Faktoren erhalten werden. Vorzugsweise wird das Polymer große, voluminöse Substituenten umfassen (beispielsweise, indem ein tertiäres Kohlenstoffatom und/oder mehr als 5 Nicht-Wasserstoffatome eingeschlossen werden). Vorzugsweise sind diese entlang der Polymerhauptkette in Abständen beabstandet, die kleiner als die kritische stabile Mikrokristallgröße sind. Auf diese Weise wird, wenn sind ein Mikrokristall auf der Oberfläche des Polymers bildet, durch sterische Faktoren verhindert, daß es zu einer Größe wächst, bei der es thermodynamisch stabil wird. Vorzugsweise sind die Substituenten ungleichmäßig beabstandet, um die Keimbildung weiter zu inhibieren.

Ways to provide hydrophobicity are discussed below.

• 2. steric factors. The inhibition of nucleation can be obtained by steric factors. Preferably, the polymer will comprise large, bulky substituents (for example, including a tertiary carbon atom and / or more than 5 non-hydrogen atoms). Preferably, these are spaced along the polymer backbone at distances less than the critical stable microcrystal size. In this way, when a microcrystal is formed on the surface of the polymer, steric factors prevent it from growing to a size where it becomes thermodynamically stable. Preferably, the substituents are unevenly spaced to further inhibit nucleation.

solubility

polymers Materials for the use in the present invention are in solutions surfactant Agent preferably soluble or dispersible, but hardly soluble or dispersible in water. The However, polymeric material may also be partially water soluble and in an aqueous solution surfactant Means of the kind as used in cleaning compositions for hard surfaces is used, soluble be. The solubility of the polymeric material in an aqueous solution of surfactant Average is suitably in the range of 0.01-50% by weight, more preferred in the range of 0.05-10 % By weight, the strongest preferably at about 0.1-1.0 Wt .-%, in particular 0.4-1.0 Wt .-%. The concentration of the surfactant is suitably in the range of 0.1-20 Wt .-%, preferably 1.0-10 Wt .-% or 6 wt .-%.

Types of polymers:

The The present application can be used with many types of polymers of suitable structure carried out to achieve the characteristics described above. The following non-limiting Examples are given.

polymers the for the use in the present invention are suitable in a suitable polymerization process, for example emulsion or solution polymerization, getting produced. Copolymers can for example by grafting, block or mass copolymerization getting produced.

For example, hydrophobicity can be imparted to polymers by introducing hydrophobic side chains such as C ₈ -C ₂₂ alkyl, alkenyl, or alkylaryl chains. These may be introduced, for example, as esters of C ₈ -C ₂₂ alcohols or the like.

polymers used in the present invention include natural polymers like strengths and gums modified with nitrogen-containing species. For example For example, the polymer can be guar gum, cellulose, locust bean gum, starch, starch amylose or similar natural Include polymers. The natural Polymer can be modified by reacting the hydroxyl groups with others Groups are implemented, providing page groups, about the substantivity the polymer surface to modify or to provide the germination inhibitory effects.

For example can the natural Polymer with nitrogen-containing species such as hydroxypropyltrimethylammonium groups be modified. For example, the polymers may be cationic Guar gums such as Hydroxypropyltrimethylammoniumguargummi with a Degree of substitution in the range of 0.11 to 0.22, commercially lower the brands JAGUAR C13S, JAGUAR C14S, JAGUAR C17 and JAGUAR C-162 available, include.

A another class of polymers used in the present invention may include polyquaternary polymers like Polyquat 10, which is commercially available under the trademarks Polymer JR30M, JR125 and JR400 available is.

Hydrophobicity can be provided by modifying the natural polymer with, for example, hydrophobic substituents such as C ₈ -C ₂₂ alkyl chains, tertiary alkyl groups, etc.

Other suitable properties

Preferably is the polymeric material over the pH range of interest (3-12) not strongly colored.

Polymers found to significantly reduce nucleation are given in the table below: Product name / type (* = brand name) chemical class Ucare Polymer JR-30M * Polyquaternium-10 - cationic hydroxyethylcellulose Jaguar C162 * Hydroxypropylguarhydroxypropyltrimoniumchlorid Crotein C * collagen derivative Celquat L200 * Cationic polymer grafted onto a cellulose backbone Polymer JR 125 * Polyquaternium-10 - cationic hydroxyethylcellulose Polymer JR-400 * Polyquaternium-10 - cationic hydroxyethylcellulose Chitosoniumbetain Jaguar C-13S * guar hydroxypropyltrimonium chloride Crodacel * quaternized cellulose derivatives Crotein O * collagen derivative Celquat H-100 * Cationic polymer grafted onto a cellulose backbone Celquat SC240C * cationic derivative of hydroxyethylcellulose Chitosanessigsäuresalz chitosan Chitosan-4-hydroxy-L-proline chitosan Chitosanlactobionsäure chitosan Chitosan-2-hydroxycaprylat chitosan

Other Polymers to which the above-mentioned polymers are chemically equivalent are, can be used instead. Such polymers are known to a person skilled in the art known.

treatment compositions for hard surfaces

The polymeric material may according to the present Invention can be used in any suitable formulations.

The Formulation must be for the deposition of the polymeric material to a hard surface. The polymeric Material may be in the formulation in any suitable form, for example in the form of a solution or dispersion.

suitable Formulations include solutions Dispersions or emulsions of the polymeric material in a carrier, for example a substantially non-aqueous material, such as ethanol, but preferably water. The compositions can only be used for depositing the polymeric material, or they can additional Have features like cleaning.

The Composition can be applied by any suitable means. For example, it may surface on a container or from a spray can or poured from a spray gun applicator or sprayed become.

compositions for the Use in the present invention may include any ordinary ingredients for cleaning agents for hard surfaces contain.

Preferably comprises a cleaning composition for hard surfaces at least one detergent-active substance and optionally others Cleaning components for hard surfaces.

surfactants Medium:

The Composition according to the invention will comprise detergent-active compounds (surfactants), which are generally both anionic and nonionic cleaning active compounds are selected.

suitable anionic surface-active Agents are water-soluble Salts of organic sulfuric acid esters and sulfonic acids, containing an alkyl group in the molecular structure containing 8 to 22 carbon atoms.

• – langkettigen (d. h. 8-22 C-Atome) Alkoholsulfaten (hierin nachstehend als PAS bezeichnet), insbesondere die, erhalten durch Sulfatieren der Fettalkohole, die durch Reduzieren der Glyceride von Talg- oder Kokosnußöl erzeugt wurden;
• – Alkylbenzolsulfonaten, wie denen, in denen die Alkylgruppe 6 bis 20 Kohlenstoffatome enthält;
• – sekundären Alkansulfonaten.

Examples of such anionic surfactants are water-soluble salts of:

• Long-chain (ie 8-22 C-atoms) alcohol sulfates (hereinafter referred to as PAS), especially those obtained by sulfating the fatty alcohols produced by reducing the glycerides of tallow or coconut oil;
• Alkylbenzenesulfonates, such as those in which the alkyl group contains from 6 to 20 carbon atoms;
• - secondary alkanesulfonates.

• – Alkylglycerylethersulfaten, insbesondere den Ethern der Fettalkohole, die von Talg- und Kokosnußöl stammen;
• – Fettsäuremonoglyceridsulfaten;
• – Sulfaten des Reaktionsproduktes von einem Mol eines Fettalkohols und von 1 bis 6 Mol Ethylenoxid;
• – Alkylphenolethylenoxyethersulfaten mit 1 bis 8 Ethylenoxyeinheiten pro Molekül und bei denen die Alkylgruppen 4 bis 14 Kohlenstoffatome enthalten;
• – dem Reaktionsprodukt von Fettsäuren, verestert mit Isethionsäure und neutralisiert mit Alkali;

und Gemische davon.Also suitable are salts of:

• - Alkylglycerylethersulfaten, in particular the ethers of fatty alcohols derived from tallow and coconut oil;
• Fatty acid monoglyceride sulfates;
• Sulfates of the reaction product of one mole of a fatty alcohol and from 1 to 6 moles of ethylene oxide;
• - Alkylphenolethylenoxyethersulfaten with 1 to 8 ethyleneoxy units per molecule and in which the alkyl groups contain 4 to 14 carbon atoms;
• The reaction product of fatty acids esterified with isethionic acid and neutralized with alkali;

and mixtures thereof.

The preferred water-soluble synthetic anionic surface active Agents are the alkali metal (such as sodium and potassium) and alkaline earth metal (such as Calcium and magnesium) salts of alkylbenzenesulfonates and mixtures with olefin sulfonates and alkyl sulfates and the fatty acid mono-glyceride sulfates. The strongest preferred anionic surface active Means are alkylaromatic sulfonates such as alkylbenzenesulfonates, containing 6 to 20 carbon atoms in the alkyl group in one straight or branched chain, particular examples of which are sodium salts of alkylbenzenesulfonates or of alkyltoluene, xylene or phenolsulfonates, Alkylnaphthalenesulfonates, Ammoniumdiamylnaphthalinsulfonat and Sodium dinonylnaphthalenesulfonate are.

Should used a synthetic anionic surfactant be, the amount that is in the compositions of the invention generally at least 0.5%, preferably at least 1.0%, stronger preferably at least 2.0%, but not more than 20%, preferably at the most 10%, even stronger preferably at most 8%.

suitable nonionic surfactant Means can are largely described as compounds by the condensation of alkylene oxide groups which are hydrophilic in nature with a organic hydrophobic compound which is aliphatic or alkylaromatic Nature can be produced. The length of the hydrophilic or polyoxyalkylene radical, which is bound to a particular hydrophobic group can without be further adjusted, creating a water-soluble compound with the desired Obtained balance between hydrophilic and hydrophobic elements becomes. this makes possible the choice of non-ionic surfactants with the correct HLB, considering the presence of the organic solvent and one possible Hydrocarbon co-solvent taken into account in the composition.

Specific Examples include the condensation product of aliphatic alcohols having 8 to 22 carbon atoms in either straight or branched chain Configuration with ethylene oxide, such as coconut oil ethylene oxide condensates with 2 to 15 moles of ethylene oxide per mole of coconut alcohol; Condensates of alkylphenols, whose alkyl group contains 6 to 12 carbon atoms, with 5 to 25 mol of ethylene oxide per mole of alkylphenol; Condensates of the reaction product of ethylenediamine and propylene oxide with ethylene oxide, the condensates containing 40 to 80% by weight Contain ethyleneoxy groups and a molecular weight of 5,000 to 11,000.

Other examples are: alkyl glycosides which are condensation products of long chain aliphatic alcohols and saccharides; tertiary amine oxides of the structure RRRNO, wherein one R is an alkyl group of 8 to 18 carbon atoms and the other Rs are each alkyl or hydroxyalkyl groups of 1 to 3 carbon atoms, for example dimethyldodecylamine oxide; tertiary phosphine oxides of the structure RRRPO, wherein one R is an alkyl group of 8 to 18 carbon atoms and the other Rs are each alkyl or hydroxyalkyl groups of 1 to 3 carbon atoms, for example, dimethyl-dodecylphosphine oxide; and dialkyl sulfoxides of the structure RRSO, where one R is an alkyl group of 10 to 18 carbon atoms and the other is Me ethyl or ethyl, for example methyl tetra decyl sulfoxide; Fatty; Alkylene oxide condensates of fatty acid alkylolamides and alkylmercaptans. Ethoxylated aliphatic alcohols are particularly preferred.

The Amount of to be used in the cleaning composition of the invention nonionic surfactant Agent is preferably at least 0.2%, more preferably at least 0.5%, the strongest preferably at least 1%. The maximum amount is appropriate 15%, preferably 10% and the strongest preferably 7%.

The Compositions can Amounts of both anionic and nonionic surfactants Contain agents which are selected so that the content taken into account in the present electrolyte, that one structured liquid Cleaning composition is provided, d. h., one that is "self-thickening." Therefore, despite the presence of organic solvent, thickened liquid Cleaning compositions can be prepared without any more thickening agent must be used, and they still have a long shelf life over one wide temperature range.

The weight ratio of anionic surfactant Agent for non-ionic surfactant Means may vary, taking into account the above considerations depend on their nature, however, is preferably in the range of 1: 9 to 9: 1, more preferred 1: 4 to 4: 1 and ideally over 1: 1.

According to an embodiment illustrating this aspect of the invention, the cleaning compositions are 0 to 10% by weight of a water-soluble, synthetic anionic sulfate or sulfonate anionic surfactant salt containing a C ₈ -C ₂₂ alkyl group and 0.5 to 7% by weight. % of a nonionic ethoxylated alcohol surfactant having a C ₈ -C ₂₂ alkyl group and 2 to 15 ethyleneoxy groups.

It can optional as well amphoteric, cationic or zwitterionic surfactant Agent in the compositions of the invention be included.

suitable amphoteric surfactant Agents that can be used optionally are derivatives of aliphatic ones secondary and tertiary Amines containing an alkyl group having 8 to 18 carbon atoms and an aliphatic group substituted by an anionic one water-soluble Group, for example, sodium 3-dodecylaminopropionate, sodium 3-dodecylaminopropanesulfonate and sodium N-2-hydroxydodecyl-N-methyl taurate.

suitable cationic surfactant Means are quaternary ammonium salts with one or two aliphatic groups of 8 to 18 carbon atoms and two or three small aliphatic (e.g., methyl) groups, for example, cetyltrimethylammonium bromide.

suitable zwitterionic surface-active Agents that can be used optionally are derivatives of aliphatic ones quaternary Ammonium, sulfonium and phosphonium compounds with an aliphatic Group having 8 to 18 carbon atoms and an aliphatic group, substituted by an anionic water-soluble group, for example 3- (N, N-Dimethyl-N-hexadecylammonium) propane-1-sulfonate betaine, 3- (dodecylmethylsulfonium) propane-1-sulfonate betaine and 3- (cetylmethylphosphonium) ethanesulfonate betaine.

Further Examples of suitable surface-active Means are compounds that are common as a surface-active Means are used in the well-known manuals "Surface Active Agents, Volume I by Schwartz and Perry and "Surface Active Agents and Detergents ", Volume II of Schwartz, Perry and Berch are given.

Should surfactants Agents are present in the compositions of the present invention is the total amount of surface-active compound to be used in general 0.5 to 20%. Preferably, the amount is at least 1%, stronger preferably at least 3%. The maximum amount is usually 15% or less, preferably not more than 10%. Preferably, the nature of the surface active Means and its amount selected so that there is no with the polymer Complex that is not held, dissolved or in the composition can be dispersed.

The compositions according to the present invention may contain other ingredients which aid in cleaning performance. For example, the compositions can be insoluble abrasives such as calcite, silica, and other materials known in the art, or builders such as nitrilotriacetates, polycarboxylates, citrates, dicarboxylic acids, water-soluble phosphates (especially ortho-, pyrophosphates, or polyphosphates or mixtures thereof), zeolites, and mixtures thereof in one Amount of up to 25% included. In addition, some of these detergency builders may act as abrasives if they are present in excess of that required for their solubility in water. If present, the detergency builder will form at least 0.1% of the composition.

Metal ion sequestrants such as ethylenediaminetetraacetates, amino-polyphosphonates (DEQUEST ^™ ) and phosphates, and a wide variety of polyfunctional organic acids and salts may optionally also be used provided they are compatible with the polymer and the optional abrasive material.

One another optional ingredient for compositions according to the invention is a lather-regulating material used in compositions can be used, which is responsible for excessive foam generation tend to be in use. An example of a lather-regulating Material is soap. Soaps are salts of fatty acids and include alkali metal and ammonium salts of fatty acids, containing from about 8 to about 24 carbon atoms, and preferably from about 10 to about 20 carbon atoms. Especially useful the sodium and potassium and mono-, di- and tri-ethanolamine salts the mixtures of fatty acids, which come from coconut oil and peanut oil. When used, the amount of soap may be at least 0.005%, preferably 0.1% to 2% by weight of the composition. Another example of soap scum regulating material is Silicone oil.

One another optional ingredient used in the compositions of the invention Can be used is an acidic material that removes supported the scale deposits. Examples of this are in the art are well known and include phosphoric acid and many di- and polycarboxylic acids.

compositions according to the invention can Furthermore additionally to the components already mentioned various other optional Ingredients such as colorants, Whiteners, optical brighteners, soil carriers, cleaning enzymes, compatible bleaches, such as active chlorine compounds or hydrogen peroxide, gelling control agents, Freeze-thaw stabilizers, bactericides, preservatives (e.g. 1,2-benzisothiazolin-3-one), perfumes and hydrotropes.

The Composition for the treatment of hard surfaces may have any suitable pH. The compositions, however, are either weakly alkaline (especially when used as surface cleaning compositions formulated to enhance the effect of the surfactants), neutral or slightly acidic (especially if they are cationic species or Amine groups include those that are protonated and in an acidic environment become cationic to aid deposition). The compositions However, they should preferably not be too acidic to cause damage to acid-sensitive ones Surfaces too avoid. In particular, it is important to mask the presence organic acids, which tend to surfaces How to attack, minimize or avoid enamel. Preferably the pH is in the range of 3-12, the ranges being 3.5-6.0 and from 10-12 are particularly preferred. In any case, the pH is suitably above 3.0 and stronger preferably over 3.5.

The Use of polymeric material according to the present invention can, in addition to luster inhibiting effects a longer lasting shine better appearance of the surface, a smoother feeling the treated surfaces to lend.

compositions according to the present Invention are for the treatment of household surfaces in, for example, kitchens and Bathrooms, including walls floors, Toilets, dishwashers, and work surfaces usable. They are especially useful for treating surfaces usually stay in contact with water for a long time, such as: shower walls and floors, Bathtubs and bathtub edges, Faucets, Shower heads, Sink, sink and the same.

The The present invention will be further understood by reference to the following not restrictive Examples are described.

Examples

All percentages given herein are by weight based on the total Composition, unless specifically stated otherwise.

Surface treatment compositions were prepared according to the following formulations (* indicates nucleation inhibiting polymers): Example 1 - Bathroom cleaning formulation Alcohol ethoxylate 8EO 6.00 dicarboxylic acids 4.00 2-butoxyethoxy ethanol 2.00 phosphoric acid 0.50 coconut 0.25 Magnesium sulfate 7H ₂ O 1.00 sodium hydroxide 0.34 1,2-benzisothiazolin-3-one 0.016 perfume 0.50 * Polymer JR-30M 0.50 water on 100 Example 2 - Bathroom cleaning formulation Alcohol ethoxylate 8EO 6.00 dicarboxylic acids 4.00 2-butoxyethoxy ethanol 2.00 Magnesium sulfate 7H ₂ O 1.00 * Polymer Jag C162 0.50 water on 100

Tests to facilitate the Removal of scale from treated surfaces

Steel plates, formed from certain surfaces, were obtained from Mersey Metals. The plates were 0.9 mm thick, square with a size of 100 × 100 mm, were on a specification of 304 with a high gloss finish polished and provided on one side with plastic. The plates were thorough cleaned and rinsed using demineralized water. The Plates could then dry.

A 0.5 wt .-% aqueous polymer solution was in a flat layer on each plate using a K-bar applicator, K-bar number 0010, applied. 0.5 ml of the solution was poured over the near the top of the plate of the K-bar pipetted. The drive speed of the K-bar was set to 16.5 cm / s.

The Plates could for dry for up to 24 hours.

The dried plates were then horizontal at an angle of 10 ° attached. Each plate was then washed with 200 ml demineralized water rinsed, that by means of a peristaltic pump at a speed of 812 ml / min over the plate was pumped. The plate was then laid horizontally to dry.

Plastic stencils in the form of square sheets of acetate film with a square hole in the middle were adhered to each plate. 0.5 ml of Prenton water (27 ° FH) was added to each plate in the square defined by the plastic template. The drop could dry. The step was repeated for additions of 6 x 0.5 ml of Prenton water, each time with drying. The treated panels were then subjected to a cleaning test using a WIRA (Wool Institute Research Association) machine. This device measures the number of cycles required to clean a defined area. The surface to be cleaned corresponds to the exposed surface defined by the plastic template. The plates were cleaned using a damp J-cloth ^™ on a WIRA machine operated for 4 cycles (16 x 4 = 64 actuations under maximum load). When the panels were cleaned, they were allowed to dry and rated for scale and tarnish. Scale and tarnish were rated subjectively and ranked on a scale of 1 to 4, with 1 corresponding to no or very little distance and 4 corresponding to a completely clean surface.

Results

The procedure of Example 2 was carried out with the polymeric materials listed in the table below. The start-up results were evaluated and the ratings are listed below. treatment Average rating (uncertainty for a 95% confidence limit in brackets) cleaned with Jif (brand) 1.93 (7) cleaned with surfactant only 1.7 (2) Celquat L200 (brand) 2.9 (3) JR-30-M (brand) 3.6 (2) Jaguar C162 (brand) 3,4 (4) Crotein C (brand) 3.6 (4)

Measurement of nucleation density

The above-described device for the measurement of nucleation density can be used as follows to study the effect of the polymer on nucleation density on the surface.

A Stainless steel sample with a diameter of 10 mm (steel type 304), polished to a finish of 0.05 microns, was masked on one half. The other half was treated with a 0.5 wt% aqueous polymer solution.

Solution A comprises calcium chloride (obtained from Aldrich, greater than 99.99% pure) in 0.1 M NaCl (obtained from Fisons, greater than 99.9% pure) and solution B comprises NaHCO ₃ (obtained from BDH, greater than 99 , 5% pure) in 0.1 M NaCl. The concentrations of calcium chloride and sodium bicarbonate were changed to obtain supersaturation of calcium carbonate in a manner known to those skilled in the art.

Of the pH was adjusted to 8.5 using NaOH (obtained from Fisons, greater than 86% pure) or HCl (obtained from Aldrich, 0.5098N, ACS grade).

The experiment was repeated with a variety of different polymer types. The results are shown in the following table: Polymer (all indicated by the brand) Number of crystals per m ² treated half Number of crystals per m ^{2 of} untreated half Ratio of nucleation density % Reduction in nucleation density Celquat L200 5,280e7 2,139e8 1: 4.1 75% JR-30M 2,934e7 1,630e8 1: 5.6 82% Ucare LK 5,128e8 1,439e9 1: 2.8 64% Alcogum L520 3,876e8 6,431e8 1: 1.7 40% Narlex ST15 1,852e9 8,718e8 1: 0.5 -112%

Narlex ST15 is not a polymer according to the invention and is included in the table as a comparative example.

Claims (10)

Use of a polymeric material to reduce the heterogeneous nucleation of calcium and magnesium salts a hard surface, comprising depositing a polymeric material which comprises natural Polymer modified by nitrogen-containing species and wherein the polymeric material further comprises a weight average Molecular weight of more than 10,000 and cationic groups or groups which become cationic at the use pH, on the hard surface. Use according to claim 1, wherein a reduction the nucleation density on the hard surface of at least 10% at least one salt selected from the group consisting of calcium carbonate, calcium sulfate, magnesium sulfate, Magnesium carbonate and mixtures thereof, as described herein Method using the device for measuring the reduction the nucleation density as described herein and using a test disc selected made of stainless steel, ceramic, enamel, glass or Plexiglas. Use according to claim 1, wherein a polymeric material which is a decrease in nucleation density of at least 10% with both calcium carbonate and calcium sulfate all surfaces of the group consisting of steel, glass, ceramics and enamel. Use according to claims 1 and 2, wherein the polymeric Material identifies hydrophobic parts. Use according to claims 1 and 2, wherein the polymeric Material voluminous Substituent includes. Use according to any preceding claim, wherein the polymeric material quaternary Ammonium or tertiary Amine groups included. Use according to any preceding claim, wherein the natural one Polymer of guar gum, cellulose, locust bean gum, starch or Amylose selected is. Use according to claim 6, wherein the polymeric material is a cationic guar gum or a polyquaternary polymer. Use according to any preceding claim, wherein the polymeric material of a cleaning composition for hard Surfaces, comprising at least one surface-active Medium and other optional cleaning components for hard Surfaces, is deposited. Method for preventing scale from forming or on metal, glassy or hard plastic surfaces adhering comprising applying a cleaning composition, the one cleaning active substance and a polymeric material, such as in any of the preceding claims, comprises the surface.