ES2304360T3 - USE OF POLYMER MATERIAL IN THE TREATMENT OF HARD SURFACES. - Google Patents

Abstract

The use of a polymeric material to reduce the heterogeneous nucleation of calcium and magnesium salts on a hard surface, which comprises depositing on the hard surface a polymeric material that is a natural polymer modified with nitrogen-containing species and in which additionally the material The polymer has a weight average molecular weight greater than 10,000 and has cationic groups or groups that become cationic at the use pH.

Description

Use of polymer material in the treatment of hard surfaces.

The present invention relates to the use of a polymer material in the treatment of hard surfaces, for take care of the calcium salts forming scale. The inlays are an important dirt in the bathrooms and kitchens and that is not easy to suppress. Water supplies in the Household contain varying levels of calcium and magnesium salts. He wastewater after, for example, a bath, shower, washing dishes, rinsing, etc. will evaporate eventually leading to deposit of calcium salts on the surfaces in the form of scale.

Inlay deposits formed can be unsightly, hard and very difficult to suppress. This It can occur particularly quickly in areas with water hard in which the level of calcium in domestic water is high.

Conventional surface cleaners hard can comprise an acid or abrasive in order to help Inlay suppression. However, the surfaces of enamels and marble are susceptible to deterioration with acids and all surfaces may be scratched unsightly because to excessive use of an abrasive.

Polymeric materials have been used in the water treatment technique to prevent precipitation of salt-forming salts from the water at rest. In hard domestic surfaces, the water droplets they contain calcium or magnesium salts will eventually evaporate to dryness and inevitably calcium salts will be deposited.

Attempts have been made in the technique of depositing a polymer material on hard surfaces to allow the subsequently deposited dirt, such as grease, is easily suppressed

However, it has generally been believed in technique that is possible to provide a suppressor polymer for lime deposits

WO 99/60086 describes compositions Acids comprising polyvinylpyrrolidone and a polysaccharide as xanthan. The compositions provide a cleaning advantage for next time and it is said that they reduce or prevent the formation of lime inlay However, no data is provided for base this statement.

EP 0.875.555 describes compositions acids that comprise a polysaccharide such as xanthan. Again, the compositions provide a cleaning advantage for the next time and is said to reduce or prevent the formation of scale of lime, but again no data is provided to base this affirmation.

The present inventors have verified that, although it may not be possible to avoid the deposit of salts from calcium, it will be possible to regulate the salt deposition mechanism of calcium and thus affect the resistance of the union between the salts of calcium and hard surface.

The inlays can be deposited on the Domestic surfaces in two main ways:

(a) Crystallization in the mass solution : in this case, the inlays can be formed by homogeneous nucleation or by heterogeneous nucleation on, for example, dust particles that can act as seeds for nucleation. Heterogeneous nucleation and homogeneous mass nucleation require high supersaturation of scale-forming salts and can be rapid. Inlays formed under these conditions are prone to being amorphous and adhere only weakly to the substrate. Inlays that nucleate through a heterogeneous mass nucleation on dust particles can form at lower supersaturations and tend to form more slowly; therefore, they are prone to be more crystalline, but they will still adhere only weakly to the domestic surface.

(b) Crystallization on the hard surface : in this case, the crystals can be formed by a heterogeneous nucleation in which the domestic surface acts as the site for nucleation. In this case, the embedding is formed at a low supersaturation; The procedure is comparatively slow and results in crystalline deposits that are compact and intimately bond to the surface.

The present inventors have verified that a polymer material can be deposited on a hard surface to inhibit heterogeneous nucleation on that surface. The majority of the nucleation will then occur in the mass solution, leading to the deposit of the scale forming salts They are easy to suppress. The polymer also reduces a additional aggregation and hardening of new inlays on deposit deposits already existing.

In addition to this, it has been found that these polymers provide an anticorrosion advantage when so applied to metal surfaces.

Preventing the scale from forming or adhere to household surfaces will retain the smoothness of the surface and will avoid its tarnished. This is particularly important for surfaces that are prone to enter a excessive contact with water, as can be found in rooms bathroom, toilets, kitchens and the like. These surfaces are often made of vitreous metallic materials or hard plastics.

Summary of the invention

Consequently, the present invention provides the use of a polymer material to reduce the heterogeneous nucleation of calcium and magnesium salts on surfaces hard, which includes depositing a material on the hard surface polymer that is a natural polymer modified with species that contain nitrogen and in which additionally the polymer material it has a weight average molecular weight greater than 10,000 and has cationic groups or groups that become cationic at the use pH.

The invention also provides a procedure to prevent inlays from forming or forming adhere to metallic, vitreous or hard plastic surfaces, which comprises applying to the surface a cleaning composition that comprises a detergent surfactant and a polymeric material as described above.

Detailed description of the invention Polymer material

Many types of polymer material are suitable to be used in the present invention. It is required that the polymer is one that, when deposited on a hard surface at an appropriate level, reduce heterogeneous salt nucleation inlays on that surface. Preferably, the polymer material achieves a reduction in the speed of nucleation (number of cores per unit area per unit of time) of surface-forming salts. He following test has been derived to determine if a material polymer achieves a reduction in nucleation density (number of cores per unit area), which can be easily converted at a nucleation rate and the duration is also recorded of the experiment

The test comprises applying a solution of polymer of known concentration to a sample of a first area of a hard surface, provided a sample of a second hard surface area that has no polymer on the same and making a supersaturated solution of a salt flow inlay maker on each area sample of the surface lasts for a known period of time and comparing the number of cores formed per unit area and per unit of time for the area sample treated with the polymer material with the number of cores formed per unit area and per unit of time for the untreated area sample, to obtain a heterogeneous nucleation velocity reduction estimate on the hard surface.

The device for measuring the density reduction of nucleation

The apparatus is described below to be used in the test to determine if a polymer material is suitable for reducing nucleation density in a surface:

The apparatus 1 comprises means for supplying two solutions that, when mixed, will produce a solution supersaturated of an inlaying salt. The device to supply the two solutions comprises a pair of syringes 2 and 3. Syringes 2 and 3 contain solutions A and B, respectively. In order to ensure that the flow rates of the solutions A and B are the same, a mechanism 4 of Common drive for two syringes. The mechanism 4 is configured to provide a constant flow of solutions A and B. The mechanism 4 may comprise a syringe pump of dual drive that can be obtained from the CP company Instruments, Model 200. A mixing cell 5 is provided, which will be described further below, to mix the solutions A and B. The mixed solutions A and B are directed then on a surface to be tested, of a so that it will be described further below. The Exhausted solution is evacuated.

All the tubes used in the apparatus comprise PTFE tubes, for example, OD (external diameter) of 3.2 mm, ID (internal diameter) of 1.55 mm, obtained from the Omnifit company (Commercial brand). The device is encased in nitrogen to ensure that carbon dioxide is not absorbed again.

The mixing cell 5 comprises a block of PTFE that has a spherical space 7 formed inside. He spherical space 7 has a volume of 1 mm 3. Projecting to through the block and in space 7 are two capillary tubes 8 and 9, through which solutions A and B are supplied, respectively. Capillary tubes 8 and 9 end in nozzles close to the center of the hollow space 7. Solutions A and B are directed towards each other and mixed in the center of the hollow space 7. As the block is formed by PTFE, even if it is formed a supersaturated solution in space 7, is not produced substantially no adhesion or precipitation of material lens on the surface of the space 7. The mixed solution resulting salt from space 7 through a conduit 10, from the which is supplied to the experimental surface that is going to be rehearsed Capillaries 8 and 9 have openings at the ends 100 micrometers in diameter.

The solution mix is directed on a surface to be tested. The surface 11 that is going to be tested is arranged under a nozzle 12, through the which mixed solution of mixing cell 5 is supplied to surface 11. The resulting flow model is a model of jet-wall flow, which is well understood by The expert in the art. The flow is radial outward from the center of the surface 11 to be tested, and is uniform.

The nozzle 12 is a TPFE nozzle with a 0.8 mm internal diameter placed 3 mm above the surface  11. The mixed solution is supplied at a flow rate of 4 cm3 / min. The jet-wall apparatus 6 is jacketed in nitrogen to prevent the absorption of CO2.

All experiments were carried out in a laboratory with air conditioning. The temperature is measured at Beginning of each experiment. Temperatures are normally of 23 ° C.

The device allows continuous cooling of the surface with a solution of known composition that allows that crystal growth occurs under conditions of constant supersaturation.

Method

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

A supersaturated solution is created in a way known to one skilled in the art by mixing two together stable solutions below saturation. The solutions are degassed before using N2 to separate CO2 without dissolve.

The solution is flowed over the surface It will be treated for a fixed period of time. A time Adequate is 45 minutes.

As a consequence of the solution flow over the surface 11 to be treated, the salt forming Inlays are deposited on the surface. At the end of each experiment, any crystals on the interfacial surface of air / water are separated by suction using a small piece of tube attached to a water pump. Then the surface of the apparatus 6, briefly rinse with a saturated salt solution inlayer, dried with nitrogen and inspected under a microscope

The characterization of the degree of growth of crystals on a surface to be tested can be get using a digitized surface map, produced by micrographic means. This map can then be treated. using an image analysis computer program (for example, Aequitas, Dynamic Data Links Ltd) that allows measurements Automated size, number and distribution of crystals over an area of choice This allows density to be measured of nucleation.

The surfaces to be tested can be prepared and treated in any way to the extent that the surface remain reasonably smooth. The surfaces of the samples are preferably polished to a 1/20 finish micrometers using gamma-alumina 0.05 from the company Buehler

In order to study the effect of the polymer deposited on surface 11 to be tested, half of the surface is masked and the other half is treated with a solution or dispersion of the polymer material. A drop of 50 microliters of the polymer solution in half without mask the surface of the sample and let it moisten that part of the surface. The drop is left until it dries and washes with 10 sprays of deionized water from a gun trigger sprayer. The drying time can be 5 minutes to 20 hours, to the appropriate extent.

Preferably, the surface 11 that will be tested is in the form of a disk.

Preferably, a set of discs is used of the same size, which consist of a stainless steel disc, a ceramic disk, an enamel coated disk, a glass disk and a polymethacrylate disk.

The nucleation density of the untreated half can then be compared with the nucleation density of Half treated.

The experiment can be repeated with types different from calcium salt, for example, calcium carbonate or calcium sulfate or magnesium salts such as magnesium carbonate or magnesium sulfate.

Polymers that are particularly suitable to be used in the present invention reduce the density of surface nucleation at least 10% over at least one of The test surfaces (glass, steel, ceramic, enamel or methacrylate) with at least one of the salts (calcium carbonate, calcium sulfate, magnesium sulfate or magnesium carbonate). More preferably, the polymer will reduce the speed of nucleation at least 20%, even more preferably at minus 30% and most preferably at least 50%.

It is additionally preferred that the polymer achieve a reduction in nucleation density of at least 10%, more preferably at least 20% with both calcium carbonate and with calcium sulfate, and on any one of the surfaces, more preferably both steel and glass and, most preferably, in all steel, glass, ceramics and enamel.

It has also been found that there is a correlation between the contact angle constituted by a drop of water in a steel surface treated with polymer on the one hand and the ease of cleaning the steel surface of tanks embedded (measured as discussed below) and reduction of nucleation density on the other hand. Therefore, it has found that the polymers that cause the contact angle either <30º or> 60º cause a significant increase in cleaning score compared to polymers that they cause a contact angle within these limits. They are preferred polymers that cause the contact angle to be <20º, even more preferred are those that cause it to be> 60º or even ≥ 65 °.

Although theoretical links are not desired, it believe that the contact angle is a manifestation of energy superficial on the interfacial surface between the water and the polymer treated surface which, in turn, determines the degree in which the nuclei of crystals that develop inlays are They bind to the surface. It seems that this union is stronger for surfaces that cause the contact angle to be between 30º and 60º.

The contact angle constituted by a drop of water on the treated steel surface can be measured by any of the commonly known methods. For the For purposes of this invention, measurements can be made using a displacement microscope with a simple goniometer head, in which the eye device is equipped with a lens. He objective in the microscope's eye device is aligned with so that the horizontal mark is aligned with the surface of steel (that is, along the interfacial surface of steel / water) The center of the target is aligned with the point of three phase contact (i.e. the interfacial surface of water / steel / air). The objectives are then rotated to align with the edge of the water drop (that is, along the interfacial air / water surface) and the resulting angle is read on the goniometer scale.

Deposit of polymer material

Polymers to be used herein invention are preferably deposited well on surfaces hard. They can be applied in any way known in the state of technique Preferably, they are applied in the form of a liquid composition containing the polymer in solution or dispersion. More preferably, these compositions are liquid. aqueous.

Compositions containing polymers to be used in the present invention can be applied in a a number of ways, as will be discussed later. By example, they can be applied to a surface and left in contact to evaporate to dryness. In this case, it is simply necessary that the polymer is not able to form a thin and smooth layer, adequately of the order of a few layers Molecules of submicron thickness. Other may be applied. surface compositions with the intention that the surface be subsequently cleaned and dried. In these cases, it is preferable that the polymer also has an increased tendency to adsorb itself to the hard surface.

Examples of compositions containing the Polymers are cleaning compositions that have the effect additional deposit of a polymer to inhibit nucleation in the surface to be treated. These compositions normally will contain one or more detergent surfactants in addition to the polymer.

It is preferred that the polymer has activity in solid / liquid interfacial surface. Is particularly preferred that the polymer adhere strongly enough to the surface to be resistant to suppression by cleared up. However, the polymer should not adhere so too strong to the surface, otherwise there may be a tendency for the polymer to accumulate on the surface, which it can lead to negative effects, for example, an appearance poor.

Some surfaces that are particularly prone to scale deposits, such as those made of steel, ceramics, glass and enamel, they are known to have a load negative. The polymer must have cationic groups or groups that are make cationic at the use pH. It is preferred that the polymer comprise amino groups, particularly quaternary ammonium groups or tertiary amino.

The polymer deposit can be assisted also if it has a relatively high molecular weight. The weight molecular weight average is greater than 10,000, preferably greater than 50,000

The polymer deposit can be assisted also if the polymer or polymer complex with a surfactant It is rigid or semi-rigid. The polymer material can have an inflexible main chain, for example, due to a unsaturation or the presence of rings. Alternatively, you can have a positive charge, permanently or temporarily, at the pH of the composition, the restrictive conformation of the main chain due to repulsion between charges, it may have a chain principal that is flexible in principle but restricted in the molecular conformation derived from the polymer architecture, by example, by ramifications, unsaturation, rings or groups bulky sides.

If the polymer itself does not have a charge net positive (for example, if it has a negative or neutral charge), the polymer deposit can also be favored by use of a deposit adjuvant as a polymer or surfactant with cationic charge

Effect of nucleation inhibition

In order to provide a polymer that inhibit nucleation on the surface where it will be deposited,  it is preferred that the polymer material has at least one of the following properties:

1. Hydrophobicity . The polymer material may have hydrophobic parts. As indicated above, in order to improve the deposition of the polymer on surfaces such as steel, glass, etc., it is preferred that the polymer also has hydrophilic parts. Consequently, it is particularly preferred in this case that the polymer has surface activity, having hydrophilic and hydrophobic parts on different parts of the molecule, for example, on different sides of the polymer's main chain.

Ways to provide are set out below. hydrophobicity

2. Steric factors . Inhibition of nucleation can be obtained by steric factors. Preferably, the polymer will comprise large and bulky substituents (for example, which incorporate a tertiary carbon atom and / or more than 5 non-hydrogen atoms). Preferably, these are separated along the main polymer chain at distances that are smaller than the critical stable microcrystalline size. In this way, if a microcrystal is formed on the polymer surface, it will be avoided by steric factors that grow to a size that is thermodynamically stable. Preferably, the substituents are non-uniformly separated to further inhibit nucleation.

Solubility

Polymeric materials to be used in the present invention are preferably soluble or dispersible in a surfactant solution but hardly soluble or water dispersible However, the polymer material can be also partially in water and soluble in an aqueous solution of surfactants of the type used in cleaning compositions of hard surfaces. The solubility of the polymer material in a aqueous surfactant solution is suitably in the range 0.01-50% by weight, more preferably in the range of 0.50-10%, most preferably of about 0.1-1.0%, particularly 0.4-1.0% by weight. The concentration of surfactants is adequately in the range of 0.1-20% in weight, preferably 1.0-10% or 6% by weight.

Types of polymers

The present application can be carried out with many types of polymers of suitable structure to achieve the properties described above. You can provide the following non-limiting examples.

Polymers suitable for use in the Present invention can be produced by any method of suitable polymerization, for example, emulsion polymerization or in solution. The copolymers can be produced, for example, by graft, block or mass copolymerization.

Hydrophobicity can be introduced into the polymers, for example, including hydrophobic side chains, as C 8 -C 22 alkyl chains, alkenyl or rented. These can be introduced, for example, in form of esters of C 8 -C 22 alcohols or Similar.

The polymers used herein invention comprise natural polymers, such as starches and gums, modified with nitrogen-containing species. For example, him polymer can comprise guar gum, cellulose, locust bean gum, starch, starch amylose or similar natural polymers. He Natural polymer can be modified by reaction of the hydroxyl groups with other groups, to provide groups lateral to modify the substantivity of the surface of the polymer or to provide inhibitory effects of the nucleation

For example, the natural polymer can be modified with species containing nitrogen as groups hydroxypropyl trimethylammonium. For example, the polymers can comprise cationic guar gums such as guma guar de hydroxypropyl-trimethylammonium with a degree of replacement in the range of 0.11 to 0.22, available in the trade under the JAGUAR C13S, JAGUAR C14S trademarks, JAGUAR C17 and JAGUAR C-162.

Another class of polymers that can be used in the present invention comprises polymoternary polymers commo Polyquat 10, which is commercially available under the brands Polymer JR30M, JR125 and JR400.

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

Other suitable properties

Preferably, the polymer material is not highly colored within the pH range of interest (3-12).

Polymers are provided in the following table which has been found to significantly reduce the nucleation

one

Other polymers that are chemically equivalent to the aforementioned polymers can be Used instead. These polymers are known to the expert in The technique.

Hard surface treatment compositions

The polymer material can be used according to the present invention in any suitable formulation.

The formulation must be adequate to deposit The polymer material on a hard surface. The material polymer can be present in the formulation in any form adapt, for example, in the form of a solution or dispersion.

Suitable formulations include solutions, dispersions or emulsions of the polymer material in a vehicle, by example, a substantially non-aqueous material such as ethanol, but preferably water. The compositions can only be used to deposit polymer material, or they may have functional additional as cleaning.

The composition can be applied by any adequate medium. For example, it can be poured or sprayed on the surface of a container or from an aerosol can or from a spray gun applicator.

The compositions to be used herein invention may include any of the normal ingredients for hard surface cleaning compositions.

Preferably, a cleaning composition of hard surfaces comprises at least one detergent surfactant and Other optional hard surface cleaning components.

Surfactants

The composition according to the invention will comprise active components such as detergents (surfactants) that they are generally chosen among detergent active components both anionic and nonionic.

Suitable anionic surfactants are salts water soluble esters of organic sulfuric acids and acids sulfonic acids that have an alkyl group in the molecular structure It contains 8 to 22 carbon atoms.

Examples of these anionic surfactants are water soluble salts of:

- chain alcohol sulfates long (i.e. 8-22 C atoms) (hereafter called PAS), especially those obtained by sulfating the fatty alcohols produced by reducing glycerides of tallow or coconut oil;

- alkyl benzene sulphonates, such as those in which the alkyl group contains from 6 to 20 atoms of carbon;

- alkane sulphonates secondary.

       \ vskip1.000000 \ baselineskip
    

Also suitable are salts of:

- alkyl glyceryl ether sulfates, especially the ethers of the oil-derived fatty alcohols tallow and coconut;

- monoglyceride sulfates of fatty acids;

- sulfates of the reaction product of one mole of a fatty acid and 1 to 6 moles of ethylene oxide;

- salts of alkylphenol ethyleneoxy ether sulfates with 1 to 8 ethyleneoxy units per molecule and in which the alkyl groups contain from 4 to 14 carbon atoms;

- the reaction product of fatty acids esterified with isethionic acid and neutralized with a alkali;

and their mixtures.

Soluble synthetic anionic surfactants Preferred in water are alkali metal salts (such as sodium and potassium) and alkaline earth metals (such as calcium and magnesium) of alkylbenzenesulfonates and mixtures with oliphenesulfonates and alkyl sulfates, and acid mono-glyceride sulfates fatty The most preferred anionic surfactants are sulfonates alkyl aromatics such as alkylbenzenesulfonates which they contain 6 to 20 carbon atoms in the alkyl group in a linear or branched chain. of which are particular examples sodium salts of alkylbenzenesulfonates or alkyl toluene-, -xylene- or -phenolsulfonates, alkylnafatalene sulfonates, ammonium diamilnafatalene sulfonate and sodium dinonylnaphthalene sulphonate.

If the anionic surfactant will be used synthetic, the amount present in the compositions of the invention  it will generally be at least 0.5%, preferably at least 1.0%, more preferably at least 2.0%, but not more than 20%, preferably at most 10%, more preferably at most 8%

Suitable nonionic surfactants can be widely described as compounds produced by the condensation of alkylene oxide groups, which are of nature hydrophilic, with an organic hydrophobic compound that can be of aliphatic or alkyl aromatic nature. The length of the hydrophilic or polyoxyalkylene radical which is attached to any particular hydrophobic group can be easily adjusted to produce a water soluble compound that has the balance desired between hydrophilic and hydrophobic elements. This makes possible the choice of nonionic surfactants with the correct HLB, taking into account the presence of the organic solvent and a possible hydrocarbon co-solvent in the composition.

Particular examples include the product of condensation of aliphatic alcohols having 8 to 22 atoms of carbon in one with linear or branched chain figuration with ethylene oxide, such as coconut oil condensates of ethylene having 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 moles of oxide ethylene per mole of alkylphenol; product condensates of reaction of ethylenediamine and propylene oxide with ethylene, condensates containing 40 to 80% of groups ethyleneoxy by weight and having a molecular weight of 5,000 to 11,000

Other examples are: alkyl glycosides that are condensation products of long chain aliphatic alcohols and saccharides; tertiary amine oxides of RRNO structure, in which R is an alkyl group of 8 to 18 carbon atoms and the other R are each alkyl or hydroxyalkyl groups of 1 to 3 carbon atoms, for example dimethyldedecylamine oxide; phosphine oxides tertiary structure RRRPO, in which R is an alkyl group of 8 to 18 carbon atoms and the other R are each alkyl groups or hydroxyalkyl of 1 to 3 carbon atoms, for example, oxide of dimethyl dodecylphosphine; Y dialkyl sulfoxides of RRSO structure in which R it is an alkyl group of 10 to 18 carbon atoms and the other is methyl or ethyl, for example, methyltetradecyl sulfoxide; fatty acid alkylamides; alkylene oxide condensates of fatty acid alkylamides and alkyl mercaptans. They are particularly preferred. aliphatic ethoxylated alcohols.

The amount of nonionic surfactant that is going to be employed in the cleaning composition of the invention will be preferably at least 0.2%, more preferably at least 0.5%, most preferably at least 1%. The maximum amount is suitably 15%, preferably 10% and most preferably 7%

The compositions may contain amounts of both anionic and nonionic surfactants that are chosen, taking into account the level of electrolyte present, with the in order to provide a liquid detergent composition structured, that is, one that is "self-thickened". Therefore, despite the presence of organic solvent, cleaning compositions thickened liquids can be prepared without using no additional thickening agent that, however, has a Long storage life for a wide range of temperatures

The weight ratio of anionic surfactant to nonionic surfactant may vary, taking into account previous considerations, and will depend on its nature, but it is preferably in the range of 1: 9 to 9: 1, more preferably from 1: 4 to 4: 1 and ideally above 1: 1.

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

It is also possible to optionally include amphoteric, cationic or hybrid ion surfactants in the Compositions according to the invention.

Suitable amphoteric surfactants that can be optionally employed are derivatives of aliphatic amines secondary and tertiary that contain an alkyl group from 8 to 18 carbon atoms and an aliphatic group substituted with a group water-solubilizing anionic, for example, Sodium 3-Dodecylamino-Propionate, 3-dodecylaminopropane sulphonate sodium and N-2-hydroxidedecyl-N-methyl-taurate of sodium.

Suitable cationic surfactants are salts of quaternary ammonium that have one or two aliphatic groups of 8 to 18 carbon atoms and two or three small aliphatic groups (per example, methyl), for example, bromide cetyltrimethyl ammonium.

Suitable hybrid ion surfactants which may be optionally employed are derivatives of compounds aliphatics of quaternary ammonium, sulfonium and phosphonium that have a aliphatic group of 8 to 18 carbon atoms and an aliphatic group substituted with a water-solubilizing anionic group, for example, propane-1-sulfonate-betaine  from 3- (N, N-dimethyl-N-hexadecylammonium), propane-1-sulfonate-betaine of 3- (dodecyl methyl sulfonium) and ethane sulfonate betaine from 3- (cetylmethyl phosphonium).

Additional examples of suitable surfactants they are compounds commonly used as activity agents superficial in well-known textbooks "Surface Active Agents ", Volume I, by Schwartz and Perry and" Surface Active Agents and Detergents ", Volume II, by Schwartz, Perry and Berch

If surfactants will be present in the compositions of the present invention, the total amount of surfactant compound to be used will generally be of 0.5 to 20%. Preferably, the amount is at least 1%, plus preferably at least 3%. The maximum amount is usually 15% or less, preferably not more than 10%. Preferably, the type of surfactant and its amount are chosen so that it does not form a complex with the polymer that cannot be kept dissolved or dispersed in the composition.

The compositions according to the present invention they may contain other ingredients that help in their performance of cleaning. For example, the compositions may contain abrasives. insoluble such as calcites, silica and other abrasive materials known in the art, or may contain improvers of the detergency such as nitrilotriacetates, polycarboxylates, citrates, dicarboxylic acids, water soluble phosphates (especially ortho-, pyro- or polyphosphates or mixtures thereof), Zeolites and their mixtures in an amount up to 25%. Some of these detergency builders can additionally act as abrasives if they are present in an amount above their water solubility. If present, the improver of the detergency will preferably form at least 0.1% of the composition.

They can also be used optionally metal ion sequestrants such as ethylenediaminetetraacetates, amino polyphosphonates (DEQUEST®) and phosphates and a wide variety of acids and organic salts poly-functional, provided they are compatible with polymer and optional abrasive material.

An additional optional ingredient for compositions according to the invention is a regulatory material of the foaming, which can be used in compositions that have a tendency to produce excessive foams in use. A example of a foam forming regulator material is a soap. Soaps are salts of fatty acids and include salts of alkali metal and ammonium fatty acid containing about 8 to about 24 carbon atoms and, preferably, from about 10 to about 20 atoms carbon Sodium and potassium salts are particularly useful and mono-di- and tri-ethanolamine of the mixtures of fatty acids derived from coconut oil and peanut oil. When employed, the amount of soap can form at least 0.005%, preferably 0.1% to 2% by weight of the composition. A Additional example of foam forming regulator material is silicone oil

An additional optional ingredient that can be used in the compositions according to the invention is an acidic material that helps suppress deposits of scale. Examples of they are well known in the art and include phosphoric acid and many di- and polycarboxylic acids.

The compositions according to the invention can also contain, in addition to the aforementioned ingredients, others various optional ingredients such as dyes, bleach, optical brighteners, dirt suspending agents, detergent enzymes, compatible bleaching agents such as active chlorine compounds or hydrogen peroxide agents gelation control, stabilizers freeze-thaw, bactericides, preservatives (for example, 1,2-benzothiazolin-3-one), perfumes and hydrotropes.

The surface treatment composition Hard can have any suitable pH. However, it is preferred that the compositions be mildly alkaline (particularly if they are formulated as surface cleaning compositions, with in order to improve the effect of surfactants), neutral or slightly acidic (particularly if they include cationic species or amino groups that are protonated and cationic in an environment acid, in order to help the deposit). However, it is preferred that the compositions are not too acidic, in order to avoid deterioration of acid sensitive surfaces. In In particular, it is important to minimize or avoid the presence of acids organic sequestrants that are prone to attack surfaces such as enamels Preferably, the pH is in the zone of 3-12, with intervals being particularly preferred from 3.5-6.0 and 10-12. In any case, the pH is adequately above 3.0 and more preferably above 3.5.

The use of a polymer material according to the present invention can provide, in addition to the inhibitory effects of the inlays, a longer lasting shine, better appearance of the surface and a smooth texture to the treated surfaces.

The compositions according to the present invention they are useful for treating domestic surfaces, for example, in kitchens and bathrooms, including walls, floors, toilets, sinks and work surfaces. They are particularly suitable for treating surfaces that are prone to remain in contact Prolonging with water such as: walls and floors of showers, tubes and bath edges, faucets, shower heads, sinks, sinks and Similar.

The present invention will be described. additionally by reference to the following examples no limiting

Examples

All percentages mentioned herein Descriptive report are by weight, based on the total composition, unless specifically mentioned otherwise.

Surface treatment compositions they were prepared according to the following formulations (* indicates the nucleation inhibitor polymers):

Example 1 Bath cleaning formulation

101

Example 2 Bath cleaning formulation

102

Tests to facilitate the suppression of surface deposits treated

Steel tiles formed of certain surfaces of the Mersey Metals company. The tiles had  0.9 mm thick, 100 x 100 mm square in size, finished with a beveled 304 and specular finish and countersunk on one side. The tiles are thoroughly cleaned and rinsed using water demineralized Then the tiles are allowed to dry.

A 0.5% by weight aqueous solution is applied in a uniform layer to each tile using an applicator K-bar, number K-bar 0010. It pipette 0.5 ml of solution through the upper edge of the tile next to the K-bar. The speed of K-bar drive adjusts to 16.5 cm / s.

The tiles are allowed to dry for up to 24 hours.

The dry tiles are then arranged to 10º with respect to the horizontal. Then each tile is cleared with 200 ml of demineralized water flooded through the tile by a peristaltic pump at a speed of 812 ml / min. Then the tile is allowed to dry in a horizontal position.

Plastic templates in the form of sheets squares of acetate film having a square hole in The center are attached to each tile. 0.5 ml of water are added Prenton (27ºFH: French hardness) to each tile in the square defined by the plastic template. The goda is allowed to dry. This stage is repeated for additions of 6 x 0.5 ml of Prenton water, each one of which is allowed to dry. The treated tiles are submitted then a cleaning test using a WIRA machine (Wool Institute Research Association). This device measures the number of cycles needed to clean a defined area. The area that is going to to be cleaned corresponds to the exposed area defined by the template of plastic. The tiles are cleaned using a J-cloth® immersion in a WIRA machine that Operates for 4 cycles (16 x 4 = 64 routes under the maximum load). Once clean, the tiles are allowed to dry and value in terms of scale formation and tarnish. The inlay formation and tarnish are valued subjectively and are scored on a scale of 1 to 4, in which 1 corresponds to nothing or very little suppression and 4 corresponds to a completely clean surface.

Results

The method of Example 2 is performed with the polymer materials collected in the following table. They were valued the tarnished results and scores are exposed to continuation.

103

Nucleation Density Measurement

The apparatus described above to measure the Nucleation density can be used to test the effect of polymer on the surface nucleation density, such as follow.

A sample of 10 mm stainless steel diameter (type 304 steel) polished to a finish of 0.05 Micrometers was masked in one half. The other mitas was treated with a 0.5% by weight aqueous solution of polymer.

Solution A comprises calcium chloride (obtained from Aldrich 99.99% pure plus) in 0.1 M NaCl (obtained from Fisons, 99.9 plus pure) and solution B comprises NaHCO 3 (obtained from BDH, 99.5% pure plus) in 0.1 M NaCl. The concentrations of calcium chloride and baking soda are altered to get the supersaturation of calcium carbonate in a known way to The expert in the art.

The pH is regulated to 8.5 using NaOH (which is you can get from the company Fisons, 86% plus pure) or HCl (which You can get from the company Aldrich, 0.5098 N, ACS quality).

The experiment was repeated with a certain number of different types of polymer. The results are shown in the following table:

104

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

Claims (10)

1. The use of a polymer material to reduce the heterogeneous nucleation of calcium and magnesium salts in a hard surface, which include depositing on the hard surface a polymer material that is a natural polymer modified with nitrogen-containing species and in which additionally the polymer material has a weight average molecular weight greater than 10,000 and has cationic groups or groups that become cationic at pH of use. 2. The use according to claim 1, wherein a reduction in the hard surface nucleation density of at least 10% is achieved with at least one salt selected from the group consisting of calcium carbonate, calcium sulfate, magnesium sulfate, magnesium carbonate and mixtures thereof, and the method described herein uses the apparatus to measure the reduction of nucleation density as described herein and using a disk of test chosen from stainless steel, ceramic, enamel, glass or methacrylate 3. The use according to claim 1, wherein use a polymer material that achieves a reduction in density at least 10% nucleation with calcium carbonate and sulfate calcium on all surfaces of the group consisting of steel, glass, ceramics and enamel. 4. The use according to claims 1 and 2, in that the polymer material has hydrophobic parts. 5. The use according to claims 1 and 2, in which the polymer material comprises bulky substituents. 6. Use according to any of the previous claims, wherein the polymer material it comprises quaternary ammonium or tertiary amino groups. 7. Use according to any of the previous claims, wherein the natural polymer is chosen from guar gum, cellulose, locust bean gum, starch or amylose 8. The use according to claim 6, wherein The polymer material is a cationic guar gum or a polymer polyquaternary 9. Use according to any of the previous claims, wherein the polymer material is deposited from a hard surface cleaning composition comprising at least one surfactant and other components of optional hard surface cleaning. 10. A procedure to prevent training adhesions of encrustations to metallic, vitreous or hard plastics, which comprises applying to the surface a cleaning composition comprising a detergent surfactant and a polymeric material as described in any of the previous claims.