Liquid abrasion detergent compositions

FIELD: producing detergent compositions.

SUBSTANCE: water alkaline abrasion detergent composition comprises, in mass %, 55-80 of abrasion agent, 0.15-0.40 of anion polymer, 0-0.4 of surface active agent and does not comprise thickening clays or thickening silicon dioxide. The detergent compositions can be ready for use or concentrated with at least 55% in mass of abrasion agent, which a consumer can be diluted up to the product ready for use without loss of long-term stability. The composition is allowed to be packed or canned.

EFFECT: enhanced efficiency.

9 cl, 2 tbl, 3 ex

The technical field to which the invention relates.

The present invention relates to aqueous liquid compositions that include an abrasive material and a polymeric thickening agent, which supports the abrasive material suspended in a liquid. The invention can be used in the production of detergents.

The level of technology

Liquid abrasive cleaning compositions are well known in the art and they usually contain a combination of detergent surfactants, especially anionic and nonionic surfactants, which together form a layered micellar phase and thereby cause the thickening of the liquid. Layered phase acts as suspendida system that keeps the abrasive material in a stable suspension. In order to further improve the stability of the suspension, are often added to the electrolyte.

However, detergent surfactants are expensive components, and it is not always obvious whether they give a contribution to the efficiency of the cleaning composition, in addition to their thickening and suspending action. Therefore, various efforts have been made to reduce the amount of surface-active substances and to provide thickening and suspenders ability, which is necessary for the preservation of abrasive material in the stable the first suspension, by adding a polymeric thickener.

So, in document WO 91/08283 disclosed a liquid abrasive cleanser composition containing 0.02 to 20% detergent, 1-70% granular abrasive material and 0.01-10% thickening mixtures containing linear non-starch polymer type and polymer type of branched starch (amylopectin). The non-starch polymer type include various natural resins and synthetic polymers. Especially preferred partially acetylated xanthan gum. In practice, the required amount of thickening of the mixture is approximately 3% by weight of the entire composition, and all of the examples listed 1,5% non-ionic surfactants.

In document WO 95/08619 disclosed a liquid abrasive cleanser composition containing cross-linked polyacrylate, or at least one nonionic surfactant, or a combination of anionic surfactant and nonionic surfactant, an agent regulating the pH and abrasive is calcium carbonate. Indicates that the composition containing 0.1-2% of a polyacrylate polymer, 0.1 to 10% nonionic and up to 10% anionic surfactants, and 5-60% of abrasive material. In practice, in accordance with the examples, compositions containing 0.25-0.4% polymer, 0.5% or more nonionic surfactants, and 40% of the abrasive material. Nonionic p is supercial-active substance required for to ensure a good frictional properties. Similar compositions disclosed in document EP 649898, with the additional condition that they contain hypochlorite and which surfactant is stable at bleaching.

In document WO 96/35771 disclosed a liquid abrasive cleanser composition containing 10-30% inorganic abrasive material and a thickening system which comprises at least from cross-linked polyacrylate polymer and clay smectite type, the clay is preferably approximately 50-80% of the thickening system. Preferably the thickening system is 1-2,5% of the composition. In practice, all the cleaning compositions contain at least 0.5% polyacrylate and at least 0.75 percent clay.

In document EP 352258 described suspension of very fine powders on the basis of silicon dioxide, such as zeolite, comprising an organic polymer compound with hydroxyl groups and a molecular weight above 1500, as suspendida agents that require the presence of certain cationic or amponsah surfactants as stabilizers. The particle size suspendiruemye zeolites is usually from 0.5 to 10 μm, and the mass of material has a particle size less than 6 microns. The only example of polymers is a combination of the guar and can anovas resins.

In the document EP-A 0875557 described aqueous thickener composition, suitable for many end uses, which contains 0.04-30 wt.% a mixture of at least two surfactants in a predetermined ratio and the difference in hydrophilic/lipophilic balance of at least one unit, and 0.01-5 wt.% associate thickener selected from hydrophobically modified hydroxyethyl cellulose, hydrophobically modified nonionic polyol and a hydrophobic modified emulsion polymer, soluble in alkalis. In practice, the number of associate thickener is 1-2%, and the amount of the mixture of surfactants is 1-10%.

In document EP 301885 disclosed a liquid abrasive cleanser composition containing up to 70% of an abrasive, water suspenders environment obtained by the combination of anionic surfactant and electrolyte, and also containing polyacrylate material having a molecular weight of between 500 and 3000. In practice, these compositions contain at least 3.5% of the surfactant.

Liquid abrasive cleaning compositions are usually sold in a form ready for consumption, and contain 10-50%, usually 20-45% of solid abrasive material. Such compositions cannot be diluted, for example, to the presence of solid abrasive mA is Arial 10-20% without losing their stability, which leads to the deposition. Although the patent literature indicates that the content of the abrasive reaches 70%, industrial products usually contain less abrasive.

Brief description of the invention

The problem solved by the invention is to develop such a stable liquid aqueous abrasive cleanser compositions that do not require the presence of a detergent surfactant to obtain a stable suspension.

A further object of the invention is also developing liquid water abrasive cleaning compositions in which the abrasive material suspended with a polymeric thickening agent.

Another objective of this invention to provide an aqueous abrasive cleanser compositions, which may be provided either in the form of ready to use or concentrated form that the consumer may be diluted until the product is ready to use, without loss of long-term stability.

Accordingly, this invention provides a liquid aqueous abrasive cleanser compositions containing insoluble abrasive material and anionic thickening polymer.

Detailed description of the invention

Everything listed in the description of the components represented in wt.% calculated on the whole composition. Used herein, the term "liquid" refers to the mother of the lamas, which have an easy fluidity, as well as to materials that are thick, almost pasty, but due to the inherent property of fluidity, can physically be classified as a liquid.

According to the invention, the liquid aqueous abrasive cleanser compositions contain more than 55-80% of solid abrasive material, 0,15-0,40% anionic thickening polymer and not necessarily from 0 to 0.4 wt.% surface-active substances.

Dispersed, suspended solid powdered abrasive material is an essential ingredient of the liquid abrasive compositions according to the present invention. Preferably, the amount of abrasive material, as mentioned above, is at least 55% and for practical purposes usually does not exceed 80%, more preferably not more than 75%.

Products can be made up in a mixture and Packed in the form of compositions ready for use with the above content of abrasive materials. Such compositions can take the form of a viscous (thick, almost paste-like products. Thick, viscous products in the form of ready to use, preferably contain greater than 50%, preferably at least 55%, most preferably 60% solid abrasive material.

In the alternative, the compositions of the invention can be the process of constructing the s in the mixture and Packed in the form of concentrates, which is diluted prior to use by adding a suitable amount of water. Such compositions have the advantage that they require smaller packaging for the same finite amount of product ready to use, and thus provides an advantage in storage and transportation. The composition can be prepared and transported in bulk form as intermediate products for the production equipment located close to the consumers, where the composition is diluted with water and then packaged and sold as products ready to use. On the other hand, the composition can be packaged directly and sell in the form of concentrates, which the consumer will dilute it with water at home.

These products have a high content of abrasive materials above 50%, preferably at least 55%, most preferably at least 60%.

Preferred abrasives have a Mohs hardness is below 6, but greater than 1, although for special applications can be used abrasives with higher hardness. Preferably, the Mohs ' hardness equal to at least two.

Suitable abrasive materials can be selected from inorganic abrasives, such as zeolites, silicas, silicates, carbonates, oxides of aluminum, and the organic polymeric abrasives, such as polyethylene, polycarbonate, polyurethane, polystyrene, polypropylene, polyethylene terephthalate, polymethylmethacrylate, nylon, and mixtures thereof. The preferred abrasive materials are: calcium carbonate (as calcite), a mixture of carbonates of calcium and magnesium (dolomite), zeolite, alumina, hydrated alumina, feldspar, talc and silicon dioxide. Especially preferred are calcite, dolomite and mixtures thereof with low silica content, especially amorphous silica, due to their low cost and good abrasive properties.

The preferred average particle size of the abrasive material is in the range of 0.5-500 μm, with values from about 10 to 100 microns are especially preferred. In this interval an acceptable compromise between good performance when cleaning and low degree of damage to the substrate. However, in the case of silica in combination with calcite or dolomite, is also very suitable are particles having an average size in the range of 100-500 microns.

Anionic polymers are used to obtain a stable suspension of abrasive particles in the aquatic environment. They are available in different forms supplied by various manufacturers, for example, in the form of aqueous suspensions or in the form of firmly what about the powder. Moreover, these polymers can be hydrophobically modified and/or custom made. For products with a high content of abrasive materials, i.e. products that contain abrasive material above 50%, preferably at least 55%, most preferably at least 60%, the polymers are preferably used in amounts of at least 0,07%, more preferably at least 0.1 percent, most preferably 0.15% or more. For these products the maximum content of polymers is usually no more than 0,45%, preferably below 0,40 or even 0,35%.

Suitable polymers are high molecular weight products, that is, they have a molecular weight of at least 10000, in particular at least 50000 or even 100000. Suitable polymers can be found among the polymers polycarboxylate type, such as different a polyacrylate homopolymers and copolymers, which typically have a molecular weight of 500,000 or higher, often much higher than 1000000, and various polysaccharides, such as carboxymethylcellulose, hydroxyethylcellulose, hypromellose, carrageen (pearl moss), alginate, resin tragakant, resin carob, guar and xanthan resin.

Very suitable are synthetic polycarboxylate polymers, such as hydrophobically modified emulsion floor the measures and carbomer (solid powdered polyacrylic acid). The first polymers are particularly effective for products with low content of abrasive material, while the latter are particularly effective for products with a high content of abrasive material. Suitable hydrophobically modified emulsion polymers should preferably have a value of the initial viscosity η₀at least 1000 PA·C.

Some of these thickening polymers such as Carbopol ETD-30 2690 lose their thickening properties in the presence of appreciable quantities of calcium ions. Therefore, when used kaltsitnykh or similar calcium-containing abrasive material, it is necessary to take appropriate measures and make use of thickening polymers, insensitive to calcium (such as Carbopol 674).

Other thickening agents, such as thickening of clay or thickening of silicon dioxide, is not necessary to achieve the desired stability of the suspension, and in preferred embodiments the embodiment of the invention such thickeners are not.

As noted above, the compositions according to the invention there is no need for surface-active substance in connection with the problem of stability. However, it may be useful to add a limited amount of detergent surfactant in order to improve the cleaning properties of the product is tov for some types of contaminants and/or to provide foaming during use, which is desirable for some consumers. You can use non-ionic, anionic, afienya and amphoteric surfactants. Preferred are non-ionic surfactants. Nonionic surfactants can be combined with other classes of surfactants, especially anionic surfactants. Usually, the presence of amponsah or cationic surfactants, though possible, does not give any useful effect, and composition without such surfactants are preferred variant embodiment of the invention.

Suitable non-ionic surfactants in the broader sense can be described as compounds obtained by condensation alkalinising groups, which are hydrophilic agents, with an organic hydrophobic compound which may be aliphatic or alkylaromatic in nature. The length of the hydrophilic polyoxyalkylene group which is condensed with any particular hydrophobic group can be easily adjusted so as to obtain water-soluble compound having the desired degree of combination of hydrophilic and hydrophobic elements.

Specific examples include the condensation products of aliphatic alcohols containing from to 22 carbon atoms or a linear, or branched configuration, with ethylene oxide, such as the condensation products of coconut oil with ethylene oxide having from 2 to 15 moles of ethylene oxide per mole of coconut alcohol; the condensation products of ALKYLPHENOLS in which the alkyl group contains from 6 to 12 carbon atoms, with 5-25 by moles of ethylene oxide per mole of alkylphenol; the product of the condensation product obtained by the interaction of ethylene diamine and propylene oxide, with ethylene oxide, and these condensates contain from 40 to 80 wt.% parts of ethylene oxide and have a molecular weight of from 5,000 to 11,000; the oxides of tertiary amines patterns R3NO, where one group R is an alkyl containing from 8 to 18 carbon atoms, and each other is a metal, ethyl or hydroxyethylene group, for example an oxide dimethyldodecylamine; the tertiary phosphine oxides of structure R3NO, where one group R is an alkyl containing from 10 to 18 carbon atoms, and each other is an alkyl or hydroxyalkyl group with 1 to 3 carbon atoms, for example the oxide dimethyldodecylamine; and diallylsulfide patterns R2SO, where one group R is the alkyl containing from 10 to 18 carbon atoms and the other represents a methyl or ethyl group, for example methylcellulose; alkylolamides fatty acids; the condensation product of alkalisation and with killmyday fatty acids and allylmercaptan. Nonionic surfactants can also choose from a number of alkylpolyglycoside.

Especially suitable are surfactants ethoxylated aliphatic alcohol, such as C9-C11*5 (ethylene oxide), With a 12-C13*6.5 (ethylene oxide) and C13-C15*7 (ethylene oxide) (the number of ethylene oxide groups averaged) and oxides of tertiary amines, such as oxide dimethyldodecylamine and the oxide dimethylbenzylamine or mixture of aminoxide, with a large proportion of aminoxide.

Suitable anionic surfactants are water-soluble salts of esters of sulfonic acid and sulfuric acid, which have in their molecular structure an alkyl group containing from 6 to 22 carbon atoms. These surfactants useful to add to provide compositions good foaming properties that the consumer is often considered desirable.

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

- sulfates of long chain alcohols (i.e. 8-22 carbon atoms), in the following referred to as PIF, especially those which are formed during the sulfonation higher alcohols formed in the restoration of the glycerides of tallow or coconut oil;

- alkylbenzenesulfonates, for example those in which the alkyl group contains from 6 to 20 atomo is carbon;

- secondary alkanesulfonyl (in the following referred to as SDS).

Also acceptable salts are:

- sulfates alkylglycerols ethers, especially those ethers of higher alcohols obtained from tallow and coconut oil;

- sulphate of monoglycerides of fatty acids;

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

- salt of the sulfate ester of an alkylphenol and ethylene oxide containing from 1 to 8 units of ethylene oxide in the molecule, in which the alkyl radicals contain from 4 to 14 carbon atoms; and mixtures thereof.

Preferred water-soluble synthetic anionic surfactants are salts of sodium, potassium, magnesium and ammonium alkylbenzenesulfonate, reincorporation, and alkyl sulphates, sulphates of monoglycerides of fatty acids.

Suitable amphoteric surfactants that can be optionally used, are derivatives of aliphatic secondary and tertiary amines containing alkyl group of 8-18 carbon atoms and the aliphatic group is substituted by an anionic group, contributing to dissolution in water, such as 3-dodecylthiophene sodium 3-dodecylbenzenesulfonate sodium and N-2-hydroxydiphenyl-N-methyltaurine sodium.

Additional examples of suitable active is of detergent compounds are compounds, which are normally used as surface-active agents described in well-known directories "Surfactants", vol 1, Schwartz and Perry and "Surface active agents and detergents", volume 2, Schwartz, Perry and Berch.

Compositions according to the invention can contain the total amount of surfactant below 0.5%. Preferably, the total content of surfactants does not exceed 0,4% or even 0.3 percent. To effectively improve cleaning and/or foaming properties desirable minimum level of the total content of the surfactant is 0.01 percent, preferably at least 0.02 percent, more preferably at least 0.05% or even 0.1 percent.

The amount of non-ionic surfactants preferably should be below 0.5%, more preferably equal to or lower than 0.45%, and most preferably equal to or lower than 0.35 per cent or even 0.3 percent. To improve the cleaning properties of the composition and stability of the suspension preferably the content of the nonionic surfactant is at least 0.01 percent, more preferably at least 0.02 percent. For concentrated products, the amount of nonionic surfactant more preferably is at least 0.02 percent, most preferably at least 0,03%./p>

Compositions according to the invention have an alkaline reaction, more specifically, they have a pH value above 8, preferably 9 or higher. Thus, the compositions can be made alkaline using a suitable base such as an alkali metal hydroxide or carbonate of an alkali metal, ammonia or an organic base with an indicator of pKa greater than 9, such as triethylamine, aminomethylpropanol (AMP), aminobutanol, mono-, di - or triethanolamine, mono-Isopropylamine, or aminomethylpropanol. Particularly effective is the AMP, and preferably it is added in amounts up to 0.5%, more preferably of 0.2-0.4% in the absence of any other Foundation or 0.1-0.2% in the presence of another reason.

For the compositions according to the invention is usually no need for additional electrolyte, which differs from the potential of anionic surfactants and the base for adjusting pH. Preferably the additional content of the electrolyte is less than 0.3%, more preferably less than 0.2%.

Optional components

According to the invention the abrasive composition may contain optional components that enhance its cleansing properties, such as organic solvents known in the prior art for use in abrasive cleaning compositions, in particular dissolve Italy, whose molecules have a polar group, such as hexanol, simple alkyl ethers of ethylene and propylene glycol. The composition may also contain bleaching agents, in particular halogen bleaching agents, more specifically hypochlorite, provided that the polymers and surfactants are stable to hypochlorite.

In addition, compositions according to the invention can contain additional components, such as:

components, further improving their attractiveness to consumers, such as coloring agents, optical brighteners, especially fragrances (perfumes can give you an additional positive effect on the stability of suspension);

- fuses that prevent microbial contamination.

Properties of fluids

According to the invention a good, ready-to-use liquid abrasive cleaning compositions with a low content of abrasive material have such characteristics of liquid flow, which are stable suspensions, when not in use, but they are mobile enough to flow as a liquid from the packing container and distributed on a contaminated surface, without appearing thin and watery view. Thus, preferably, the liquid product has the following characteristics W is doctogo flow:

η₀equal to at least 1500 PA·

σ_with2.5-25

η₂₁equal to at least 0.1 PA·C

where η₀represents the viscosity at zero shear rate (determined by extrapolation); σ_withis the tension of the shift at which the viscosity is 0.1η₀; and η₂₁is the viscosity at the shear rate of 21^-1. Preferably η₀equal to at least 2000 PA·s, more preferably at least 2500.

Preferably η₂₁0.3 to 5.0, more preferably 0.6 to 1, 8, most preferably 1.0 to 1.5 PA·C.

The measurements are performed on the devices:

CSL 100 (firm TA Instruments) with a measuring system of the blades and the drum (inner diameter of the drum 48 mm diameter and the height of the blade 38 mm and 24.5 mm) in order to determine the viscosity at tension (σ) from 0.01 PA to tension necessary to obtain shear rate 1 s^-1;

for measuring the viscosity at the shear rate from 0.1 to 389^-1use the instrument Haake RV20 with the measuring nozzle M5 and measurement geometry SV2p. All the measurements were carried out at 20°C.

Good, concentrated liquid abrasive cleaning compositions with a high content of abrasive material are liquid or paste, which is convenient for razbam is placed in water 1.2-4 times, preferably 1.5 to 3 times, more preferably 2-3 times of the original volume, resulting in the formation of a stable, ready-to-use liquid abrasive cleaning composition, preferably a cleaning composition having the above characteristics of the liquid flow.

Good, concentrated liquid abrasive cleaning compositions with a high content of abrasive material are typically viscous or almost pasty liquid. Although they usually work distributed on the surface after application, they again form a smooth undistorted surface where they remain alone for a few minutes or hours in the container. Such products are preferably packaged in a container from which they must pour for distribution, but very convenient containers, such as tubes or boxes from which you can select the appropriate amount of the composition of the corresponding blade on a damp cloth or sponge, or containers, of which the composition can be submitted by survival, such as a tube.

Cooking

Compositions according to the invention can be prepared by simple mixing of the various components. Preferably, first get diluted (e.g., 1-2%) aqueous solution or dispersion of the polymer and then mixed with the other components is Tami consistently. Other components can be first introduced into the suspension with the remaining amount of water, after which the solution (dispersion) and the suspension mixed. Sometimes it is advantageous to neutralize the aqueous solution of the polymer with a part of the base prior to mixing with other components.

Examples 1-2

Concentrated abrasive cleanser composition having the composition shown in table I, are prepared, getting a 2%suspension of the polymer in water and adding it under stirring suspension of calcite, surfactants, sodium hydroxide and odorants in the remaining amount of water. Stirring is continued until a homogeneous solution.

The composition can be diluted by adding an equal volume of water and a quick shake to get ready to use cleaning composition containing 45% of abrasive material.

Samples of concentrates and diluted compositions are tested for stability, and for them not observed any noticeable sedimentation. For this part of the samples of the composition was incubated for three months at a temperature of 37,20 and 4°C. Other samples processed through three cycles of freezing/thawing. None of the samples is not observed appreciable sedimentation, i.e. the formation of sludge.

Example 3

Get ready to use product with a high content of abrasive material, which has the following composition in table II:

When this polymer is a Polygel DR, aminoacidos is Genaminox CSL, mark calcite - Omyacarb-65.

The product has a pH value of 9.8 and a density of 1.8 g/cm³. Product is stored in a tube, from which it easily otbiraet is on a damp cloth, to be applied on the surface to be cleaned. The surface of the product remaining in the tube, after soaking for half an hour again restores smooth and even appearance.

1. Aqueous alkaline liquid abrasive cleanser composition containing solid abrasive material and a thickening agent anionic polymer, characterized in that it contains an abrasive material in an amount of from 55 to 80 wt.%, anionic polymer in the amount of 0,15-0,40 wt.%, surfactant from 0 to 0.4 wt.% and does not contain thickening clay or thickening silica.

2. The composition according to claim 1, characterized in that the abrasive material is chosen from the group consisting of calcium carbonate, mixtures of calcium carbonate and magnesium carbonate, zeolite, alumina, hydrated alumina, feldspar, talc and silicon dioxide, and has a particle size of at least 10 microns.

3. The composition according to claim 2, characterized in that the abrasive material is selected from calcium carbonate and mixtures of calcium carbonate and magnesium carbonate.

4. The composition according to claim 1, characterized in that the anionic polymer is polycarboxylate polymer selected from the group consisting of polyacrylate homopolymers, polyacrylate copolymers, and polysaccharides having a molecular weight of at least 10000.

5. The composition according to claim 1, characterized who eat that contains at least 0.01 wt.% surface-active substances and does not contain amphoteric or cationic surfactant.

6. The composition according to claim 5, characterized in that it contains from 0.01 to 0.35 wt.% non-ionic surfactants.

7. The composition according to claim 6, characterized in that it contains non-ionic surfactant selected from the group consisting of ethoxylated aliphatic alcohols and oxides of tertiary amines.

8. The composition according to claim 5, characterized in that it also contains anionic surfactant.

9. The composition according to pp.5-8, characterized in that it has a pH value above 8.

10. The composition of claim 1, characterized in that it is made with the possibility of packaging in boxes or cans.