RU2265044C2 - Liquid abrasion detergent compositions - Google Patents

Abstract

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

Description

FIELD OF THE INVENTION

The present invention relates to aqueous liquid compositions that include an abrasive material and a polymeric thickening agent that keeps the abrasive material suspended in a liquid. The invention can be used in the manufacture of cleaning products.

State of the art

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

However, detergent surfactants are expensive components, and it is not always obvious whether they contribute to the effectiveness of the cleaning composition, in addition to their thickening and suspending effects. Therefore, various efforts are made to reduce the amount of surfactant and provide a thickening and suspending ability, which is necessary to maintain the abrasive material in a stable suspension, by adding a polymer thickener.

Thus, WO 91/08283 discloses liquid abrasive cleaning compositions containing 0.02-20% detergent, 1-70% loose abrasive material and 0.01-10% thickening mixture containing a linear non-starch type polymer and a branched type polymer starch (amylopectin). Non-starch type polymers include various natural resins and synthetic polymers. Partially acetylated xanthan is particularly preferred. In practice, the required amount of thickening mixture is approximately 3% by weight of the total composition, and 1.5% of non-ionic surfactant is indicated in all examples.

WO 95/08619 discloses liquid abrasive cleaning compositions comprising a crosslinked polyacrylate, or at least one nonionic surfactant, or a combination of an anionic surfactant and a nonionic surfactant, a pH adjusting agent and an abrasive material - calcium carbonate. It is indicated that the compositions contain 0.1-2% polyacrylate, 0.1-10% non-ionic and up to 10% anionic surfactants, and 5-60% abrasive material. In practice, in accordance with examples, the compositions contain 0.25-0.4% polymer, 0.5% or more non-ionic surfactant, and 40% abrasive material. A nonionic surfactant is required in order to provide good viscosity properties. Similar compositions are disclosed in EP 649898, with the additional condition that they contain hypochlorite and that the surfactant is bleach stable.

WO 96/35771 discloses liquid abrasive cleaning compositions containing 10-30% inorganic abrasive material and a thickening system that consists of at least a crosslinked polyacrylate polymer and smectite type clay, with the result that this clay is preferably approximately 50-80% thickening systems. Preferably, the thickening system is 1-2.5% of the composition. In practice, all cleansing compositions contain at least 0.5% polyacrylate and at least 0.75% clay.

EP 352258 discloses suspensions of very fine silica-based powders, such as zeolite, including organic polymer compounds with hydroxyl groups and a molecular weight higher than 1500, as suspending agents in which some cationic or amphionic surfactants are required as stabilizers. The particle size of the suspended zeolites is usually from 0.5 to 10 microns, and the mass of the material has a particle size of less than 6 microns. The only example of polymers is the combination of guar and xanthan gums.

EP-A 0875557 describes an aqueous thickener composition suitable for many end use applications, which contains 0.04-30 wt.% A mixture of at least two surfactants in a predetermined ratio and with a difference in hydrophilic / lipophilic balance, according to at least one unit, and 0.01-5 wt.% associated thickener selected from hydrophobically modified hydroxyethyl cellulose, hydrophobically modified non-ionic polyol and hydrophobically modified emulsion polymer, soluble in alkalis. In practice, the amount of associated thickener is 1-2%, and the amount of surfactant mixture is 1-10%.

EP 301885 discloses liquid abrasive cleaning compositions containing up to 70% abrasive material, an aqueous suspending medium prepared by a combination of anionic surfactants and an electrolyte, and also containing polyacrylate material having a molecular weight of between 500 and 3000. In practice, these compositions contain at least 3.5% surfactant.

Liquid abrasive cleansing compositions are usually sold in ready-to-use form and contain 10-50%, usually 20-45%, of a solid abrasive material. Such compositions cannot be diluted, for example, to a solid abrasive material content of 10-20% without loss of stability, which leads to precipitation. Although the patent literature indicates that the abrasive content reaches 70%, industrial products usually contain less abrasive.

SUMMARY OF THE INVENTION

The problem solved by the invention is the development of such stable liquid aqueous abrasive cleaning compositions in which the presence of a detergent surfactant is not required to obtain a stable suspension.

A further object of the invention is also the development of liquid aqueous abrasive cleaning compositions in which the abrasive material is suspended with a polymer thickening agent.

Another objective of this invention is the development of aqueous abrasive cleaning compositions that can be provided either in a ready-to-use form or in concentrated form that a consumer can dilute to a ready-to-use product without losing long-term stability.

Accordingly, this invention provides a liquid aqueous abrasive cleaning composition comprising an insoluble abrasive material and an anionic thickening polymer.

DETAILED DESCRIPTION OF THE INVENTION

All components described in the description are presented in wt.% Based on the entire composition. As used herein, the term “liquid” refers to materials that have easy flowability, as well as materials that are thick, almost pasty, but, due to their inherent flow property, can still be physically classified as liquids.

According to the invention, liquid aqueous abrasive cleaning compositions contain more than 55-80% of a solid abrasive material, 0.15-0.40% of an anionic thickening polymer, and optionally from 0 to 0.4% by weight of a surfactant.

Dispersed, suspended solid powder abrasive material is an essential ingredient of the liquid abrasive composition 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%.

The products may be formulated in a mixture and packaged in the form of ready-to-use compositions having the above abrasive content. Such compositions may take the form of thick, viscous, almost pasty products. Thick, viscous products in a ready-to-eat form preferably contain above 50%, preferably at least 55%, most preferably 60% of a solid abrasive material.

Alternatively, the compositions of the invention may be formulated in a mixture and packaged as concentrates, which are diluted prior to use by adding an appropriate amount of water. Such compositions have the advantage that they require smaller packaging for the same final amount of product ready for use, and thus provide an advantage in storage and transportation. Compositions can be prepared and transported in bulk, as intermediates to manufacturing equipment located close to consumers, where the compositions are diluted with water and then packaged and sold as ready-to-eat products. Alternatively, the compositions can be packaged directly and sold as concentrates that the consumer will dilute with home water.

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

Preferred abrasives have a Mohs hardness lower than 6 but higher than 1, although higher hardness abrasives can be used for special applications. Preferably, the Mohs hardness is at least two.

Suitable abrasives can be selected from inorganic abrasives, such as zeolites, silicas, silicates, carbonates, aluminum oxides, and organic polymer abrasives, such as polyethylene, polycarbonate, polyurethane, polystyrene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, and nylon, and mixtures thereof. Preferred abrasive materials are: calcium carbonate (as calcite), mixtures of calcium and magnesium carbonates (as dolomite), zeolite, alumina, hydrated alumina, feldspar, talc and silica. Calcite, dolomite and mixtures thereof with a reduced silica content, especially amorphous silica, are particularly preferred due to their low cost and good abrasive properties.

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

Anionic polymers are used to obtain a stable suspension of abrasive particles in an aqueous medium. They are available in various forms supplied by various manufacturers, for example, in the form of aqueous suspensions or in the form of a solid powder. Moreover, these polymers can be hydrophobically modified and / or crosslinked. For products with a "high abrasive content", that is, products that contain abrasive material above 50%, preferably at least 55%, most preferably at least 60%, polymers are preferably used in an amount of at least 0.07% , more preferably at least 0.1%, most preferably 0.15% or more. For these products, the maximum polymer content usually does not exceed 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 10,000, in particular at least 50,000 or even 100,000. Suitable polymers can be found among polycarboxylate type polymers, such as various polyacrylate homopolymers and copolymers, which typically have a molecular weight of 500,000 or higher, often significantly higher than 1,000,000, and various polysaccharides such as carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, carrageenan (pearl moss), alginate, resin t ragacanthus, locust bean gum, guar and xanthan gum.

Very suitable are synthetic polycarboxylate polymers, for example, hydrophobically modified emulsion polymers and carbomers (solid powdered polyacrylic acids). The former polymers are particularly effective for low abrasive products, while the latter are particularly effective for high abrasive products. Suitable hydrophobically modified emulsion polymers should preferably have an initial viscosity η ₀ of at least 1000 Pa · s.

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

For other thickening agents, such as thickening clays or thickening silica, it is not necessary to achieve the desired stability of the suspension, and in preferred embodiments of the invention, such thickeners are not contained.

As noted above, in the compositions according to the invention there is no need for a surfactant due to the stability problem. However, it may be useful to add a limited amount of detergent to the surfactant in order to improve the cleaning properties of the products on certain types of contaminants and / or provide foaming during use, which is desirable for some consumers. Nonionic, anionic, amphionic and amphoteric surfactants may be used. Non-ionic surfactants are preferred. Nonionic surfactants can be combined with other classes of surfactants, especially with anionic surfactants. Typically, the presence of amphionic or cationic surfactants, although possible, does not produce any beneficial effect, and compositions without such surfactants represent a preferred embodiment of the invention.

Suitable nonionic surfactants in a broad aspect can be described as compounds obtained by condensation of alkylene oxide groups, which are hydrophilic agents, with an organic hydrophobic compound, which may be of an aliphatic or alkyl aromatic nature. The length of the hydrophilic polyoxyalkylene group that condenses with any particular hydrophobic group can be easily adjusted so as to obtain a water soluble compound having the desired degree of combination of hydrophilic and hydrophobic elements.

Specific examples include the condensation product of aliphatic alcohols containing from 8 to 22 carbon atoms in either a linear or branched configuration with ethylene oxide, such as a condensation product of coconut oil with ethylene oxide having from 2 to 15 moles of ethylene oxide per mole of coconut alcohol; a condensation product of alkyl phenols in which the alkyl group contains from 6 to 12 carbon atoms, with 5-25 moles of ethylene oxide per mole of alkyl phenol; a condensation product of a product obtained by reacting ethylenediamine and propylene oxide with ethylene oxide, wherein these condensates contain from 40 to 80% by weight of ethylene oxide units and have a molecular weight of from 5000 to 11000; tertiary amine oxides of the R3NO structure in which one R group is alkyl containing from 8 to 18 carbon atoms and each other is a methyl, ethyl or hydroxyethyl group, for example dimethyldodecylamine oxide; tertiary phosphine oxides of the R3NO structure, in which one R group is alkyl containing from 10 to 18 carbon atoms and each other is an alkyl or hydroxyalkyl group with 1-3 carbon atoms, for example dimethyldodecylphosphine oxide; and dialkyl sulfoxides of structure R2SO, in which one R group is alkyl containing from 10 to 18 carbon atoms and the other is a methyl or ethyl group, for example methyl tetradecyl sulfoxide; fatty acid alkylolamides; condensation product of alkylene oxides with fatty acid alkylolamides and alkyl mercaptans. Nonionic surfactants can also be selected from a number of alkyl polyglycosides.

Especially suitable are ethoxylated aliphatic alcohol surfactants such as C9-C11 * 5 (ethylene oxide), C 12-C13 * 6.5 (ethylene oxide) and C13-C15 * 7 (ethylene oxide) (the number of ethylene oxide groups is averaged) and oxides tertiary amines such as dimethyldodecylamine oxide and dimethyldecylamine oxide or amine oxide mixtures containing a large proportion of amine oxides.

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

Examples of such anionic surfactants are water soluble salts:

- sulfates of long chain alcohols (i.e. 8-22 carbon atoms), hereinafter referred to as SDS, especially those that are formed by sulfonation of higher alcohols formed during the recovery of tall oil or coconut glycerides;

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

- secondary alkanesulfonates (hereinafter referred to as SDS).

Also acceptable are the salts:

- sulfates of alkyl glyceryl ethers, especially those esters of higher alcohols that are obtained from tall and coconut oil;

- sulfates 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;

- salts of sulfates of alkyl phenol ether 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 the sodium, potassium, magnesium and ammonium salts of alkyl benzene sulfonates, olefin sulfonates, and alkyl sulfates and sulfates of fatty acid monoglycerides.

Suitable amphoteric surfactants that may optionally be used are derivatives of aliphatic secondary and tertiary amines containing an alkyl group of 8-18 carbon atoms and an aliphatic group substituted by an anionic group that promotes dissolution in water, for example sodium 3-dodecylaminopropionate, Sodium 3-dodecylaminopropanesulfonate and sodium N-2-hydroxy dodecyl-N-methyltaurate.

Further examples of suitable active detergent compounds are compounds that are commonly used as surfactants, as described in the well-known Surfactants, Volume 1, Schwartz and Perry; and "Surfactants and Detergents," Volume 2, Schwartz, Perry and Berch.

Compositions according to the invention may contain a total amount of surfactant below 0.5%. Preferably, the total surfactant content does not exceed 0.4% or even 0.3%. To effectively improve the cleaning and / or foaming properties, the desired minimum level of total surfactant content is 0.01%, preferably at least 0.02%, more preferably at least 0.05% or even 0.1 %

The amount of non-ionic surfactant should preferably be lower than 0.5%, more preferably equal to or lower than 0.45%, and most preferably equal to or lower than 0.35% or even 0.3%. To improve the cleaning properties of the composition, as well as the stability of the suspension, preferably the content of non-ionic surfactant is at least 0.01%, more preferably at least 0.02%. For concentrated products, the amount of non-ionic surfactant is more preferably at least 0.02%, most preferably at least 0.03%.

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 by using a suitable base, such as an alkali metal hydroxide or alkali metal carbonate, ammonia or an organic base with a pKa value above 9, such as triethylamine, aminomethylpropanol (AMP), aminobutanol, mono-, di- or triethanolamine mono-isopropylamine, or aminomethylpropanediol. AMP is particularly effective and is preferably added in an amount of up to 0.5%, more preferably 0.2-0.4% in the absence of another base or 0.1-0.2% in the presence of another base.

For compositions according to the invention, there is usually no need for an additional electrolyte different from the possible anionic surfactant and base for adjusting the pH value. Preferably, the additional electrolyte content is below 0.3%, more preferably below 0.2%.

Optional components

According to the invention, the abrasive compositions may contain optional components that improve its cleaning properties, such as organic solvents known in the art for use in abrasive cleaning compositions, in particular solvents whose molecules have a polar group, such as hexanol, ethylene alkyl ethers - and propylene glycol. The compositions may also contain whitening agents, in particular halogen whitening agents, more specifically hypochlorite, provided that the polymers and surfactants used are stable against hypochlorite.

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

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

- fuses that prevent microbial contamination.

Fluid properties

According to the invention, good, ready-to-use, “low abrasive material” liquid abrasive cleaning compositions have such liquid flow characteristics that they are stable suspensions when not in use, however they are sufficiently mobile to leak out of the packaging container and spread out over the contaminated surface, without liquefaction and watery appearance. Thus, preferably, the liquid product has the following liquid flow characteristics:

η ₀ is at least 1500 Pa · s

σ _s is equal to 2.5-25

η ₂₁ is at least 0.1 Pa · s,

where η ₀ is the viscosity at zero shear rate (determined by extrapolation); σ _c is the shear stress at which the viscosity is 0.1η ₀ ; and η ₂₁ is the viscosity at a shear rate of 21 s ^-1 . Preferably, η ₀ is at least 2000 Pa · s, more preferably at least 2500.

Preferably, η ₂₁ is 0.3-5.0, more preferably 0.6-1.8, most preferably 1.0-1.5 Pa · s.

Measurements are taken on instruments:

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

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

Good, concentrated, high abrasive liquid abrasive cleaning compositions are liquids or pastes that are convenient for diluting with water 1.2-4 times, preferably 1.5-3 times, more preferably 2-3 times the initial volume, resulting in the formation of stable, ready-to-use liquid abrasive cleaning compositions, preferably cleaning compositions having the above liquid flow characteristics.

Good, concentrated, high abrasive cleaning liquid abrasive compositions are typically viscous or near-paste fluids. Although they are usually difficult to spread over the surface after application, they again form a smooth “undisturbed” surface when they remain at rest for several minutes or hours in the container. Such products are preferably not packaged in a container from which they must be poured for distribution, however containers are very convenient, such as tubes or boxes, from which a suitable amount of the composition can be taken with a suitable spatula on a damp cloth or sponge, or containers from which the composition can be served by survival such as a tube.

Cooking

Compositions according to the invention can be prepared by simply mixing the various components. Preferably, a dilute (e.g. 1-2%) aqueous solution or polymer dispersion is first prepared and then mixed with the other components sequentially. Other components can be first introduced into the suspension with the remaining amount of water, after which the solution (dispersion) and the suspension are mixed. It is sometimes beneficial to neutralize an aqueous polymer solution with a portion of the base before mixing with other components.

Examples 1-2

Concentrated abrasive cleaning compositions having the composition shown in Table I are prepared by preparing a 2% suspension of the polymer in water and adding it with stirring to a suspension of calcite, surfactant, sodium hydroxide and perfume in the rest of the water. Stirring is continued until a uniform solution is obtained.

The compositions can be diluted by adding an equal volume of water and briefly shaking to obtain ready-to-use cleansing compositions containing 45% abrasive material.

Table I Components Content% 1 2 NEODOL 135-7E 0.13 0.13 Calcite 70.13 70.13 CARBOPOL 674 0.28 POLYGEL DR 0.20 NaOH 0.09 0.09 Perfume 0.48 0.48 Water 28.89 28.97 Amount 100 100

Samples of concentrated as well as diluted compositions are tested for stability, and no noticeable sedimentation is observed for them. For this, part of the samples of the composition is kept for three months at a temperature of 37.20 and 4 ° C. Other samples are processed by performing three freeze / thaw cycles. None of the samples showed noticeable sedimentation, i.e. sedimentation.

Example 3

A ready-to-use “high abrasive material” product is obtained that has the composition described in Table II below:

Acusol 820 15 0.280% Genaminox CSL 0.400% Sodium hydroxide 0.051% Omyacarb 65 65.0% Proxel GXL (fuse) 0.016% Water Up to 100%

The polymer is Polygel DR, the amine oxide is Genaminox CSL, the calcite grade is Omyacarb-65.

The product has a pH of 9.8 and a density of 1.8 g / cm ³ . The product is stored in a tube, from which it is easily removed to a damp cloth to apply to the surface to be cleaned. The surface of the product remaining in the tube, after exposure for half an hour, again restores a smooth and even appearance.

Claims (10)

1. Aqueous alkaline liquid abrasive cleaning composition containing a solid abrasive material and a thickening anionic polymer, characterized in that it contains abrasive material in an amount of from 55 to 80 wt.%, Anionic polymer in an amount of 0.15-0.40 wt.%, surfactant from 0 to 0.4 wt.% and does not contain thickening clays or thickening silica. 2. The composition according to claim 1, characterized in that the abrasive material is selected 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 size particles 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 a polycarboxylate polymer selected from the group consisting of polyacrylate homopolymers, polyacrylate copolymers and polysaccharides having a molecular weight of at least 10,000. 5. The composition according to claim 1, characterized in that it contains at least 0.01 wt.% Surfactant and does not contain amphoteric or cationic surfactant. 6. The composition according to claim 5, characterized in that it contains 0.01-0.35 wt.% Non-ionic surfactants. 7. The composition according to claim 6, characterized in that it contains a non-ionic surfactant selected from the group consisting of ethoxylated aliphatic alcohols and tertiary amine oxides. 8. The composition according to claim 5, characterized in that it also contains an 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.