MXPA00007215A - Solid detergent compositions for washing fabrics and hard surfaces. - Google Patents

Abstract

The present invention discloses non-aqueous cleaning abrasive compositions, which comprise from about 0.5% to about 35% of one or more surfactants, wherein at least 10% of said surfactants are anionic having counterions of alkanolammonium, from about 0.5% to about 10% of one or more additional alkanolamines, and from about 30% to about 90% by weight of at least a particulate abrasive. Preferably, the compositions of the present invention are in a bar form, and are suitable for cleaning kitchen items and kitchen surfaces.

Description

COMPOSITIONS OF SOLID DETERGENT FOR WASHING FABRICS AND HARD SURFACES TECHNICAL FIELD The invention relates to synergistic cleaning compositions that are not liquid, containing specific anionic detergent surfactants. The compositions are suitable for cleaning fabrics or hard surfaces.

BACKGROUND AND PREVIOUS TECHNIQUE The fabric washing compositions contain, as an essential ingredient, one or more surfactants whose role is to assist in the removal of dirt from the fabric and its suspension in the wash liquor. Other important components are the detergent detergent builders together with optional components, for example: abrasives, fillers, perfumes, alkali salts and bleaching agents. The hard surfaces inside a house are the kitchen items, the kitchen floors and platforms and tarjas, floors, bathrooms, etc., and one finds different types of dirt on these surfaces. The dirt that is usually found in kitchenware is of two types, that is, the ... ..- .'t. ,? - a¡¿aa:? ... mobile or greasy dirt and that which is tenacious or difficult to remove consisting of dried or cooked food. The problem becomes more pronounced when stubborn dirt builds up over a period of time and this requires considerable effort for cleaning. Hard surface cleaning compositions typically comprise one or more surfactants and may comprise an abrasive. The surfactants are generally chosen to be anionic, non-ionic, cationic, amphoteric or zwitterionic. One or more surfactants which are selected from the primary alcohol sulfate, alkylbenzylsulfonates, alcohol ethoxylates, alkyl ether sulphates, fatty acid soaps and secondary alkylsulfonates are the most commonly used. Solvents are the well-known components of abrasive and non-abrasive cleaning compositions. Typical solvents used in cleaning compositions include alcohols (such as ethanol), ethers (such as Butyl Cellosolve ™), paraffins (such as Isopar LMR), esters and terpenes (such as d-limonene). Another known class of solvents are alkanolanes. EP-A-0 503 219 relates to a cleaning composition containing 0.1-10% of an alkanolamine. aafr a * aL Hard surface cleaners are often formulated as liquid products and several approaches have been considered for specific benefits. FR 2588013 discloses that the combination of a mixed surfactant alkylbenzene sulfonate salt system, for example, monoethanolamine and sodium alkylether sulfate together with ethanol and magnesium sulfate results in a viscous liquid which maintains its viscosity even when diluted. CA 848399 describes the use of monoethanolamine salts of alkylbenzene sulfonate and polyethylene glycol which solves the problem of low temperature stability of sodium alkyl benzene sulphonate formulations. Cleaning compositions that are not liquid, including abrasive cleaning compositions, are formulated predominantly in the form of sticks, pastes and powders. Such cleaning compositions are known in the art. In this way U.S. 4,328,131 describes detergent bars, designed primarily for use as hand or bath soap, which contain 20-80% of a mixture of synthetic anionic and amphoteric surfactants, 5-30% gelatin and gas bubbles to make it buoyant and elastic. US 4,806,273 discloses bars for laundry detergent which contain 10-35% of an anionic detergent of fatty alcohol sulfate particularly the sodium salt thereof, 10-60% of a detergent builder, 10-60% of a powder insoluble in water, 1-10% of lower alkanolamide of fatty acid and 0.2-5% of glycerol. U.S. 4,289,640 discloses a dry, powdered cleaning composition consisting of up to 95% of a dry powdered abrasive, up to 40% of a detergent builder salt and 0.1-15% of an organic detergent. WO 98/58045 discloses non-liquid abrasive cleaning compositions consisting of 50-99.5% particulate abrasives, 0.5-15% alkanolamine and at least 0.1% other base electrolyte. The compositions optionally comprise 0.1-20% surfactant and 0.1-20% solvent other than water or alkanolamine. It is said that the products are pastes, gels or powders. Typical abrasives used in these compositions include calcites, feldspar and dolomites. The bar-like cleaning compositions are economically superior compared to other product forms. The dosage of product by scrubbing from the bar is controlled to a large extent, in comparison with other forms such as a paste, gel or powder. The bar does not easily become saturated with moisture in the presence of water and the active ingredients are not lost. As described in the previous literature, mixed surfactant systems have been used to efficiently remove mobile or greasy dirt. However, a simple surfactant system does not help to remove stubborn dirt and other approaches have been considered such as the use of harsh abrasives and high alkaline compositions, in addition to using rough implements. Other important aspects considered while formulating hard surface cleaners are that they must have good foaming capacity, a satisfactory rinsing power and must be benign with the skin. There has been a problem in making products which satisfactorily cleans mobile and tenacious dirt, and still retain the other properties in use, such as foaming, benignity, etc.

BRIEF DESCRIPTION OF THE INVENTION It has now been found that non-liquid abrasive cleaning compositions comprising a minimum amount of anionic surfactant with alkanolammonium counterions, alone or in combination with other surfactants, and comprising one or more alkanolamines in free form, 20 provides a significantly superior removal of both uncropped oily dirt and stubborn dirt from fabrics or hard surfaces, compared to formulations with other conventional surfactants. Therefore, it is possible to formulate compositions which are benign with the skin and with high foaming capacity, and with good additional use properties. Therefore, according to one aspect, the invention provides detergent cleaning compositions that are not liquid, synergistic, comprising: a) 0.5-35% of one or more surfactants, wherein at least 10% of the surfactant is anionic with alkanolammonium counterions; and b) 0.5-10% of one or more additional alkanolamines; c) 30-90% particulate abrasive material.

DETAILED DESCRIPTION OF THE INVENTION The invention will now be described in greater detail, with reference to compositions for cleaning kitchenware and kitchen surfaces. The invention is not restricted to cleaning them, and can be applied to other hard surfaces and laundry in general. However, the compositions according to the invention are particularly suitable for cleaning hard surfaces, more particulate kitchen surfaces. All percentages mentioned herein are by weight, and are based on the total composition, unless specifically mentioned otherwise.

Preferably, the synergistic abrasive cleaning compositions according to the invention have a pH of at most 12, and most preferably at most 11. Preferably, the total amount of surfactant is at least 5%, more preferably at least 10% The higher amount preferably is not greater than 25%.

Preferably, at least 15% of the total amount of surfactant is anionic with alkanolammonium counter ions, more preferably at least 20%, and much more preferably at least 50%. The surfactant can consist entirely of an anionic surfactant with alkanolammonium counterions, but preferably the amount of anionic surfactant with alkanolammonium counterions is a maximum of 85%. The composition can be formulated as a powder, paste, block, tablet or bar. The stick shape is particularly suitable for the purposes for which the compositions are mainly used. By means of the synergistic cleaning composition described before the invention, during cleaning, the presence of water and the essential presence of the alkanolammonium salt of the surfactant and of the corresponding alkanolamine provide improved cleaning.

TENSOACTIVOS The compositions according to the invention comprise as an essential component an anionic surfactant with alkanolammonium counterions. This surfactant may be combined with other surfactants generally chosen from alkali metals or alkaline earth metals or ammonium salts of anionic surfactants and / or nonionic, cationic, amphoteric and zwitterionic surfactants. Particularly, nonionic surfactants can be usefully added to compositions according to the invention. Cationic, amphoteric and zwitterionic surfactants are generally less useful. Suitable anionic surfactants are water-soluble salts of organic sulfuric reaction products having in the molecular structure an alkyl group containing 8-22 C atoms or an alkylaryl group containing 6-20 C atoms in the alkyl part, and a sulfonate or sulfate group. Preferred water-soluble synthetic anionic surfactants are alkylaryl sulphonates, olefin sulfonates, alkyl sulfates and fatty acid monoglyceride sulfates, and mixtures thereof, having an alkanolammonium counter ion. The most preferred anionic surfactants are alkylaromatic sulfonates containing 6-20 carbon atoms in the alkyl group in a straight or branched chain, particular examples of which are: alkylbenzene sulphonates, alkyl toluene sulfonates, xylene or phenol, alkylnaphthalene sulfonates , diamyl naphthalene sulfonates and thionyl naphthalene sulfonates. Linear alkylbenzene sulfonates are especially preferred. Suitable alkanolammonium counterions of the anionic surfactants for use in the compositions of the present invention may be monofunctional or polyfunctional when considering the amine and hydroxy portions. Preferred alkanolamines of which are derived from those of the formula HJN-RI-OH, wherein Rx is a linear or branched alkyl chain having 2-6 carbon atoms. Preferred alkanolamines further include 2-amino-2-methyl -l-propanol, aminomethylpropane diol, mono-, di- and tri-ethanolamine, mono-, di- and tri-isopropanolamine, dimethyl-, diethyl- and dibutyl-ethanolamine, and mixtures thereof. Particularly preferred alkanolamine salt anionic surfactants are those derived from 2-amino-2-methyl-1-propanol (AMP) and monoethanolamine (MEA), and it is therefore preferred that at least 50% of the alkanolamine used for neutralizing the anionic surfactant acid consists of AMP and / or MEA, more preferably 100%. The amount of synthetic anionic surfactant to be used in the detergent composition of this invention will generally be up to 35%, and more preferably 10 to 25% by weight, wherein 10-100% of the surfactant is alkanolamine salt , and more preferably 85%. Nonionic surfactants may also be present in a useful manner in the compositions according to the invention. Suitable non-ionic surfactants can be broadly described as compounds produced by the condensation of hydrophilic alkylene oxide groups with an organic hydrophobic compound which may be aliphatic or alkylaromatic in nature. The length of the hydrophilic polyalkylenoxy group which is condensed with any particular hydrophobic group can be easily adjusted to provide a water-soluble compound having the desired degree of equilibrium between hydrophilic and hydrophobic elements. Particular examples include the condensation product of aliphatic alcohols having from 8 to 22 carbon atoms in a straight or branched chain configuration with ethylene oxide, such as condensate of ethylene oxide and coconut oil having from 2 to 15 moles of ethylene oxide per mole of coconut alcohol; condensate of alkylphenols whose alkyl group contains from 6 to 12 carbon atoms with 5 to 25 moles of ethylene oxide per mole of alkylphenol; condensates of the reaction product of ethylene diamine and propylene oxide with ethylene oxide, the condensate containing from 40 to 80% of ethyleneoxy groups by weight, and having a molecular weight of 5,000 * * '•? to 11,000; tertiary amine oxides of structure R3N0, wherein one group R is an alkyl group of 8 to 18 carbon atoms and the others are, each, methyl, ethyl and hydroxyethyl groups, for example, dimethyldodecylamine oxide; tertiary phosphine oxides of structure R3PO, wherein one group R is an alkyl group of 10 to 18 carbon atoms, and the others are each alkyl or hydroxyalkyl groups of 1 to 3 carbon atoms, for example dimethyldodecylphosphine oxide; and dialkyl sulfoxides of structure R2SO, wherein the group R is an alkyl group of 10 to 18 carbon atoms and the other is methyl or ethyl, for example methyltetradecyl sulfoxide; fatty acid alkylolamides; alkylene oxide condensate of fatty acid alkyl amides and alkyl mercaptans. The nonionic part can also be selected from a range of alkyl polyglycosides. If present, the amount of nonionic surfactant to be used in the detergent compositions of the invention will generally be from 0.5 to 15% of the total surfactant, preferably from 5 to 10% of the total surfactant. Suitable amphoteric surfactants which may optionally be used are derivatives of secondary and tertiary aliphatic amines containing an alkyl group of 8 to 18 carbon atoms and an aliphatic group substituted by an anionic group solubilizing in water, for example sodium dodecylaminopropionate, sodium dodecylaminopropane-sulfonate and sodium N-2-hydroxydecyl-N-methyltaurate. Suitable cationic detergent active compounds are quaternary ammonium salts having an aliphatic group of 8 to 18 carbon atoms, for example cetyltrimethylammonium bromide. Suitable zwitterionic surfactants which may optionally be used are derivatives of aliphatic ammonium, sulfonium and phosphonium quaternary compounds having an aliphatic group of 8 to 18 carbon atoms and an aliphatic group substituted by an anionic water solubilizing group, for example 3 - (N, N-dimethyl-N-hexadecylammonium) -propane-1-sulfonate of betaine, 3- (dodecylmethylsulfonium) -propane-1-sulfonate of betaine and 3- (cetylmethylphosphonium) -ethane-sulfonate of betaine. Additional examples of suitable surfactants are described in the 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.

ADDITIONAL ALCANOLAMINS Additional alkanolamines for use in the compositions of the present invention are generally the same as those used to provide alkanolammonium counterions of the anionic surfactant.

Particularly preferred alkanolamines especially for cleaning tenacious or aged dirt are 2-amino-2-methyl-1-propanol (AMP) and monoethanolamine (MEA). Therefore, it is preferred that at least 50% of the total alkanolamine used to neutralize the ionic surfactant acid and the additional alkanolamine consist of AMP and / or MEA, and more preferably 100%. Typical levels of additional alkanolamine in the compositions of the invention vary from 2 to 10%. Particular preference is given to using 2-amino-2-methyl-1-propanol or monoethanolamine at a level of 2 to 8%.

ABRASIVES A particulate abrasive is an essential feature of the compositions according to the present invention. Preferably, it comprises a particulate abrasive which is insoluble in water. Alternatively, the abrasive may be soluble and may be present in an excess such with respect to any water present in the composition, that the solubility of the abrasive in the aqueous phase exceeds and consequently there are solid abrasive particles in the composition. Suitable abrasives are selected from particulate zeolites, calcites, dolomites, feldspar, silicas, silicates, other carbonates, aluminas, bicarbonates, borates, sulfates and polymeric materials such as polyethylene, polypropylene, polystyrene, polycarbonate, etc. Preferred abrasives for use in the general purpose compositions have a Moh 2-6 hardness, although higher hardness abrasives may be used for specialist applications. The preferred average particle sizes for the abrasive is in the range of 0.5-400 microns, preferably 10-200 microns. Preferred levels of abrasive are at least 35%, more preferably at least 49%, while the maximum levels are preferably no greater than 85%, more preferably 60%. The presence in the compositions of the invention of a particulate solid with a liquid absorption capacity of at least 100% of its own weight is a preferred feature. The particulate solid is preferably present in an amount of up to 10%. Preferably, the amount of such a solid is at least 0.5%, more preferably at least 1% and up to 7%. The ability to properly absorb liquid is 100-300% of its weight. Suitable compounds can be selected from silica gel or precipitated or spray dried silica. The most preferred particulates are precipitated silicas.

The particulate abrasive can perform partially or totally the function of the solid with the capacity of absorption of liquid if it has the capacity of absorption of liquid that is required.

OPTIONAL INGREDIENTS The compositions according to the invention can contain other ingredients that help the cleaning operation. For example, the compositions may contain detergency builders such as nitrilotriacetates, polycarboxylates, citrates, dicarboxylic acids, water soluble phosphates, especially polyphosphates, ortho- and pyrophosphates, zeolites and mixtures thereof. Some detergency builders may additionally function as abrasives if they are present in an amount exceeding their water solubility. A binder, if present, will preferably constitute 0.1-25% by weight of the composition. More preferably, at most 15%. On the other hand, for many applications a builder is not necessary and the builder-free compositions form another particular group of embodiments of the present invention. The composition according to the invention may also contain, in addition to the aforementioned ingredients, various other optional ingredients such as structurants, colorants, bleaches, soil suspending agents, detersive enzymes, compatible bleaching agents (particularly hypohalites), and preservatives. The synergistic cleaning compositions which are not liquid, according to the invention are prepared by mixing the essential and optional ingredients in the desired amounts in a conventional manner and by processing it in a desired configuration or shape, according to the methods known in the art. For bars, various ways of processing in the literature are also described in relation to laundry bars and bars for personal cleaning. The compositions according to the invention are particularly suitable for cleaning hard surfaces by applying the compositions as such to the surface. This is preferably done directly, but can also be done using a suitable applicator such as a damp or wet cloth, a sponge or similar implement. Therefore, as indicated above, the invention also provides a process for cleaning hard surfaces comprising the step of applying the compositions as such to a surface with dirt. The compositions and process according to the invention are particularly suitable for kitchen surfaces and kitchen items such as crockery, pots, pans, etc.

The invention will be illustrated below with respect to the following non-limiting examples.

EXAMPLES Process for preparing a bar: The detergent compositions in stick, according to the invention and the respective control compositions are as described in table 1 and are prepared by the following procedure. Linear alkylbenzene sulfonate with monoethanolammonium (MEALAS) and / or sodium counterion (NaLAS) and water are placed in a mixing vessel. To this, depending on the formulation requirement, monoethanolamine (MEA) and / or aminomethylpropanol (AMP) is added and mixed thoroughly. This mixture of adjuvants is added to the abrasive particulates in a sigma mixer. Then the remaining ingredients including the structurants are added to the mixture and the resulting dough is extruded by conventional process.

TABLE 1 - li Properties in use of the composition: The compositions of Examples 1 to 7, of which Examples 4, 6 and 7 are according to the invention, are used to determine their effectiveness in effectively cleaning dirt from hard surfaces. Samples are tested for properties in use, by the following procedure. to. Cleaning of stubborn dirt (TSC).

Oil that has been polymerized by heating at high temperature is known as stubborn dirt. The vegetable oil is uniformly dispersed on a stainless steel plate and heated to obtain a film of polymerized oil on the plate. 0.12 g of the product is uniformly rubbed on the soiled plate and then rinsed with water. The operation is determined by establishing the percentage of cleaning visually by trained personnel. The experiment is carried out with replicas and analyzed statistically. b. Cleaning of unpolymerized oily dirt (UOC).

The uniform amount of vegetable oil is dispersed in stainless steel plates and the number of dirty plates that can be cleaned for a particular amount of the product is determined.

TABLE 2 The data presented in table 2 show that the combination of MEA LAS and an alkanolamine in examples 4, 6 and 7 act synergistically to significantly clean unpolymerized oily dirt and stubborn dirt and at the same time maintain a beninga composition with the skin. ^^^^^^^ fc ^^^.

Claims (14)

1. CLAIMS 1. Abrasive cleaning compositions, which are not liquid, comprising 0.5-35% by weight of one or more surfactants, wherein at least 10% of the surfactant is anionic with alkanolammonium counterions, 0.5-10% of one or more additional alkanolamines and 30-90% by weight of at least one particulate abrasive. 2. The cleaning compositions, as described in claim 1, wherein the pH is, at most, 123. The cleaning compositions, as described in claims 1 or 2, wherein the amount of surfactant is 5-25%. 4. The cleaning compositions, as described in claims 1 to 3, wherein the amount of anionic surfactant having alkanolammonium counterions is at least 20% of the total surfactant. 5. The cleaning compositions, as described in claims 1 to 4, wherein the anionic surfactants are water-soluble salts of organic sulfuric reaction products having in the molecular structure an alkyl group ^ Jjl ^ j ^^^ -attlto ^ - »- * -" "containing 8-22 C atoms or an alkylaryl group containing 6-20 C atoms in the alkyl part, and a sulfonate or sulfate group. 6. The cleaning compositions, as described in claims 1 to 5, which also contain a nonionic surfactant. 7. The cleaning compositions, as described in claims 1 to 6, wherein the amount of abrasive is 35-60%. 8. The cleaning compositions, as described in claims 1 to 7, wherein the alkanolammonium ions are derived from, and the additional alkanolamine is: 2-amino-2-methyl-1-propanol and / or monoethanolamine. 9. The cleaning compositions, as described in claims 1 to 8, which do not contain any other surfactant than anionic and optionally non-ionic. 10. The cleaning compositions, as described in claims 1 to 9, which do not contain a builder. .. », e- ^ ... .. ..... i * --.- .. 11. The cleaning compositions, as described in claims 1 to 10, which contain 0.5-10% of a particulate solid having a liquid absorptive capacity of at least 100% of its own weight. 12. The cleaning compositions, as described in claim 11, wherein the particulate solid is selected from silica gel, spray-dried silica or precipitated silica. 13. The cleaning compositions, as described in claims 1 to 12, which are in the form of a bar. 14. A Process for cleaning a substrate, comprising applying to the substrate a cleaning composition as described in any of claims 1 to 13. 13. The process as described in claim 20 14, wherein the substrate is a hard surface. 14. The process as described in claims 14 or 15, wherein the composition is applied directly to the substrate. 25 - "* - B ^ - • -. - -.-- t.,.. _ ,, ..-- -", ^ - »... -... f ??". - - »» > .