GB2037311A - Pulverulent non toxic cleaning agent for textile fittings of large surface area - Google Patents

Abstract

A pulverulent non toxic cleaning agent which comprises 70 to 30 parts by weight of a solvent mixture consisting of (a) water and (b) an organic solvent or a mixture of organic solvents selected from one or more terpenic hydrocarbons, a mixture of terpenic hydrocarbons and aliphatic hydrocarbons liquid at 20 DEG C and a mixture of aliphatic hydrocarbons and one or more glycol ether or ester solvents, absorbed on 30 to 70 parts by weight of a pulverulent carrier of which the particle size is between about 5 and 1000 mu . and consisting of starch, flour or woody material.

Description

SPECIFICATION Pulverulent non toxic cleaning agent for textile fittings of large surface area The invention relates to a pulverulent non toxic cleaning agent for rapidly and carefully cleaning carpets, furnishing textiles and othertextilefittings of large surface area.

The in situ cleaning of carpets, furnishing fabrics and upholstered furniture covered with textiles presents great practical difficulties.

The use of conventional stain-removing and cleaning products, which are in the form of anhydrous or aqueous liquids or foams, in fact presents major disadvantages.

When applying this type of product, it is not possible to avoid more or less complete impregnation in depth of some or all of the fibres which constitute the treated textile material, and this impregnation always causes a certain migration or a certain leaching of the dyes and finishing agents, as well as causing the formation of rings or sometimes even a shrinkage or felting of the treated textile material.

Furthermore, the conventional liquid cleaning agents, which generally contain surface-active cleaning substances, after drying generally leave on the fibre residues of surfactants which impart to the textile material a dull appearance and a greatly increased tendency to become soiled again.

Furthermore, the time required for drying fibres which are deeply impregnated with liquid is always very long and is another major disadvantage of the use of such products, especially in the case of permanently fitted carpets in areas of heavy traffic.

The present invention provides a novel cleaning agent for carpets and furnishing textiles which does not suffer from the disadvantages described above and which results, more rapidly than the previously known products, in better cleaning of textile surfaces soiled in various ways.

Pulverulent cleaning products for the care of textiles are already known. Thus French Patent No. 1,321,148 describes a urea-formaldehyde resin powder impregnated with a mixture of carbon tetrachloride, trichloroethylene and petrol. Such a product can only be used spot-by-spot on greasy stains and has no cleaning power whatsoever in respect of more water-soluble stains.

Other pulverulent cleaning products, which consist of a synthetic macromolecular pulverulent substance, such as polyurethane, polystyrene, polyethylene, polypropylene, polyvinyl or acrylic resins and the like, impregnated with anhydrous or aqueous solvent mixtures, are described in French Patents No. 2,015,972, 2,163,692 and 2,240,287, in German Patent Application 2,021,677 and in British Patent 1,251,972.

However, none of these products is able to produce entirely satisfactory cleaning of all the different possible types of soiling, whilst permanently imparting a fresh appearance to the treated textile.

In fact, the pulverulent product known hitherto have a lower cleaning power than that of the liquid products and furthermore have the disadvantage of subsequently being difficult to remove completely from the textile material, to the surface of which they tend to adhere and remain stuck.

The present invention overcomes these disadvantages by providing a novel cleaning agent for textile fittings of large surface area, which agent comprises the following combination of (A) + (B): (A) about 30 to 70 parts by weight of an aqueous liquid mixture of solvents comprising: (a) about 15 to 90% by weight of water, (b) about 10 to 85% by weight of an organic solvent or of a mixture of organic solvents selected from:: (a) one or more terpenic hydrocarbons which are liquid at 20"C and having boiling points, under atmospheric pressure, of between 150 to 250"C, (ss) mixtures of terpenic hydrocarbons (a) and aliphatic hydrocarbons which are liquid at 20"C and have boiling points, under atmospheric pressure, of between 90 and 300"C and (y) mixtures of aliphatic hydrocarbons as defined under (ss) and one or more oxygenated solvents selected from mono- and dialkylethers of ethylene glycol wherein the alkyl moiety has 1 to 5 carbon atoms, ethylene glycol monoacetate and the acetates of the ethylene glycol monoalkylethers as herein before defined, and (B) about 30 to 70 parts by weight of an absorbent pulverulent carrier of which the mean particle size, in non impregnated condition, is between about 5 and 1000y said carrier being selected from (i) powders of ligneous vegetable substances with an alveolar structure, (ii) starch powders, (iii) dehusked cereal grain flours, and (iv) the binary and ternary mixtures of the compounds(i), (ii) and (iii) all the proportions relating to the total weight of the liquid mixture (A).

The aqueous solvent mixture (A) according to the invention generally contains about 30 to 89% and preferably about 40 to 60% by weight of water and 11 to 60% by weight of an organic solvent selected from (a) and (ss) as hereinbefore defined. This amount of water imparts to the cleaning agent according to the invention an excellent cleaning power in respect of water-soluble stains, a large number of stains due to foodstuffs, in particular, being water-soluble.

The cleaning agents according to the invention can contain various adjuvants such as perfumes, antistatic agents, anti-redeposition agents, optical brighteners, pigments and, above all, surfactants, microbicides, fungicides and antioxidants in an amount of between 0 and 10% by weight.

It is immaterial whether these adjuvants are soluble in the aqueous phase (a) or in the oleophilic phase of the mixture of components (b) of the solvent mixture (A). They can also consist of insoluble particles dispersed homogeneously throughout the carrier (B).

These adjuvants are generally dissolved in one or other of the components (a) or (b) of the mixture (A) or are mixed with the carrier (B). They are generally present in proportions of the order of 0.05 to 10% by weight, preferably 0.05 to 5% by weight, calculated either relative to the total weight of (A) or relative to the total weight of (B).

The pulverulent cleaning agents according to the invention contain, completely and uniformly absorbed (or adsorbed) on a pulverulent carrier, an aqueous liquid mixture (A) of quite specific solvents, which allows very efficient cleaning of virtually all types of the usual stains and soiling.

According to the invention, component (b) of this mixture (A) contains an organic solvent or a mixture of organic solvents selected from (a) one or more terpenic hydrocarbons which are liquid at 20"C and have boiling points, under atmospheric pressure, of between 150 and 250"C, (ss) mixtures of terpenic hydrocarbons (a) and aliphatic hydrocarbons which are liquid at 20"C and have boiling points, under atmospheric pressure, of between 90 and 300"C and (y) mixtures at aliphatic hydrocarbons as defined under (ss) and one or more oxygenated solvents selected from mono- and dialkylethers of ethylene glycol wherein the alkyl moiety has 1 to 5 carbon atoms, ethylene glycol monoacetate and the acetates of the ethylene glycol monoalkylethers as herein before defined. A preferred cleaning agent according to the invention is that wherein the mixture (A) consists essentially of 30 to 88,9% by weight of water and of a mixture of (ss1) consisting essentially of: (Z) 10 to 50% by weight, of an aliphatic hydrocarbon or a mixture of aliphatic hydro-carbons which have boiling points, under atmospheric pressure, of between 90 and 300"C and evaporation indices at 20"C, measured relative to diethyl ether, of between 10 and 100, (Z1) 1 to 10% by weight, of a solvent or of a mixture of terpenic solvents, which have boiling points, under atmospheric pressure, of between 150 to 250"C and evaporation indices at 20"C, measured relative to diethyl ether, of between 20 and 80, (C1) 0.05 to 5% by weight of a surfactant washing agent and (C2) 0,05 to 5% by weight, of a microbicidal and/or fungicidal preservative, all the proportions relating to the total weight of (A).

The component (Z) of the mixture (P1) advantageously consists of a crude petroleum distillation cut which preferably distils at between 130 and 250"C under normal atmospheric pressure. Such a solvent can for example be white spirit, a petroleum distillation cut which distils approximately between 130 and 210"C, or any other mineral spirit.

However this component can also consist of one or more synthetic alkanes whose boiling points under atmospheric pressure are located within the limits indicated above, such as, for example, decane and/or dodecane.

The evaporation index of this component at 200C, measured relative to the time required for the evaporation of the same volume of diethyl ether, this latter time being taken as unity, can be between 10 and 100 and preferably between 20 and 80 (the evaporation index of the diethyl ether being 1). This evaporation index is measured by depositing 0.5 cm3 of the hydrocarbon on a filter paper with the aid of a pipette and determining the time required for its complete evaporation, a comparison experiment being carried out simultaneously with diethyl ether.

The terpene solvent component (a) is selected from amongst the true terpene hydrocarbons such as the terpene hydrocarbons of empirical formula CloH1G and optionally from amongst the alcohols, aldehydes and esters derived from these terpenes. A fundamental characteristic of the terpene solvent (a) is its volatility; under atmospheric pressure its boiling point is preferably between about 150 and 2508C and more advantageously still between 150 and 200"C, and its evaporation index at ordinary temperature (20"C) is preferably between 20 and 80 (relative to diethyl ether, of which the evaporation index is 1), and more advantageously still between 20 and 50.

The terpene solvent (a) can be selected, for example, from amongst pinene (boiling point 157-166"C), carene (boiling point 165 C), sabinene (boiling point 165"C), myrcene (boiling point 167"C), menthene (boiling point 168"C), phellandrene (boiling point 171-175"C), ocimene (boiling point 177"C), sylvestrene (boiling point 177"C), limonene (boiling point 177"C), dipentene (boiling point 178"C), terpinene (boiling point 176-183"C), terpinolene (boiling point 184"C) and terpinol (boiling point 168 C),which is a mixture of terpineols, terpinolene, terpinene and dipentene; amongst these terpene hydrocarbons, dipentene and above all limonene are very particularly preferred, as are the natural extracts of plants, obtained by pressing or by distillation, which contain a high proportion of these terpene solvents.

The terpene solvent (a) can furthermore consist of, or contain, terpene alcohols of empirical formula C10H16O, C10H18O and C10H20O, which exhibit the volatility characteristics set out above.

Examples of such alcohols are ocimenol (boiling point 196"C), linalol (boiling point 198 C),the terpinenols (boiling point 210-212"C), myrcenol (boiling point 213"C), methylgeraniol (boiling point 216 C), myrtenol (boiling point 224"C), citronellol (boiling point 225"C), nerol (boiling point 227"C) and geraniol (boiling point 230"C).

The terpene aldehydes (a) can for example be selected from amongst citral (boiling point 214-228"C), ethyicitral, isocyclocitral, pheliandral (boiling point 174 C), citronellal (boiling point 206"C), hydroxycitronellal, dihydrocitronnellal and the like.

The terpene esters which may constitute all or part of the solvent (a) are for example menthyl, citronellyl, bornyl, isobornyl, anisyl and dihydroterpinyl formate, acetate and propionate, and the like, which esters possess the general physical properties set out above.

These compounds are advantageously introduced into the cleaning agents according to the invention in the form of combined essences, or extracts, originating from the distillation or pressing of natural products which contain a major proportion of terpene products.

The cleaning agents according to the invention can optionally contain, in addition to components (b) and in proportions not generally exceeding 30% by weight of (A), other supplementary solvent compounds belonging to a great variety of solvent groups, for exaple cycloaliphatic hydrocarbons, halogen-containing aliphatic hydrocarbons, oxy-containing heterocyclic compounds, cycloaliphatic and araliphatic alcohols, aliphatic ethers which may or may not contain hydroxyl groups, aliphatic, cycloaliphatic and araliphatic esters, aliphatic, cycloaliphatic, terpene and aromatic ketones, and the various possible mixtures of these solvents.

Amongst the cycloaliphatic hydrocarbons there may in particular be mentioned cyclohexane, methylcyclohexane, tetralin and decal in.

The supplementary halogen-containing aliphatic hydrocarbons can be selected from amongst carbon tetrachloride, methylene chloride, chloroform, 1,1 -dichloroethane, 1 2-dichloroethane, 1,1 -dichloroethylene, 1 ,2-dichloroethylene, 1,1 ,l-trichloroethane, 1,1 ,2-trichloroethane, trichloroethylene, 1,1,2,2tetrachloroethane, tetrachloroethylene, pentachloroethane, trichlorotrifluoroethane and perfluoroethane.

The aliphatic hydroxylic compounds can for example be selected from amongst ethanol, n-propanol, isopropanol, the butanols, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol and the ethers of diols and of aliphatic alcohols, such as, for example, the monomethyl, dimethyl, monoethyl, diethyl, monopropyl and dipropyl ethers of ethylene glycol, diethylene glycol and propylene glycol, or such as butoxy-ethanol.

The araliphatic hydroxylic compounds which can be used by way of supplementary solvents are, for example, phenoxyethanol or phenoxypropanol.

Water constitutes the second obligatory constituent (a) of the solvent mixture (A). This constituent in effect ensures efficient cleaning of the more water-soluble stains and soiling.

The components (a) and (b) of the solvent mixture (A) are generally not miscible with one another in the proportions in which they are used in the cleaning agents according to the invention. This is not important because they are subsequently used in turn to impregnate the absorbent pulverulent carrier (B), forming a heterogeneous microscopic mixture of homogenous appearance.

The mixture of the solvents (ss) present in the cleaning agents of the invention has an unexpected synergistic cleaning and detaching efficiency in respect of the majority of predominantly oil-soluble stains and soiling. The simultaneous presence, in the cleaning agent according to the invention, of substantial proportions of water such as defined above considerably increases the spectrum of activity of the solvent mixture (ss) and leads to a ternary mixture of solvent components (a) + (ss) having virtually universal detaching properties and exhibiting a relatively high rate of evaporation, in spite of the high proportions of water which it contains.

By way of example, an excellent cleaning agent according to the invention is one wherein the solvent mixture (A) consists of: (a) about 3 to 7, and preferably 5 to 7, parts by weight of water and (ss) about 1 to 5 and preferably 3 to 5, parts by weight of white spirit and about 0.5 to 2 parts by weight of limonene or of orange terpene (a).

Dissolving a small amount of a surfactant washing agent in the solvent mixture, though not absolutely essential, is nevertheless advantageous because it permits a rather substantial increase in the detergency of the cleaning agent according to the invention. This surfactant can be anionic, nonionic, cationic or amphoteric in nature.

This surfactant is generally present in the solvent medium in proportions of the order of 0.05 to 10% by weight and preferably of the order of 0.05 to 5% by weight, calculated relative to the total weight of component (A).

Preferably a rather hydrophilic surfactant is chosen, or a mixture of oleophilic and/or hydrophilic surfactants which are preferably soluble in water.

Surfactants exhibiting these properties are to be found in the majority of the chemical groups of surfactants.

Amongst these, the anionic surfactants are particularly advantageous to use; they are, for example, alkyl-sulfonates, alkylbenzenesulfonates, sulfosuccinic acid esters, sulfates of fatty alcohols, or condensation products of an alkylene oxide with high molecular weight fatty alcohols, with amides of fatty acids or with propylene glycols have molecular weight of between 900 and 4,000. Preferred anionic surfactants are those which are in the form of their lithium salts.

The cleaning agents according to the invention also preferably contain a preservative capable of protecting the final product against microbial and fungal deterioration. The preservative is preferably introduced into the aqueous phase of (A): it can be selected from amongst all known microbicidal substances such as, for example, sodium ortho-phenyiphenates, hexyiresorcinol, methyl, propyl and benzyl para-hydroxybenzoate, para-chloro-meta-cresol, triethanolamine ortho-, meta- and para-hydroxybenzoate, dichloroacetamide and the like.

They can also contain antioxidants, for example butylhydroxyanisols, butylhydroxytoluene, citric acid and mixtures of these products.

The fundamental characteristic of the pulverulent carrier (B) is its absorption capacity and the mean size of the particles of which it is composed.

The pulverulent carrier (B) is preferably capable of absorbing at least 80 to 300% by weight of liquid (A), these proportions relating to the weight of non-impregnated carrier.

The mean size of the particles of which it can consists is preferably between 5 and 1000p and more particularly between 50 and 300F- Numerous pulverulent carriers capable of providing excellent cleaning agents by absorption of the solvent mixture (A) according to the invention are described in the prior art.

Such pulverulent carriers are for example inorganic powders, such as powders of inorganic oxides, and of alkali metal, alkaline earth metal and ammonium salts, which may be natural or synthetic, for example hydrated aluminas, silicas, silicates, clays, glass microspheres, carbonates, bicarbonates such as ammonium bicarbonate, borates, chlorides, phosphates, citrates, various sulfates and the like.

Other examples of pulverulent carriers are various polymeric or copolymeric resins and pulverulent solid synthetic polycondensation products derived from ethylene, propylene, styrene, acrylates, acrylonitrile, alkadienes, amides or maleic anhydride, urea-formaldehyde resins, phenol-formaldehyde resins, polyurethanes and the like.

Yet other examples of pulverulent carriers are the various pulverulent artificial cellulosic materials, for example the regenerated celluloses and the cellulose acetates.

However, the preferred carrier for the cleaning agents according to the invention is selected from amongst the natural organic substances of vegetable origin and in particular powders of ligneous substances, dehusked cereal grain flours and starch powders.

The carrier (B) of the cleaning agents according to the invention can in particular consist entirely of one or other of these materials of vegetable origin provided that the particle size of this material and its absorption capacity are in accordance with the fundamental characteristics mentioned above.

The material or materials of vegetable origin capable of forming the carrier (B) are for example selected from amongst wood flour, cork powder, cereal husk powder, maize cob powder, brewer's draff, flours of cereals such as wheat, tapioca, maize, rice, rye, soya, barley, oats and the like and starch powders extracted from potato, wheat, arrowroot, oats, garden peas, beans, rice, maize, buckwheat, rye, barley and the like.

A particularly absorbent carrier (B) which has excellent mechanical properties and which ensures optimum cleaning efficiency of the cleaning agent according to the invention comprises: (a) about 40 to 80% by weight of a ligneous vegetable substance (i), preferably of alveolar structure, capable of absorbing at least 100 per cent of its weight, in the dry state, of solvent mixture (A), (ss) about 15 to 40% by weight of a starch powder (ii) and (y) about 5 to 20% by weight of a cereal flour (iii), all the proportions by weight relating to the total weight of the carrier (B).

The preferred ligneous vegetable substances are those which at one and the same time have great hardness and a preferably cellular structure, making it possible to absorb or adsorb reversibly large amounts of liquids.

A particularly valued ligneous material in the compositions according to the invention is a maize cob powder; in fact, it has good hardness and a cellular structure which permits both good absorption of the liquid (A), and its rapid liberation onto the fibre during the cleaning operation.

The mean size of the particles of ligneous material (a) is preferably between 100 and 300fit, and the ideal mean dimensions are about 1 to 200fit.

During the cleaning operation the particles of ligneous vegetable material of this size in fact exert a mechanical rubbing action on the fibre, which, without damaging the surface of the fibre, facilitates the detachment of soiling matter which is solubilized by one or other of the components (a) or (b) of the solvent mixture, yielded up to the fibre by the carrier (B), and is then immediately absorbed by the same carrier (B).

The presence, in the carrier (B), of a cereal flour of which the mean particle size is also advantageously between 5 and 1000,a, but preferably between about 100 and 300it, efficiently rounds off the properties of the cleaning agent according to the invention, in that it facilitates rapid and homogeneous spreading over the entire textile surface and considerably increases the ease with which the powder which remains on the fibre after the evaporation of the solvent mixture can be removed from the fibre.

The ideal mean particle size of the cereal flour grains is preferably within the limits of 125 to 280u.

Amongst the cereal flours mentioned above, rice powder is particularly valuable in the cleaning agents according to the invention because of the hardness, density and rounded shape of the particles of which it is composed.

The cleaning agents according to the invention also advantageously contain a starch, which because of its very special granular structure and because of the mean size of its particles, which is between 25 and 250,a, imparts to the pulverulent cleaning mixture excellent mechanical properties, fluidity properties, storage characteristics and slippage on the fibres, without in any way increasing its adhesion to the textile materials.

The optimum mean particle size of the starch powder used in the cleaning agents according to the invention is advantageously between 40 and 200sot.

The pulverulent carrier (B) according to the invention has the advantage that it can absorb all the solvent mixture (A) without losing its dry or semi-dry pulverulent appearance and whilst retaining excellent fluidity properties, which it does even after very long storage. This carrier further has the advantage that it does not clog the bags of vacuum cleaners and above all does not cause them to tear.

This pulverulent carrier (B) furthermore has the advantage that it absorbs several solvent components which are immiscible with one another that it can, when the absorbate is brought into contact with a textile materia, liberate the greater part of its solvent components, absorb the soiling matter and dry out to become converted to a powder of which the various particles in no way adhere to the textile fibres and can thus easily be removed by simple brushing or by means of a medium-power vacuum cleaner.

The cleaning agents according to the invention are prepared by simple impregnation of the whole of the pulverulent absorbent mixture (B) with successive small amounts of each solvent component, followed by homogenisation.

Preferably, the pulverulent carrier (B) is first impregnated with the homogeneous mixture consisting of the solvents (b) and, when the entire amount of solvents (b) has been uniformly distributed over this powder, water and the remainder of the ingredients are added in successive small amounts until the pulverulent mixture has been completely homogenised.

After screening, a dry, semi-dry or moist powder is obtained which does not release dust when it is spread over a textile surface, and which can, after drying, be removed from this carpet or the like by brushing or by vacuum-cleaning, without raising dust.

In order to clean a textile surface or a carpet with the aid of the composition according to the invention, about 10 to 50 grams, preferably 25 to 40 grams, of product are spread uniformly per square metre of textile surface and thereafter the product is rapidly rubber over the entire surface of the carpet by brushing with a broom. After drying, the composition does not adhere to the carpet in any way and can be immediately and easily removed, without leaving traces, by means of a medium-power vacuum cleaner; the carpet cleaned in this way exhibits a clean, fluffy and fresh appearance.

The use of a composition according to the invention offers numerous advantages. It makes it possible to clean a carpet or an upholstery fabric efficiently and rapidly without wetting it deeply. It also makes it possible frequently to repeat the cleaning operations without damage to the carpet or upholstery fabric treated in this way.

Complete drying takes place very rapidly, generally in 20 to 30 minutes. It is possible to walk over the carpet immediately after the application of the product, without the risk of damage to the carpet and without the risk of counteracting the effect of the product. This drying is very rapid because the pulverulent composition according to the invention in no way wets the substrate, which always takes a very long time to dry if the cleaning is carried out with the various conventional products, and only very slightly wets the fibres which are being cleaned.

In fact, the cleaning compositions according to the invention only liberate onto the fibre the amounts of solvents strictly necessary for detachment of the soiling matter.

Another advantage in using a composition according to the invention resides in the fact that there is no danger of the composition forming rings or dulling the colours, as happens very frequently with compositions in the form of solutions or foams. Furthermore, the dust and the soiling matter detached from the fibre during the treatment are immediately absorbed by the pulverulent carrier and there is no danger that they might blow off, or redeposit, finally leaving a matt and dull appearance of the carpet. Furthermore, the cleaning agent according to the invention can advantageously be employed for cleaning fragile textile materials, without any detriment to these.

Further, the compositions according to the invention make it possible to cause oil-soluble stains, which are the most common and the most tenacious stains, to disappear very easily, whilst the essentially aqueous shampoos only very partially remove such stains.

After treatment with a composition according to the invention, the carpet acquires a durable clean and fluffy appearance. It exhibits resistance to soiling comparable to that of a new carpet, which is not the case with carpets treated with aqueous shampoos and more particularly with shampoos which contain surfactants.

An important characteristic of the compositions according to the invention resides in the fact that preferably they contain one or more detergents or surfactants which after cleaning do not leave any electrostatic or sticky residue on the fibre.

The use of the compositions according to the invention is furthermore particularly advantageous because it does not require any special apparatus. The compositions are suitable for all types of vegetable, animal or synthetic fibres, such as wool, cotton, jute, silk, regenerated cellulose, acetate rayon, polyamide fibres, polyester fibres, polyolefin fibres, polyvinylidene chloride fibres, polyacrylic fibres and mixtures of these fibres, and furthermore for all types of dyeings of these fibres.

The compositions according to the invention are particularly suitable for the care of all types of carpets, such as tufted carpets, need-punched carpets and more particularly long-pile (looped) carpets, which are always very difficult to maintain with liquid compositions or compositions in the form of a foam because these products tend to stick the pile hairs to one another.

In the Examples which follow, the parts and percentages, unless stated otherwise, are by weight, calculated relative to the total weight of the composition.

Examples 1 to 9 600 g of each of the compositions described in Table I (the figures indicated correspond to parts by weight) are prepared by mixing for 10 minutes, in a powder mixer, the pulverulent compounds which constitute the solid carrier of the formulation. Thereafter the total amount of solvents (b) are added, preferably by spraying, followed by the aqueous component (a). The mixing is continued for one hour.

TABLE I Composition 1 2 3 4 5 6 7 8 9 Wood flour 30 26 Brewer's draff 15 10 Urea-formalde hyde resin powder 3 Bran 25 Pulverised cork 15 Maize cob powder (1) 30 30 25 27 Rice powder 8 7 20 10 10 Rye flour 8 Pearl barley 27 Maize starch (2) 14 15 26 22 Potato starch 22 21 5 White spirit (a) 19 20 19 19 20 15 20 19 20 Isopropylglycol 5 Dipentene 3.5 2.5 2 5 Limonene 3.5 10 3.5 Terpenes from oranges (b) 3.5 1.5 4 Perfume 0.5 i Water 24 24 24 24 15.5 26.5 30 24 29.5 Chloroacetamide(c) 0.3 0.2 0.3 0.3 0.5 0.3 1 0.3 Ultravon W (d) 1.2 1.2 1.2 1.2 1.5 1.2 4 1.2 0.5 Anti-soil redepo sition product 0.2 Antistatic product 0.3 I (1) Product derived from the woody ring which constitutes the hard cylindrical part of the maize fob, and obtained by grinding and screening through a sieve which allows particles of diameter less than or equal to 170 microns to pass.

(2) A pulverulent product of which about 93% of the particles have a diameter of between 40 and 80 microns, with the remainder of the particles having a diameter which can range up to 200 microns.

(a) Aliphatic hydrocarbons containing 5% of aromatic hydrocarbons Distillation range- 149-195 C.

Evaporation index relative to diethyl ether. 21.

(b) (b) Terpene products obtained by extraction from orange peel essence; the greater part of this solvent consists of limonene.

Distillation range: 170-185"C.

Evaporation index relative to diethyl ether: 49.

(c) Dichloroacetamide of the formula CHC12-CO-NH2.

(d) Sodium 2-heptadecyl-benzimidazole-disulfonate, manufactured by CIBA-GEIGY AG of Basle.

Example 10 Experimentl Comparison of the cleaning power of the products described in the present invention with the cleaning power of conventional liquid shampoos and aerosol products.

The substrates used consist of a vertical loop-pile tufted carpet, of beige colour. The fibres consist of a mixture of 60% of polyamide and of 40% of polyester.

The underside consists of a styrene-butadiene foam.

The thickness of this tufted carpet is 6 millimetres and its weight is about 1,300 grams per square metre.

The substrates used are square of 10 cm side length.

The tests consist of soiling the substrates with a standard soiling composition and of then cleaning them with an appropriate product, the cleaning product being removed with the aid of a vacuum cleaner.

This process is repeated 6 times in succession.

This makes it possible at one and the same time to measure the cleaning power of the products and to judge their possible tendency to foul the textile material by leaving on the fibres detergents which are not completely removed by the vacuum cleaner.

The soiling of the substrates is carried out by means of a rotating drum, using 1 gram of standard soiling composition per 10 substrates of size 10 x 10 cm.

The standard soiling composition is ground and screened to 100 microns.

It has the following composition (proportions being by weight): 39.0% of humus 17.7% of cement 18.0% of natural silica 0.5% of carbon blacks 0.3% of ferric oxide 2.5% of vasoline oil having a viscosity of 5.1 degrees Engler at 500C 18.0% of clay 2.0% of stearic acid 2.0% of oleic acid.

The cleaning power of each product is evaluated by carrying out photometric measurements with the Dr.

Lange photoelectric brilliance-meter, built by ERICHSEN, at Hemer-Sundwig (Federal Republic of Germany).

The product described in Example No.4 was then compared with 5 products A, B, C, D and E which are the most representative products of the current French market, and comprise 3 liquid shampoos and 2 upholstery fabric cleaning products packaged in aerosol containers.

The reflectometric values thus obtained are shown in Table II below: TABLE II REFLECTOMETRIC VALUES Aero- Aero- Pro Liquid Liquid Liquid sol sol duct shampoo shampoo shampoo pro- pro- of A B C duct duct Example D E No.4 Starting sample 9.1 91.7 92.1 90.7 90.7 90.3 After 1 st soiling 81.0 83.2 84.4 81.5 84.7 83.7 After 1 sot cleaning* 87.4 87.1 87.4 84.9 85.9 87.2 After 2nd soiling 81.0 83.2 84.4 81.5 84.7 83.7 After 2nd cleaning 86.7 86.0 87.3 86.1 86.6 88.6 After 3rd soiling 80.7 81.2 81.4 81.2 79.1 80.7 After 3rd cleaning 85.2 84.9 95.1 84.0 84.1 87.4 After 4th soiling 79.2 78.9 80.3 79.0 76.5 78.2 After 4th cleaning 83.0 82.8 82.4 79.8 79.4 86.4 After 5th soiling 78.6 78.4 78.5 75.7 75.2 76.2 After 5th cleaning 82.5 81.7 81.9 76.8 78.0 84.7 After 6th soiling 76.9 76.5 77.3 71.3 73.0 74.4 After 6th cleaning 81.8 80.1 80.6 72.7 76.3 83.4 * Amounts of shampoo used in accordance with the doses and method of use recommended by the manufacturer (and expressed in weight of product used for a 10 cm x 10 cm substrate): 0.50 gram of LIQUID SHAMPOOA 0.25 gram of LIQUID SHAMPOO B 0.25 gram of LIQUID SHAMPOO C 0.35 gram of AEROSOL product D 0.35 gram of AEROSOL product E 0.40 gram of the product of Example No.4.

These results show that the use of a composition according to the invention ultimately leads to more thorough cleaning of the fibre than the conventional liquid or aerosol products.

Example 11 Experiment II Comparison of the drying time of the products described in the present invention with the drying time of the conventional liquid shampoos and aerosol products.

A loop-pile tufted carpet of grey-beige colour and consisting of 100% polyamide fibres is used. The underside consists of polyvinyl chloride.

The thickness is 8 millimetres and the weight is about 1,875 grams per square metre.

The substrates used have a surface of 3 square metres (rectangular of size 2 metres x 1.50 metres).

The products mentioned in Example 1 are used in accordance with the use doses recommended by the manufacturers, namely: 50 grams of LIQUID SHAMPOO A per square metre of textile floor covering, to be diluted with 150 grams of water, 25 grams of LIQUID SHAMPOO B per square metre of textile floor covering, to be diluted with 300 grams of water, 25 grams of LIQUID SHAMPOO C per square metre of textile floor covering, to be diluted with 175 grams of water, 35 grams of AEROSOL PRODUCT D per square metre of textile floor covering, to be used without rubbing, 35 grams of AEROSOL PRODUCT E per square metre of textile floor covering, to be used with rubbing, 40 grams of PRODUCT of Example No. 4 per square metre of textile floor covering.

The times required for complete drying of the product are shown in Table III below: TABLE III Drying time Liquid shampoo A : 8hours Liquid shampoo B : 12 hours Liquid shampoo C : 9 hours Aerosol shampoo D : 1 hour 30 miriutes Aerosol shampoo E : 5 hours 30 minutes Product of Example No. 4 : 30 minutes These results show that the drying time of the product according to the present invention is 3 to 24 times shorter than that of the conventional liquid products or "aerosol" products.

Claims (24)

1. A pulverulent non toxic cleaning agent for textile fittings of large surface area, which comprises the following combination (A) + (B): (A) about 30 to 70 parts by weight of an aqueous liquid mixture of solvents comprising: (a) about 15 to 90 % by weight of water, (b) about 10 to 85 % by weight of an organic solvent or of a mixture of organic solvents selected from:: (a) one or more terpenic hydrocarbons which are liquid at 20"C and have boiling points, under atmospheric pressure, of between 150 and 250"C, (ss) mixtures of terpenic hydrocarbons (a) and aliphatic hydrocarbons which are liquid at 20"C and have boiling points, under atmospheric pressure, of between 90 and 300"C and (y) mixtures of aliphatic hydrocarbons as defined under (ss) and one or more oxygenated solvents selected from mono- and dialkylethers of ethylene glycol wherein the alkyl moiety has 1 to 5 carbon atoms, ethylene glycol monoacetate and the acetates of the ethylene glycol monoalkylethers as herein before defined, and (B) about 30 to 70 parts by weight of an absorbent pulverulent carrier of which the mean particle size, in non impregnated condition, is between about 5 F and 1000 , said carrier being selected from (i) powders of ligneous vegetable substances with an alveolar structure, (ii) starch powders, (iii) dehusked cereal grain flours, and (iv) the binary and ternary mixtures of the components (i), (ii) and (iii) all the proportions relating to the total weight of the liquid mixture (A).

2. A cleaning agent according to claim 1, wherein the solvent mixture (A) essentially comprises: (a) 30 to 89 % by weight of water, (b) 11 to 60 % by weight of an organic solvent or of a mixture of organic solvents selected from: (a) one or more terpenic hydrocarbons which are liquid at 20"C, and have boiling points, under atmospheric pressure, of between 150 and 250"C, (ss) mixtures of terpenic solvents (a) and aliphatic hydrocarbons, which are liquid at 20"C and have boiling points, under atmospheric pressure, of between 90 and 300"C and (c) O to 10 % by weight of one or more adjuvants and the particles of the component (B) have an average size of between 5,u and 500y.

3. A cleaning agent according to claim 2, which contains about 0,05 to 10% by weight, calculated relative to the weight of the liquid (A), of one or more adjuvants (c).

4. A cleaning agent according to claim 3, wherein the solvent mixture (A) essentially comprises 30 to 88,9% by weight of water and of a mixture (ssl) ) essentially consisting of: (Z) 10 to 50 % by weight of an aliphatic hydrocarbon or of a mixture of aliphatic hydrocarbons which have boiling points, under atmospheric pressure, of between 90 and 300"C and evaporation indices at 20"C, measured relative to diethyl ether, of between 10 and 100, (Z1) 1 to 10 % by weight, of a solvent or of a mixture of terpenic solvents, which have boiling points, under atmospheric pressure, of between 150 and 250"C and evaporation indices at 20"C, measured relative to diethyl ether, of between 20 and 80, (C1) 0,05 to 5 % by weight of a surfactant washing agent and (C2) 0,05 to 5 % by weight of a microbicidal and/or fungicidal preservative, all the proportions relating to the total weight of (A).

5. A cleaning agent according to claim 4, wherein the component (Z) of the mixture (A) essentially consists of a crude petroleum distillation cut which has a boiling point of between 130 and 250"C.

6. A cleaning agent according to claim 3, wherein the component (a) of the mixture (A) essentially consist of limonene.

7. A cleaning agent according to claim 3, wherein the component (a) of the mixture (A) essentially consists of citrus fruit peel essences.

8. A cleaning agent according to claim 3, wherein the component (b) of the mixture (A) essentially consists of orange terpenes.

9. A cleaning agent according to claim 2, wherein mixture (A) essentially consists of: (a) about 3 to 7 parts by weight of water and (ss) about 1 to 5 parts by weight of white spirit and about 0.5 to 2 parts by weight of limonene (a).

10. A cleaning agent according to claim 2, which contains, dissolved in water, 0.05 to 5 % by weight, relative to the weight of (A), of a sodium 2-alkyl-benzimidazole-sulfonate or -disulfonate, in which the alkyl group contains 10 to 20 carbon atoms as component (c).

11. A cleaning agent according to claim 10, wherein the solvent (A) contains 0,05 to 5 % by weight, relative to the weight of (A), of sodium 2-heptadecyl-benzimidazole-disulfonate as component (c).

12. A cleaning agent according to claim 1, wherein the pulverulent carrier (B) essentially consists of one or more natural organic materials of vegetable origin, the mean particle size being between about 5 and 500 > .

13. A cleaning agent according to claim 12, wherein the carrier (B) essentially consists of a mixture of one or more pulverulent ligneous vegetable substances, one or more dehusked cereal grain flours, and a starch powder.

14. A cleaning agent according to claim 13, wherein the carrier (B) comprises: (a) about 40 to 80% by weight of one or more ligneous vegetable substances with alveolar structure (i), (ss) about 15 to 40 % by weight of a starch powder (ii) and (y) about 5 to 20 % by weight of one or more dehusked cereal grains flours (iii), all the proportions by weight being relative to the total weight of (B).

15. A cleaning agent according to claim 14, wherein the pulverulent ligneous vegetable substance (a) is a maize cob powders

16. A cleaning agent according to claim 15, wherein the pulverulent carrier (B) essentially consists of particles of mean diameter less than 300for, comprising: (a) maize cob powder, (ss) maize starch and (y) rice powder.

17. A cleaning agent according to claim 16 which contains from 0.05 to 5 % by weight, calculated relative to the weight of the liquid (A), of dichloroacetamide.

18. A cleaning agent according to claim 1 substantially as described with reference to any of Examples 1 to9.

19. A method of cleaning textile fittings of large surface area, which comprises uniformly spreading about 10 to 80 grams, per square metre of textile surface area, of a cleaning agent according to claim 1, then spreading the cleaning agent by rubbing it uniformly over the entire textile surface and removing the cleaning agent after drying for ten to thirty minutes.

20. A method according to claim 19 substantially as described with reference to Example 10 or 11.

21. Textile fittings of large surface area when cleaned by a method claimed in claim 19 or 20.

22. A process for the manufacture of a cleaning agent according to claim 1, which comprises two operations (i) and (ii) of impregnating an absorbent pulverulent carrier (B) whereof the mean particles size is between about 5 and 500 y, these two operations being carried out in optional sequence, with one operation consisting of (i) uniformly impregnating the said carrier (B) or a fraction of the carrier (B) with the organic solvents (b), separately or as a mixture, these solvents optionally containing one or more dissolved adjuvants (c), whilst the other operation consists of (ii) uniformly impregnating the said carrier (B) or a fraction of the carrier (B) with the aqueous component (a) which optionally contains one or more dissolved adjuvants (c), the homogenisation of the final cleaning agent obtained after mixing all the components being continued until a powder of uniform appearance is obtained, in which the various components are present in a uniformly distributed form.

23. A process according to claim 22 substantially as described with reference to any of Examples 1 to 9.

24. A cleaning agent according to claim 1 when produced by a process claimed in claim 22 or 23.