EP0379544A1 - Fabric cleaning and sanitizing compositions - Google Patents

Abstract

Acaricidal detergent compositions for cleaning carpets, upholstery, bed sheets and the like comprise a mixture of surfactants, an alcohol such as a benzyl alcohol having acaricidal properties, a glycol or a solvent alkyl glycol, such as monoethyl ether of diethylene glycol, as well as an alkanolamine or an amine such as a monoethanolamine in a combination so as to effectively soak the hydrophobic surfaces of mites, their larvae and oocytes, and thus eliminate said mites and their allergens.

Description

Title:- "Fabric Cleaning And Sanitizing ComDCsitions"

This invention relates to a composition end method for reduction of ar eradication of ai lergens particularly dust mites in car^pet.

For the sake of brevity, the invention wil l z>e described mainiy in relation to dust mites but the invention is by no means limited thereto, as wil l be evident.

Health problems related to bacteria and insects in household furnishings and fabrics are an increasing problem. Caroets, upholstery, wal l decorations, curtains, rugs, bedding, sheets, pil low slips, dooncs, and like fabrics and articles are recognised as capable of harbouring microbes, insets and other microscopic animals which give rise to health problems such as al lergies.

Such fabrics and articles are subjected to soiling in regular use and soil is frequently a food source and/or habitat for unwanted microbial or other life. Food and drink remnants, cooking oils, soils tracked onto floors, human soils, air borne soils and dusts and most of al l, human and animal skin scales, of which the average adult human sheds between 2 and 4 grams per day, al l constitute nutrients for microbial or other life.

The household dust mite (Dermatophagoides spp.) is undoubtedly the most troublesome micro-organism found in the household and industrial environment. The dust mite is widely implicated in human al lergies, especial ly in the nasal and upper respiratory area, although skin allergies are not infrequently reported. Allergies from the dust mite have also been linked with asthma in susceptible people. Moreover, allergies due to dust mites are regarded as a source of immune al lergy reactions both in young children and adults. Practical ways of control ling, if not eliminating, dust mites from within the average household is a major area of medical and scientific research, with wide potential for improving the health of an increasingly large proportion of the population.

Allergies due to the dust mite arise as a result of both living and dead mites. The primary source of allergen is thought to be one or more of the glycoproteins found in significant concentration in the gut and the excreta produced by living mites. Dead mites retain the al lergen within their digestive system and release the al lergen to the surrounding environment, expedited by such physical action as walking on the carpet. Living mites excrete into their habitat up to 20 times a day. High populations of dust mites can therefore produce large quantities of al lergens which increase with time unless the growth of mites is restricted or the allergen is either removed or shielded or reacted with a composition which wil l prevent allergic reactions on contact with humans.

The female mite lays larvae within the pile of a carpet or in shielded areas of fabrics, and the larvae take from three to four weeks to hatch. The coating of the larvae is impervious to most household chemicals, insecticides and detergents, like oocysts of some protozoan parasites, are very difficult to kill by chemicai means. Thus, while means are known to kil l living dust mites, hitherto there has not been a practical way of penetrating or wetting the surface of dust mite larvae to prevent recolonization. Further, larvae are found well below the surface of carpet and fabrics and therefore are relatively inaccessable to normal cleaning methods.

Australian Patent Application No. 44606/85 discloses a method of spraying carpets and fabrics with an alcoholic solution of a benzyl alcohol- tannic acid complex.

The specification teaches that the solution kil ls living dust mites and that tannic acid in the formulation contributes to neutralising the allergy reaction caused by the aforementioned al lergen found in both live and dead mites. However, the solution has a number of serious drawbacks. Firstly, it is highly flammable; secondly, it is very difficult to apply evenly; thirdly, it does not kill larvae; and lastly, it leaves additional chemical residues in or on fabrics. Tannic acid residue discolours with age and causes light-coloured fabric to progressively discolour (by air oxidisation to coloured molecules) especial ly when the product is used repeatedly, and the tannic acid being highly polar may also serve to bind some soil already on textile surfaces. Further, the product has no cleaning action therefore what is sprayed onto surfaces remains where it is sprayed, once the benzyl alcohol has evaporated. The spray then becomes another chemical residue on the fabric surface, and, of itself a potential allergen.

As indicated in Patent Application No. 44606/85 dust mite allergen is not destroyed by oxidising agents, reducing agents, di- and trivσlent metal ions, alkalis, mild acids, aldehyde, or proteolytic enzymes. In addition, in our own experiments we have found that dust mites are not "wetted" by common pretroleum solvents or by the types of surfactants found in normal household detergents or carpet cleaning operations. We believe this explains why dust mites survive normal household cleaning operations. Indeed, we have found thαt two widely used highly efficient fluorocαrbon surfactants h C 120 and FC 99 (3M COMPANY, INC) both of which give very low surface and interfacial tensions do not "wet" mites.

Carpets in specialised areas such as in hospitals and health care institutions also suffer from particular problems from bacterially con¬ taminated spil lages and other distinctive hospital residues. Carpets and fabrics can be fouled accidentally or by nursing procedures with human blood, body f luids, exudate, urine, faeces, vomitus, saliva and aerosols. These may be contaminated with a range of pathogenic bacteria and viruses capable of causing cross infection between patients. Dried bacteria in spore form may become air borne under foot traffic in hospital wards. It is therefore desirable that any method of cleaning fabric be capable of not only kil ling dust mites but, as well, capable of destroying the widest possible range of microbes resident within hospital fabrics and surfaces.

It is preferable that the removal of spots and stains, as wel l as heavy soiling, occur quickly and efficiently while biocidal action takes place.

Dust mites resident in normal household carpet survive normal industrial injection cleaning using an efficient carpet detergent and this is illustrated in a recent publication entitled, "D.J.J. Wassenaar, Effectiveness of Vacuum Cleaning and Wet Cleaning in Reducing House-Dust Mites, Fungi and Mite Allergen in a Cotton Carpet: A Case Study - Experimental and Applied Acaroioty, 4 ( 1 88) 53-62". The study concluded that the procedures used (vacuuming followed by wet spray extraction cleaning) to combat house dust mites, "may have had an adverse effect in the long run". The number of mites and mite eggs found after cleaning actual ly increased while the level of al lergen was diminished. Both mites and their eggs survived wet cleaning with an efficient spray injection detergent.

Other published work has shown that common household insecticides have little if any affect upon dust mites, neither do disinfectant substances. The first successful report of control ling dust mites was published in 1975 (Clinical Allergy, Vol. 5, 109- 1 14) which used a combination of a terpene and a biocide in a solvent base. Unfortunately, field experience did not support laboratory findings and the claim of acaricidal action was not pursued.

The truly hydrophobic nature of the coating of the dust mite, its shed skin and its larvae remain the major obstacle to developing a commercially viable acaricidal detergent. Solving the problem of wettability is the first and important step to conveying to the mite a suitable toxin at the optimal dose. While this can be achieved with volatile alcoholic solvents and by benzyl alcohol and some terpenes, the products are flammable, lack cleaning ability and are ineffective against larvae which later hatch and reinfest fabrics. it is an object of this invention to provide a detergent composition which is capable of wetting mites, particularly dust mites, and by this means, to provide a vehicle for transporting chemicals singly or in multiples to kil l the mites. It is also an object that the composition of the invention wil l render larvae infertile and, significantly, reduce the allergy response to the proteinaceous allergen found in mites and their excreta. It is believed that the latter occurrence is due to the constituent groups on the protein becoming hydrogen bonded to either or both the surfactants or solvents incorporated in composition of the present invention. The present invention provides a new and major finding of significant practical benefit in control ling the population of mites, particularly dust mites. A further object of the present invention is to provide a simple, safe detergent for washing fabrics particularly househouid fabrics such as sheets, pillow cases and curtains whilst erradicating microbes, particularly dust mites and their larvae.

In accordance with the present invention there is provided a acaricidal detergent composition comprising (a) a glycol or alkyl glycol, (b) one or more long chain alkyi alcohols, cyclic or aromatic alcohols, (c) an alkanolamine or amine, and fd) one or more surfactants.

To achieve detergency required in stain removal and emulsification of organic soils a highly polar glycol, ether or ketone solvent is preferred. This may be chosen from ethylene glycol, propylene glycol, diethylene glycol, diproylene glycol, triethylene glycol or their respective mono or dϊ, methyl, ehtyl, propyl or butyl ethers, ethyl 3-ethoxypropionate or 3-methyl methoxy butanol and alkyl substituted propylene glycol ethers. The amount preferred depends upon ultimate surface activity and the need to solubilise other components with low water solubility within the micelle structure of the acaricidal composition.

The preferred glycols of the present invention are the common mono- and diethers of ethylene glycol, diethylene glycol, propvlene glycol, dipropylene glycol and triethylene glycol although other low molecular weight hydric solvents of similar range may also show similar effect and/or benefit including 3-methy! methoxy butanol and ethyl 3-etnoxypropionate. The amount required varies with the quantity and relative proportion of other ingredients which mav require solubilization in an aqueous medium. The quantity of glycol or like solvent may vary from 1.0 to 45.0 percent preferably from 1.0 to 5.0 percent in ready-to-use products and from 3.5 to 40.0 percent in dilutable products.

To further assist in cleaning as a co-solvent and, at the same time, to act as an additional toxin to dust mites, the addition of an aromatic or cyclic alcohol is found most useful.

The preferred alcohols are aromatic alcohols, such as benzyl alcohol and 2-phenolethanol and phenoxy ethanol; although smal ler quantities of some aliphatic alcohols such as 4-chlorobutanol, n-pentanol, n-hexanol. n-octanol, n-decanol, and n-dodecanol may also be incorporated as part of the acaricidal system. The specific alcohols referred to are only partly soluble or insoluble in water and it is therefore necessary to adjust the composition of the present invention by addition of a lower alcohol such as ethanol or isoproponol, a glycol or a known detergent hydrotrope such as urea, sodium xylene sulphonate or toluene suiphonate, to obtain solubilization of the less soluble alcohol. The preferred percentage of sodium xylene sulphonate is between 0.05 percent for use in ready-to-use compositions and 25 percent for use in non-aqueous concentrates. More preferably, the percentage range is between 5.0 to 15.0 percent for use in aqueous dilutable concentrates.

We have found that the toxic effect of aromatic alcohols is increased by the addition of terpenes. Preferred terpenes are those derived from either pine, eucalyptus, peppermint, citrous or tea-tree oils, of which dipentene, terpineol, terpinolene, cineol, citral, citronel la, pinene, terpinen-4-ol and Y- terpene are most preferred.

Similar cyclic molecules with a strongly polar hydroxyl group are also appropriate. By adding an aromatic nucleus into the micel le system there is achieved a significant amplification in both cleaning and acaricidal properties. The combination of a lower molecular weight glycol and an aromatic alcohol appear synergystic, especial ly in terms of practical detergency in the compositions of the present invention.

The choice of solvent and its relationship to the surfactant system is critical. It has been found important to combine glycol-type solvents with the previously nominated ingredients both to promote interfaciai behaviour and solubilise other less soluble chemicals in the compositions of the invention, including a smal l quantity of a terpene solvent which contributes to the ability of these formulations to overcome the hydrophobic effect of the skin of the mite and, presumably the natural impermeability of the outer layer of mite oocysts.

To provide alkalinity and to contribute to the solvency of the detergent towards hydrophobic surfaces and stains, especially stains of an anionic nature, a water soluble amine or alkanolamine may be included. The amine may be chosen from cyclic amines such as pyrolodones or either mono, di or triethanolamine or isopropanolamine, and the quantity adjusted according to the pH and interfacial behaviour desired in the formulation. In a preferred embodiment, the amine is present 0.5 to 5.0 weight percent and the preferred pH of the detergent is in the range of 9.0 - 12.5 as a concentrate.

The addition of a smal l quantity of an alkanolamine such as monoethanolamine, isopropanolamine, diethanoiamine, triethanolamine, di- ethyl aminoethanol or other odourless amine or hydroxy amine also assists in the process of overcoming the resistance of mites and their larvae, presumably by contributing hydroxy I ions to aqueous solutions as well as providing additional solvency. These two effects also contribute materially to the cleaning ability of the surfactant aspect of these products by a phenomenon well understood by those skilled in the art.

The combination of glycol, an aromatic alcohol and alkanolamine is further assisted as a detergent and stain remover by the incorporation of a smal l quanity of naturally derived terpene. it is known by those skil led in the art to also become incorporated into micelles and thereby to contribute to increased detergency. The quantity needed to solubilise the terpene in a particular composition will vary with the basic surfactant system, the choice of cyciic, aromatic or aliphatic alcohol, the dispersing system and the choice of glycol. In ready-to-use products it is preferred to use from 0.05 to 0.25 percent while in dilutable concentrates the amount wil l vary from 0.25 to 10.0 percent.

The composition of the present invention preferably has a surfactant system which has an extremely low interfacial tension to both polar and non- polar oils and solvents as well as surfaces. The surfactant system preferably consists of two to five surfactants of more than one basic type which when blended together wil l display spontaneous emulsification of paraffin oil, lubricating oils and food oils like olive oil, which is quite surface active itself. Such surfactant systems are generally found only in very specialised industrial degreasing material which are totally unsuitable for use as textile detergents or for use on protein based finishes such as leather and silk. In α preferred embodiment, the total quantity of surfactant required in the composition ranges from 0.05 to 30.0 percent, typical ly 0.05 to 0.5 percent in ready-to-use compositions or from 2.5 to 30.0 percent in concentrates which are dilutable before use.

The surfactant substances may be anionic, non-ionic, amphoteric or catonic and preferably comprises in part a detergent having one or more chemicals to promote rapid release of common fabric stains but which also contribute to an efficient biocidal and pesticidal system. The detergent is preferably a non-ionic detergent system which may contain one or more non- ionic detergents capable of efficiently emulsifying mineral oils, fats and cooking oils. Such detergents may be either long chain alkyl (e.g.C_Q - C , ^) substituted phenol polyethoxylate or an ethoxylated alcohol with an alkyl chain length from 8 to 20 saturated carbon atoms. The non-ionic surfactants preferably comprise from ! to 27.5 percent of product depending on the formulation desired. Surface tension may vary from 25 to 40 dynes per centimetre. Fatty acid alkanolamides may be incorporated with the non- ionic detergents, the two being compatible and occasional ly synergistic in detergency.

In a preferred embodiment the surfactant may comprise two or more anionic surfactants chosen from the group consisting of alkyl, aryl, sodium, calcium, magnesium, ammonium, potassium, mono, di or triethanolamine or isopropylamide, sodium olefin sulphonate, sodium alkyl or dialkyl naphthan- lene sulphonate, alkyl (C . -C . -.), sodium, calcium, magnesium, ammonium, or lithium sulphate, and sodium, potassium, calcium or other neutralised dioctyl sulphosuccinate, substituted, sulphonated or half ester of a sulphonated sulphosuccinate derivative, alkyl (C _| «-C _| ^) diphenyl oxide, sodium, calcium, ammonium or alkanolamide disulphonate, anionic f lurocarbon surfactants.

While the surfactant system may wet dust mites this alone will not ensure that living mites wil l be kil led or the infertility of mite larvae. Instead the expanded micelle principle is used to incorporate into the detergent micel le solvents and other chemicals which aid in cleaning process and are fatal to microbial life including dust mites. Additional ly, and to add wide spectrum bacterial action, it is preferred to incorporate one or more biocides of the general group alkyl dimethyl benzyl ammonium chloride, bromide or iodide, diaklyl dimethyl ammonium chloride, bromide or iodide, alkyl trimethyl ammonium bromide, chloride or iodide or like molecule of which an alkyldimethylbenzyl ammonium chloride is a preferred example; although most strongly bϊocidal ly active cationic surfactants, which may be either single or branched chain, or where the hydrophobe is substituted with a halogen, and in which the cation is reacted with a chloride, bromide or iodide or indeed where nitrogen is substituted by phosphonus in the active cation, can be employed by appropriate adjustment to the different interfacial behaviour resulting from the different cation species. The preferred amount of cationic surfactant is up to 35.0 percent of the total surfactant content and varies from 0.025 to 1.0 percent for ready-to-use compositions or from 1.0 to 10.0 percent for dilutable products.

The cationic surfactant can be supplemented by a second biocide, preferably of a proton donor type which is not generally micelle attracted. This is often indicated for specialised industrial purposes, including use in veternary and agricultural industries. The preferred commercial biocides are formaldehyde, glyoxal, glutaraldehyde, succϊndiaidehyde, crotondϊaldehyde or a cyclic or semi-cyclic aldehyde or ketone; Dantogard and Glydant (Glyco Inc. USA), Kathon CG/1CP (Rhom & Haas Inc, USA), DMDH Hydantoin; Ger all I 15 (Sutton Laboratories Inc. USA); Givgard DXN (Givaudan,USA) and many other similar biocides are envisaged and may be used. The amount of secondary biocide may vary from 0.0 ! to 0.25 percent for ready-to-use compositions to 0.5 to 7.5 percent for dilutable formulations.

As will be evident from the foregoing, some of the Ingredients may simultaneously serve more than one function in the composition. Thus certain surfactants may be acaricidal or bactericidal: certain alcohols may be both acaricidal and serve as solvents or co-solvents; the alkanolamϊnes both assist in achieving detergency by raising the pH to value where the solvent wil l readily react with fatty acids and also assist in solubilising al lergen proteins.

A major feature of the compositions in accordance with the invention is that they provide acaricidal compounds In a solvent/detergent system which effectively wets the surface of dust mites, their larvae and the al lergen proteins, and therefore brings the acaricide into intimate contact with the target material. Generally a micelle structure is set up in aqueous compositions as used, with the various solvents, glycols, alcohols, alkanolamine and surfactant largely associated in the micel les which contribute very efficiently to the interfacial behaviour of the composition.

In addition, it is most preferred to Incorporate in the compositions of the invention a conventional solids dispersing and suspending system, which wil l also soften hard water. Such systems are found in al l modern textile detergents, but in this case the system chosen must be compatible with the acaricidal and bactericidal aspect of each composition disclosed herein.

A soil suspending system is preferred to assist detergency, soften water and help prevent redeposition of soil once removed from the fabric. A choice may be made from a polymeric phosphate, for example sodium tri- polyphosphate, tetrasodium pyrophosphate, tetrapotassium pyrophosphate, sodium hexametaphosphate or like neutralised phosphate polymer. Alter¬ natively, or in addition to the polymeric phosphate, a chelating agent such as tetrasodium ethylene diamine acetate or analogues of substituted derivatives of ethylene diamine may be incorporated. Preferably, an inorganical ly neutralised polyacrylate or polyacrylate copolymers with proven soil suspension properties may be used.

The soil dispersing system can be of a type common to modern detergents and therefore well understood to those skil led in the art. The chemicals chosen, however, should not contribute to resoiling, after use from unrinsed residues. Preferably the system comprises a combination of either sodium carbonate, sodium citrate, sodium bicarbonate, a polymeric phosphate such as sodium tripolyphosphate, tetrapotassium pyrophosphate, tetrasodium pyrophosphate or sodium tetraphosphate, a chelating agent of the group ethylene diamine tetracεtate, sodium nitrilo triacetate, disodium aluminium silicate, trisodium nitrilo triacetate, tetresodium ethyenediamine acetate or an equivalent substituted ethyene-diamine derivative, a polyacrylate disperson, polyvinyl pyrrolidone, sodium carboxymethyl cel lulose, a zeolite or sodium aluminium silicate, or the ammonium salt of a styrene maleic anhydride resin. The quantity required is proportional to the amount of surfactants in the formulation and preferably lies within the range of from 0. 1 to 5.0 percent according to the balance of the formulation.

The pH of the formulation should be adjusted in the range 7.5 to 1 2.5 by the use of either a polymeric phosphate or a buffer such as sodium citrate or a combination thereof, or by an alkanolamine chosen from aforementioned alternatives. The pH at the recommended dilution for use should be in the range of 4.5 to 10.0, however in special cases, the pH may be made more acidic by use of a laundry sour such as ammonium, magnesium, or zinc f luoro silicate, the pH in the range of 3.0 to 5.0 thereby necessitating 0. 10 to 5.0 percent of sour in the particular composition. The purpose of the acidic formula is to serve as a soil break or release agent, or as they are more commonly known a "prespray", before use of the principal composition. In addition, a non-substantive dye may be included to give a distinctive colour to the composition, ft is also envisaged that appropriate quantities of perfume may be incorporated. To stabilise the solution a small amount of a hydrotrope, such as sodium xylene sulphonate or low molecular weight alcohol such as ethanol or isopropanol, may be required as previously mentioned. The amount of hydrotrope may vary according to the composition but wil l preferably be in the range of 1.0 to 25.0 percent of the composition. The preferred hydrotropes are dependent on the formulation of the preferred compositions.

A method according to the invention comprises the steps of firstly prespraying the surface with the composition of the invention diluted I part with 3 to 6 parts of water and allowing the formulation to remain on the surface for I to 2 hours, secondly injection cleaning either by spraying under pressure or by flooding under vacuum a solution comprising I part of the composition of this invention to 15 to 40 parts of cold or warm water, then removing the excess solution by strong vacuum as fitted to commercial and domestic carpet cleaning machines. The surface Is left moist and al lowed to dry over a 2 to 8 hour period wherein the composition remains active and continues to exert its acaricidal and bactericidal action. The prespray may be omitted in the case of many domestic carpets in favour of a wet cleaning process of the kind in which a cleaning solution Is applied to the carpet and simultaneously picked-up after being drawn through the carpet pile. When a particularly badly soiled carpet is encountered It Is advantageous to use a mildly acid "sour type" prespray to release aged, packed and tightly bound soil prior to injection cleaning.

By way of il lustration only, preferred embodiments of the invention will now be described with reference to Examples I to IX which set out preferred elements of a range of compositions in accordance with the present invention. EXAMPLE 1

Surfactants: Teric X 5 ( 1 ) 2.5%

Teric N I 5 (2) 1.0%

Teric I 2A8 (3) 0.65%

Teric N50 (4) 2.5%

Coconut diethanolamide 0.8%

Lauryl dimethyl amine oxide 0.35%

Gardiquat 1480 (5) 1.6%

Glycol: Diethyleneglycol monoethyl ether 5.0%

Alcohol: Benzyl alcohol 7.5%

Amine: Monoethanolamine 1.3%

Other ingredients: Cineol 0. 1 % Ethanol 10.0% Urea 4.3%

Tetrapotassium pyrophosphate 1.0% EDTA, Na3 1 .0% Citric acid 1.8% Water balance.

( 1) Teric X 5 - a commercial ly available non-ionic surfactant comprising octyl phenol ethoxylate with 5 moles of ethylene oxide (IC1)

(2) Teric N 15 - a commercially available non-ionic surfactant comprising nonyl phenol ethoxylate with 15 moles of ethylene oxide (ICI)

(3) Teric I 2A8 - a commercial ly available non-ionic surfactant comprising a C , -. alcohol ethoxylate with 8 moles of ethylene oxide (ICO

(4) Teric N50 - a commercially available non-ionic surfactant comprising nonyl phenol ethoxylate with 50 moles ethylene oxide.

(5) Gardiquat 1480 - 80% active alkyl dimethyl benzyl ammonium chloride in ethanol (Albright & Wilson Limited) Exαmple II

Surfactants: Teric X 10 (6) Teric 12A4 (7) 0.65% Teric N50 Gardiquat 1480 1.75%

Glycol: Diethylene glycol monoethyl ether 7.5%

Alcohol: Benzyl alcohol 8.0%

Amine: Isopropanolamine 2.0%

Other ingredients: Limonene 0.15%

Urea 1.5%

Citric acid 0.8%

Sodium polyacrylate dispersion 2.5%

Water balance

(6) Teric X 10 - a commercially available non-ionic surfactant comprising octyl phenol ethoxylate with 10 moles of ethyiene oxide (IC1)

(7) Teric I 2A4 - a commercially available non-ionic surfactant comprising a synthetic straight chain (average C , -,) alcohol

I _- ethoxylate with 4.5 moies of ethylene oxide (ICl).

Example 111

Surfactants: Teric X 10 0.9%

Teric 9A5 (8) 1.25%

Teric N50 1.3%

Coconut diethanolamide 0.5%

Bardac 22 (9) 3.0%

Glycol: monoethyl ether 21 .0%

Alcohol: Benzyl alcohol 10.0%

Amine: Monoethanolam i ne 2.5%

Other ingredients: Cineol 0. 1 %

Ethanol 17.5%

Urea 2.3%

EDTA, Na3 1.75%

Citric acid 0.8%

Sodium polyacylate dispersion 2.5%

Water balanc

(8) Teric 9A5 - a commercially available non-ionic surfactant comprising a synthetic straight chain (Cg-C . , ) alcohol ethoxylate with 5 moles ethylene oxide (1CI)

(9) Bardac 22 - a commercial ly available dual chain alkyl methyl benzyl ammonium chloride (Lonza Inc. U.S. ) Example IV

Surfactants: Teric 12A8 4.0%

Amphoterge 251 (10) 2.55%

Lauryl dimethyl amine oxide 1.0%

Gardiquat 1480 3.0%

Glycol: Diethylene glycol monoethyl ether 18.0%

Alcohol: Benzyl alcohol 9.0%

Amine: Monoethano I am ine 2.0%

Other ingredients: Ethanol 7.5%

Urea 3.0%

Tetrapotassium pryophosphate 1.25%

Sodium polyacrylate dispersion 2.5%

Water balance

( 10) Amphoterge 251 - a commercial ly available amphoteric surfactant

(Lonza Inc. U.S. A)

Example V

Surfactants: Teric X 5 2.0%

Teric N 15 2.5%

Teric N50 3.0%

Coconut diethanolamide 2.5%

Gardiquat 1480 4.5%

Glycol: Diethyleneglycol monoethyl ether 40.0%

Alcohol: Benzyl alcohol 20.0% n Decanol 5.0%

Amine: Monoethanolamine 3.0%

Other ingredients: Cineol 1.0% Ethanol 16.0% Citric acid 1.0% Trisodium nitrilo triacetate

(Note: Water Nil)

Example VI

Surfactants: Teric X 10 2.0%

Teric 12A4 2.5%

Coconut diethanolamide 1.0%

Bardac 22 4.0%

Petro 22 ( l l) 0.5%

monoethyl ether 16.0%

Alcohol: Benzyl alcohol 8.5%

Amine: Monoethanolamine 1.5%

Other Ingredients: Cineol 0.25%

Ethanol 12.0%

Trisodium nitrilo triacetate 1.8%

Water balance

(1 I) Petro 22 - a commercially available sulphonated substituted naphthalene derivative (Soneborn Oil Co., U.S. A.)

Example VII

Surfactants: Teric X 5 3.0%

Teric 12 A 12 ( 12) 1.5%

Teric 9A5 1.0%

Teric N50 r.5%

Coconut diethanolamide 0.5%

Lauryl dimethyl amine oxide 1.5%

Gardiquat 1480 3.0% Glycol: Diethyleneglycol monoethyl ether 18.0%

Alcohol: Benzyl alcohol 7.0%

Amine: Diethylamine ethanol 1.5%

Other ingredients: Cineol 0. 15%

Ethanol 8.0%

Urea 2.5%

Citric acid 1.0%

Trisodium nitrilo triacetate 2.0%

Sodium polyacrylate dispersion 2.0%

Water balanc

( 12) Teric I 2A 12 - a commercial ly available non-ionic surfactant comprising lauryl alcohol ethoxylate with 12 moles of ethylene oxide (IC1).

Example Vlll

Surfactants: Teric N 15 2.0%

Teric I 2A4 1.5%

Bardac 22 4.0%

Glycol: Diethyleneglycol monoethyl ether 15.0*3

Alcohol: Benzyl alcohol 7.5%

Amine: Monoethanolamine Other inαredients: Cineol 0.1 %

Glyoxαl 0.25%

Ethanol 8.0%

Citric acid 1.0%

Trisodium nitrilo triacetate 1.5%

Sodium polyacrylate dispersion 2.5%

Water balance

Example IX

Surfactants: Teric I 2A4 .8% Sarkosyi NL30 ( 13) 3.0% Gardiquat 1480 Petro 22 .0%

Glycol: Diethyleneglycol monoethyl ether 17.5%

Alcohol: Benzyl alcohol 8.0%

Amine: Monoethanolamine 2.5%

Other ingredients: Cineol 0. 1 %

Ethanol 1.80%

Citric acid 1.0%

Trisodium nitrilo triacetate 1.5%

Sodium polyacrylate dispersion 2.5%

Water balance

( 13) Sarkosyi NL-30 - a commercially available amphoteric surfactant

(Ciba-Geigy Inc). EXAMPLE X

Surfactants: Teric X 5 1.0%

Teric I 2A 12 1.0%

Teric 9A5 1.5%

Teric N50 1.5%

Lauryl dimethyl amine oxide (50%) 1.0%

Gardiquat 1480 3.0%

Glycol: Diethyleneglycol monoethyl ether 13.5%

Alcohol: Benzyl alcohol 7.5%

Amine: Monoethanolamine 1.5%

Other ingredients: Ethanol 7.5%

Urea 2.0%

Sodium polyacrylate dispersion 2.0%

Magnesium fluorosilicate 1.5%

Water balance

Whilst in the above Examples the glycol used throughout is diethyleneglycol monoethyl ether, other glycols as previously mentioned may be sustituted. Likewise, whilst the aromatic alcohol used throughout is benzyl alcohol, others could be substituted and for powder compositions long chain alkyl alcohols could be employed. By combining the appropriate elements in the aqueous (or in the case of a concentrate for use with a powdered formulation a non-aqueous) medium it is possible to prepare an acaricidal biocidal cleaning powder, for example, by absorbing from 0.5 to 10.0 percent of Example V on a powder or mixture of powders having high solvent absorbency. Such a mixture may be an equal part by weight of sodium bicαrbonαte and diatomaceous earth. Other inorganic chemicals can be used such as sodium sulphate, sodium borate or sodium tripolyphosphate, as can some ground natural products such as cereals. Crumbed or spray dried polymers with high solvent absorbency are also suitable for this purpose. Powdered products made this way must be capable of solvent transference to allow cleaning to occur and to release the σcaricide and biocide onto fibre surfaces. This type of formula is very important where water cannot be used on some types of textiles.

To manufacture the compounds shown in Examples I to X it is desirable to first mix together the surfactants and glycols. These are then diluted with the water where required and other ingredients dissolved individually. Finally, if the solution is not clear then either the hydrotrope or ethanol or both are added until the desired stability is achieved. Finally dye is added and pH adjusted as appropriate.

The basic surfactant system may be formulated by those experienced In the art in a number of different ways, provided that any residues left on fibres or drying wil l not cause either damage to textile fibres, destruction or partial loss of dyes, change in surface characteristics or promote resoiling after application of the preferred composition. Examples I to X set out a number of ways in which a suitable surfactant system can be formulated but it is by no means exclusive. Within any single molecular species of the surfactants nominated it is possible to vary either the length, branching or substitution of the hydrophobe section of the molecule or to vary either the degree of ethoxylσta ion by use of a mixture of ethylene and propylene oxides or propylene oxide alone to form non-ionic surfactants: or to react the terminal -OH group to form sulphate or phosphate. The latter are then neutralised by alkali salt, ammonia or an alkanolamide. Various types of zwitterion surfactants are available each with distinctive surface-active properties and behaviour. In the range of anionic surfactants, alkyl benzene sulphonates, alkyl sulphates, olefin sulphonates, substituted alkyl napththa- lene sulphonates which may be neutralised by a mono or divalent cation or by ammonia or an alkanolamide.

A person skilled in the art will be able to choose from these and other commercially available surfactants in order to achieve a surfactant system which exhibits the interfacial behaviour described above, which, when combined with the other ingredients in the proportions described wil l give products which are both good textile detergents and are both acaricidaily and biocidal ly active when used as specified. In general the compositions comprise combinations of:-

(a) surfactants including non-ionic, cationic and some anionic for low foaming compositions: some anionic, alkanoiamides and amphoterics for moderate foaming compositions; and some amphoterics and sulphated or sulphonated surfactants for high foam compositions;

(b) water miscible solvents such as alkylglycols, ketones and ethers;

(c) at least partially water immisabie solvents such as aromatic solvents and terpenes;

(d) acaricides such as aromatic alcohols, C,-C-,.- alkyl alcohols;

(e) detergent builders such as phosphates, citrates, polyacylates, substituted celluloses, silicates, alumino silicates, polyinyl pyrollidones;

(f) chelating agents such as tetrasodium EDTA, trisodium nitrilo triacetate;

(g) absorbents such as sodium carbonate, diatomaceous earth, crumbed plastics, where required.

The acaricidal performance of Example IV is shown in the fol lowing Table. This compares the properties of the commercial acaricide ALLERSEARCH DMS made according to Australian Patent Application No. 44606/85 with the composition of Example IV.

Time to Kil l Dust Mites in Minutes

Dilution 1/2 1 /4 1 /8 1 / 16 1 /32

Example IV 6 14.5 17 23 50

Allersearch

7 9.5 21 45 59 DMS

It wil l be seen that at high strength both products are comparable acaricidal ly but at lower dilutions, 1 / 16 Example IV shows far superior action. Whereαs ALLERSEARCH DMS does not kill oocysts, Example IV will prevent fertilisation whe~ used in the recommended manner.

The rapic^* _carϊcidal action is believed to arise primarily from the combination of aromatic alcohol, alkyl glycol and alkanolamine in an aqueous detergent system such that these materials are to a significant extent (but not wholly) taken up into micelle structures exhibiting the necessary interfacial behaviour to attach to the mites and their larvae.

The aromatic or long chain aliphatic alcohols exhibit the major acaricidal activity. Aliphatic alcohols may be used primarily in a non-aqueous powdered composition because of their insufficient solubility in aqueous systems, for which aromatic alcohols are to be preferred.

The glycols assist in providing the required interfacial behaviour including contributing to detergency and solubilisϊng the allergens of the dust mites. The alkanolamine also assists in solubilizing the allergens and raises the pH of the system to promote reaction with fatty acids, thus further improving detergency.

An additional organic solvent is useful for improving the cleaning action, particularly aromatic solvents such as terpenes which are themselves potentially acaricidal.

A method according to the invention is as follows:-

1. The carpet Is presprayed lightly (so that it is evenly moist but not wet) with the product say Example IV, diluted 1 part with 3 to 6 parts of tap water. This is allowed to stay on the carpet for 1 to 2 hours, during which time it both precleans and releases spots and stains as well as penetrates to the base of the carpet or fabric.

2. The carpet is then injection cleaned with a machine which injects detergent into carpet then withdraws it under vacuum to a recovery tank using a mixture of I part Example IV and 15 to 40 parts of water. A wide variety of heavy industrial injection (steam) cleaning machines can also be used depending upon the concentration, fibre type and location of carpet. In some cases it is practical to eliminate the prespraying step for normal domestic carpet cleaning. The stronger solution may, instead, be used for prespotting spots and stains immediately before wet washing.

After cleaning the carpet is left moist with Example IV which gradually dries over a 2 to 8 hour period depending on weather and machine used. During the drying period the product e.g. Example IV, remains active and continues to exert its acaricidal and bactericidal action. As mentioned earlier, when particular^ badly soiled carpet is encountered it may be advantageous to use a mildly acid "sour type" prespray to release aged, packed and tightly bound soil prior to injection (steam) cleaning. The formulation of Example X describes this type of acaricidal prespray which can be used also in exceptional ly hard water.

The features disclosed in the foregoing description, or the accom¬ panying drawings expressed in their specific forms or in terms of a means for performing the disclosed function, or a method or process for attaining the disclosed results, may, separately or in any combination of such features, be utilised for realising the invention in diverse forms thereof.

Claims

CLAIMS:-

1. An acaricidal detergent composition comprising (a) a glycol or alkyl glycol, (b) one or more long chain alkyl alcohols, cyclic or aromatic alcohols, (c) a alkanolamine or amine, and (d) one or more surfactants.

2. A composition according to Claim I wherein the glycol or alkyl glycol is selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol or their respective mono or di, methyl, ethyl, propyl or butyl ethers, ethyl 3-ethoxypropionate or 3-methyl methoxy butanol.

3. A composition according to Claim 2 wherein the glycol or alkyl alcohol is present in the range of 1.0 to 45.0 percent of the composition.

4. A composition according to Claim I wherein the alcohols are soluble or insoluble or partly soluble in aqueous solution.

5. A composition according to Claim 4 wherein the alcohols are selected from the group consisting of benzyl or phenylethyl alcohol or phenoxyethanol.

6. A composition according to Claim 5 wherein the alcohol is present in the range of 0.05 to 25 percent of the composition.

7. A composition according to Claim I further comprising an additional organic solvent.

8. A composition according to Claim 7 wherein the solvent is a terpene.

9. A composition according to Claim 8 wherein the terpene is selected from the group consisting of dipentene, terpinolene, terpineol, cineol, citral, citronella, pinene, limonene, terpinen-4-ol, Y-terpϊnene.

10. A composition according to Claim 7 wherein the solvent is present in the range of 0.25 to 10.0 percent of the composition.

1 1 . A composition according to Claim I wherein the alkanolamine or amine is selected from the group consisting of monoethanolamine, isopro¬ panolamine, diethyl amino ethanol, diethanolamine or triethanolamine.

12. A composition according to Claim I I wherein the alkanolamine or amine is in the amount of 0.25 to 5.0 percent of the composition.

13. A composition according to Claim I wherein the surfactant is anionic, nonionic, amphoteric or cationic.

14. A composition according to Claim 1 3 wherein the surfactant is present in the range of 0.05 to 30.0 percent of the composition.

15. A composition in accordance with Claim I comprising an additional soil dispersing and suspending component.

1 . A composition in accordance with Claim 15 wherein said additional component comprises one or more of sodium carbonate, sodium citrate, sodium bicarbonate, sodium tripoly phosphate, tetrasodium pyrophsphate, tetrapotassium pyrophosphate, sodium tetraphosphate, trisodium nitrilo triacetate, tetresodium ethyenediamine acetate or an equivalent substituted ethyenediamine derivative, a polyacrylate disperson, polyvinyl pyrrolidone. sodium carboxymethyl cel lulose, a zeolite or sodium aluminium silicate, or the ammonium salt of a styrene maleic anhydride resin.

17. A composition in accordance with Claim 15 wherein the additional component is present in the range of 0. 1 to 5.0 percent of the total composition.

18. A composition in accordance with Claim I further comprising a hydrotrope in a predetermined amount necessary to stabilize the composition,

19. A composition in accordance with Claim 18 wherein the hydrotrope is chosen from the group consisting of urea, ethanol, isopropanol, sodium xylene sulphonate or toluene sulphonate.

20. A composition in accordance with Claim 19 wherein the hydrotrope is present in the range of 0.5 to 25.0 percent of the total composition.

21. A composition according to Claim I in which up to 35.0 percent of the surfactant is a cationic biocide of the general group alkyl dimethyl benzyl ammonium chloride, bromide or iodide, diaklyl dimethyl ammonium chloride, bromide or iodide, alkyl trimethyl ammonium bromide, chloride or iodide or like molecule.

22. A composition according to Claim 21 wherein an additional biocide of the proton donor type is provided which Is selected from the group consisting of formaldehyde, glyoxal, glutaraldehyde, succindialdehyde, crotondϊaldehyde or a cyclic or semcyclic aldehyde or ketone.

23. A composition in accordance with Claim 21 wherein the additional biocide is present in the range of 0.01 to 7.5 percent of the composition.

24. A composition in accordance with Claim I in the form of a liquid or powder which when dissolved in water in a concentration of 0.25 to 25.0 percent will yield a pH of 4.5 to 10.0 at its recommended use dilution.

25. A composition according to Claim 1 which is a acidified by the addition of either ammonium, magnesium or zinc fluorosilϊcate, to form a product usable as a soil release agent.

26. A composition in accordance with Claim 25 wherein the fluorosilicate addition is present in the range of 0.10 to 5.0 percent of the composition.

27. A composition according to Claim I on a powdered absorbent which is selected from the group consisting of sodium bicarbonate, sodium sulphate, sodium borate, sodium tripolyphosphate, a diatomaceous earth or a crumbled or spray dried polymer with high solvent absorbency but which is chemically stable when mixed.

28. A composition in accordance with Claim I wherein the surfactant comprises two or more anionic surfactants chosen from the group consisting of αlkyl, σryl, sodium calcium, magnesium, ammonium, potassium, mono, di or triethanolamine or isopropylamide, sodium olefin sulphonate, sodium alkyl or dialkyl naphthalene sulphonate, alkyl (C , p C . p), sodium, calcium, magnesium, ammonium, or lithium sulphate, and sodium, potassium, calcium or other neutralised dioctyl sulphosuccinate, substituted, sulphonated or half ester of a sulphonated sulphosuccinate derivative, alkyl (C _{ι n}-C , diphenyl

I U 1 6 oxide, sodium, calcium, ammonium and alkanolamide disulphonate, anionic f luorocarbon surfactants.

29. A composition in accordance with Claim 28 wherein from 5.0 to 50.0 percent of the anionic surfactant is substituted by an amphoteric surfactant which on drying in air yields a non-hygroscopic powdered residue.

30. A composition in accordance with Claim I wherein the composition is in aqueous or powdered form.

3 1 . An acaricidal composition substantially as hereinbefore described with reference to Examples I to X