BACKGROUND ART Spot remover compositions for use on fabric materials such as clothing, carpets and upholstery have existed for many years (see for example, British Patent No. 1,397, 475 (Loudas)). These types of products are used on relatively small areas of fabrics to remove soil and stains due to food or oily materials. Water-based stains require polar solvents while oily soil or stains require relatively non-polar solvents for proper removal. These solvents are often difficult to combine into a homogeneous composition. For convenience, aerosol formulations are used so the user can simply spray the composition onto the fabric. Preferably, the compositions can remove the stain without appreciably wetting the fabric which can spread the stain out rather than removing it. Drying time is often critical for garment spot removal because the stain is often only noticed at the time the garment is to be worn.

"Dry"cleaning compositions are also important where the garment is sensitive to water and must be commercially dry cleaned rather than simply laundered in water.

In addition to long drying times, significant amounts of water to remove stains can cause shrinkage and warping of carpeting and also may promote mould growth.

Thus, it would be desirable to have an aerosol composition that can spot dry clean fabrics without leaving the fabric wet to a significant degree.

Many attempts to provide self-pressurized aerosol spot dry cleaning compositions for fabrics have been made. The flammability of such compositions is of concern since the hydrocarbon solvents that are useful in removing oil-based stains tend to be flammable as are the lower alkyl hydrocarbon propellants used in conventional self- pressurised aerosol spray formulations.

European Patent No. 0 890 670 A2 (de Jager) teaches a self-pressurized aerosol composition for spot dry cleaning of a textile comprising a propellant [preferably dime- thyl ether (DME)]., a volatile hydrocarbon solvent for removing stains, a particulate absorbent material capable of absorbing a stain from a textile on to which it is sprayed, and a water-in-oil microemulsion in an amount of from 5% to 50% by weight of the total composition including propellant, said aerosol composition containing from 2.5% to 25% by weight of water based on weight of the total composition includ- ing propellant.

U. S. Patent No. 3, 161, 460 (Huber) teaches a self-pressurized aerosol degreasing agent composed of a solvent for fat and grease like difluoromethane or monochloro- difluoromethane and a finely divided solid absorbent such as talcum powder, silica gel or siliceous earth One solvent must be a low boiling solvent such as a fluori- nated solvent, unsubstituted aliphatic hydrocarbon, aliphatic alcohol or ketone. The compositions can be used to dry shampoo human hair as well as to spot clean tex- tiles.

U. S. Patent No. 3,714, 049 (Charte et al.) teaches self-pressurized aerosols com- posed of a stain removing agent such as a chlorinated hydrocarbon with an isopro- panol diluent or a hydrocarbon, a finely divided solid absorbent such as"silicon" powder or talcum powder, and a propellant such as a saturated lower aliphatic hy- drocarbon or halogenated hydrocarbon where either or both the stain removing agent and the absorbent are microencapsulated.

However, all these aerosols of the prior art are disadvantageous in that: 1. they may contain significant quantities of water which serves to prolong the drying time and may even damage or mark certain fabric types 2. the may contain chlorinated or fluorinated solvents which are not environmentally acceptable and 3. their level of performance for removing certain stains from fabrics is insufficient.

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to provide an aerosol fabric spot dry cleaner composition which not only provides good removal of various oil-based stains or soil, but in addition is formulated so as to avoid any hazard for the environment and for humans utilizing such cleaner compositions in a household application.

This object is achieved according to the present invention by a self-pressurized aero- sol composition for spot dry cleaning of fabrics the composition containing a combi- nation of low molecular weight aliphatic and cycloaliphatic hydrocarbons; optionally a co-solvent, an emulsifier, an aesthetic amount of perfume, and an absorbent such as silica powder and at least one liquified petroleum gas (isobutane, n-butane and pro- pane) as the propellant to provide an aerosol fabric spot dry cleaner composition which not only provides good removal of various oil-based stains or soil, but in addi- tion is formulated so as to avoid the hazard classifications'IRRITANT' (St Andrews Crooss symbol) and'DANGEROUS FOR THE ENVIRONMENT' (Dead Fish Dead Tree symbol) under the EU Dangerous Preparations Directive (1999/45/EC), which hazard symbols on a household consumer product could potentially adversely affect consumer purchase intent and therefore sales volumes and market share.

The subject-matter of the present invention is according to a first aspect a self- pressurized aerosol composition for the spot dry cleaning of a fabric mainly compris- ing a propellant, a volatile hydrocarbon solvent system for removing stains from a fabric and a particulate absorbent capable of absorbing the stain.

According to preferred embodiments of the aerosol compositions of the present in- vention as defined above the propellant is a blend of liquefied petroleum gases, preferably a blend of liquefied C3-C4 petroleum gases, more preferably a blend of propane, iso-butane and n- butane, especially a butane: propane mixture containing from about 50 to 80, pref- erably 70 wt. % of butane and from about 50 to 20, preferably 30 wt. % of propane.

The propellant is present in the aerosol composition of the present invention in an amount of from about 40 to about 60 wt. %, preferably from about 45 to about 55 wt. %, more preferably in an amount of from about 44 to 46 wt. % of the total composi- tion; the volatile hydrocarbon solvent system is a mixture of a low molecular weight C5-C7 paraffinic aliphatic hydrocarbon solvent consisting of one or more components, at least one cycloaliphatic C5-C7 hydrocarbon solvent and optionally at least one oxy- genated solvent ; the paraffinic aliphatic hydrocarbon solvent is a blend of aliphatic 5-C7 hydrocarbon solvents, preferably a blend of pentane, hexane, heptane and methyl-cyclohexane, more preferably a blend of pentane, heptane and methyl-cyclohexane in a weight ratio of about (30 to 40): (45 to 55): (10 to 15), in particularly in a weight ratio of about 37: 52: 11; the paraffinic aliphatic C5-C7 hydrocarbon solvent is present in an amount of from about 5 to about 20 wt. %, more preferably of from about 10 to about 20 wt. %, most preferably in an amount of about 19.5 wt. %, based on the total composition; the cycloaliphatic hydrocarbon solvent is a cycloaliphatic C5-C7 hydrocarbon solvent, preferably cyclopentane ; the cycloaliphatic C5-C7 hydrocarbon solvent is present in an amount of from about 15 to about 35 wt. %, preferably from about 20 to about 30 wt. %, more preferably in an amount of about 25 wt. %, based on the total composition; the oxygenated solvent, if present, is selected from the group consisting of lower alcohols containing 1 to 4 carbon atoms, preferably is isopropanol ; the solvent, if present, is used in an amount of up to about 10 wt. %, preferably from about 1 to about 5 wt. %, more preferably in an amount of about 3 wt. %, based on the total composition; the particulate absorbent is selected from the group consisting of fumed silicas, pyro- genic silicas, precipitated silicas, surface-treated silicas, calcium silicate, calcium carbonate, magnesium silicate, clays, talc and magnesium oxide ; the particulate absorbent has an average particle size of no more than about 5 to about 30 um, preferably from about 10 to about 20 um, more preferably from about 12 to about 15 um. the particulate absorbent is present in an amount of from about 1 to about 20 wt. %, preferably in an amount of from about 5 to about 12 wt. %, more preferably in an amount of about 7 wt. %, based on the total composition; the aerosol composition of the present invention additionally may contain at least one electrostatic charge limiting substance, preferably oleyl imidazoline, which preferably, if present, is present in an amount of from up to about 2 wt. %, more preferably of about 0.1 to about 2.0 wt. %, most preferably of about 0.1 to about 0.5 wt. %, based on the total composition; the aerosol composition of the present invention may additionally contain at least one perfume, if present, preferably in an amount of from up to about 1.0 wt. %, more pref- erably from about 0.01 to about 1.0 wt. % and most preferably in an amount of about 0.05 wt. %, based on the total composition; According to further aspects the subject-matter of the present invention is an aerosol composition as defined above comprising from about 40 to about 60 wt. %, preferably from about 45 to about 55 wt. % of the C3- C4 liquified petroleum gas, most preferably from about 44 to about 46 wt. %, espe- cially about 45 wt. % of a butane/propane (70/30) mixture; from about 5 to about 20 wt. %, preferably from about 15 to about 20 wt. % of the paraffinic aliphatic C5-C7 hydrocarbon solvent, most preferably from about 19 to about 20 wt. % of a pentane/heptane/methylcyclohexane (37152111) mixture; from about 15 to about 35 wt. %, preferably from about 20 to about 30 wt. % of the cycloaliphatic hydrocarbon solvent, more preferably from about 22 to about 25 wt. %, of cyclopentane ; from about 0.1 to about 10 wt. %, preferably from about 1 to about 8 wt. % of the solvent, most preferably from about 0.1 to about 3 wt. %, of isopropanol ; from about 0.1 to about 2.0 wt. %, preferably from about 0.1 to about 1.0 wt. %, more preferably from about 0.1 to about 0.5 wt. % of the electrostatic charge limiting sub- stance, most preferably about 0.35 wt. % of oleyl imidazoline ; from about 0.05 to about 1.0 wt. %, preferably from about 0.01 to about 0.1 wt. % of a perfume, and from about 1 to about 20 wt. %, preferably from about 5 to about 12 wt. % of the par- ticulate absorbent, most preferably about 5 to about 8 wt. % of a particulate absorbent selected from the group consisting of fumed silica, pyrogenic silica, precipitated silica and surface-treated silica.

The self-pressurized aerosol compositions for spot dry cleaning of woven or non- woven fabrics and textiles of the present invention as defined above are suitable for removing stains from garments such as dresses, suits, ties and shirts as well as for carpets, rugs and upholstery and pile fabrics that are cleaned in place. These com- positions leave a powder behind which absorbs and removes the stain from the fab- ric and can then be brushed or vacuumed away from the fabric. Furthermore, the aerosol fabric spot cleaner compositions of the invention not only provide good re- moval of various oil-based stains or soil, but in addition are formulated so as to avoid the hazard classifications'IRRITANT'and'DANGEROUS FOR THE ENVIRON- MENT'under the EU Dangerous Preparations Directive (1999/45/EC), which means that they are formulated in such manner that they are not harmful by inhalation, by ingestion and by skin contact and do not irritate the skin of consumers and therefore are especially suitable for household application.

Due to their improved stain removal characteristics and less hazardous environ- mental and European Commission human health hazard classification the aerosol compositions of the present invention represent a substantial progress over the prior art aerosol compositions.

BEST MODE FOR CARRYING OUT THE INVENTION The self-pressurized aerosol spot dry cleaning compositions of the present invention are low viscosity liquids which are typically less than about 300 centipoise (0.300 pascal. seconds) in viscosity at 25 °C and are suitable for delivery by spraying.

They are readily made simply by mixing the liquid components other than the propel- lant together at room temperature (25 °C) followed by the addition of the absorbent with vigorous stirring or with the application of shear by means of a homogeniser to enhance dispersion. This mixture is then added to a suitable metal aerosol container followed by the liquefied petroleum gas propellant. Preferably a conventional metal container such as a tin-plated steel container is used. The container is sealed with a conventional pressurized aerosol valve and fitted with a suitable aerosol spray actua- tor button capable of delivering the desired type or pattern of spray. Optionally, the liquefied petroleum gas can be added to the composition after the container is sealed by adding it through the valve under pressure. Those of ordinary skill in the art can select appropriate aerosol dispensing containers and components for use in spraying the compositions of the present invention. Examples of known containers can be seen from an examination of U. S. Patent Nos. 3,207, 386 and 4,322, 037 noted above.

The self-pressurized spot dry cleaning compositions of the present invention may be used by shaking the container to ensure good dispersion of the absorbent followed by spraying a quantity of the composition at room temperature onto a stained area of the fabric and allowing it to dry. The absorbent cooperates with the solvent system so that after the solvents dissolve the stain, the solvents carry the stain into the absorb- ent. Upon drying, a light powder of absorbent containing the absorbed stain is left on the fabric which is then brushed or vacuumed away from the fabric to leave a clean fabric surface behind.

Thus, the self-pressurized spot dry cleaning compositions of the present invention can be used in the same manner as have other conventional spot dry cleaning com- positions to clean away stains on fabrics such as garments, carpets, upholstery and pile fabrics while leaving the fabric relatively dry to the touch so that the fabric item can be used rather quickly after the cleaning operation is finished.

The propellant used in the self-pressurised aerosol compositions of the present in- vention is liquefied petroleum gas. If the gases are exhausted by misuse, then the contents of the container may not be fully dispensed from the container. From about 20% to about 70%, preferably from about 40% to 60%, and most preferably, from about 45% to 55%, by weight of the total composition is liquefied petroleum gas. A sufficient amount of liquefied petroleum gas is used to adequately pressurize the ae- rosol container used to dispense the spot dry cleaning compositions of the present invention.

Due to its solvent characteristics and less hazardous environmental and human health European Commission hazard classification, cyclopentane presents a signifi- cant advantage as a solvent in the compositions of the present invention.

Another required component of the present invention is from about 1% to about 20%, preferably from about 5% to 12%, and most preferably, from about 6% to 8%, by weight of the total composition of at least one particulate absorbent capable of absorbing a stain from the fabric onto which the composition is sprayed and has an average particles size which permits it to be sprayed from a self-pressurised aerosol dispenser. Examples of such particulate absorbents are fumed or pyrogenic silica, precipitated silica, surface-treated silica, calcium silicate, calcium carbonate, ma- gnesium silicate, starch, clays, talc, magnesium oxide, and similar such materials.

The mean average particle size of such absorbents should be such as to permit spraying from a self-pressurised aerosol dispenser. As described in U. S. Patent No.

3,161, 460, the mean average particle size should be less than about 100 microns, more preferably less than about 50 microns, and most preferably, no more than about 5 to 30 microns. Presently, fumed or pyrogenic silicas and precipitated silicas are preferred. Fumed or pyrogenic silicas are more preferred where the compositi- ons are to be packaged in tin-plated steel aerosol dispenser containers because precipitated silicas tend to contain trace amounts of salts such as chlorides and sulphates which create corrosion problems. Talc, calcium silicate and clays tend to settle to the bottom of the containers after the compositions are prepared and requi- re a greater amount of shaking to redisperse them than do compositions made using the silicas as absorbents.

The self-pressurised aerosol compositions of the present invention principally rely on the solvent power of paraffinic and cycloparaffinic short chain length aliphatic hydro- carbons of high volatility and low kinematic viscosity.

Optionally, other organic solvents can be used in amounts of no more than about 10% and more preferably, no more than about 5% by weight of the total composition to improve the stain removal characteristics of the compositions of the present inven- tion. Hydrocarbon solvents which are volatile at 250 °C such as pentane, hexane, heptane, methyl-cyclohexane, aliphatic naphthas and similar such solvents can be included to improve the effectiveness of the compositions of the present invention against oil-based stains.

Other optional ingredients can be conventional additives such as perfumes, preser- vatives, and the like which do not adversely affect the fabrics to be cleaned. These optional ingredients are usually included in minor amounts which do not exceed about 5% by weight of the total composition and more preferably are no more than about 1% by weight of the total composition.

Another optional component of the present invention is from up to about 15%, pre- ferably from about 1% to 5%, and most preferably, from about 2% to 4%, by weight of the total composition of at least one co-solvent for the aliphatic and cycloaliphatic hydrocarbon solvents. The co-solvent serves several purposes. One is to permit the formation of homogeneous solutions of the liquid ingredients used in the compositi- ons of the present invention. Examples of useful co-solvents are lower alcohols con- taining preferably 1 to about 4 carbon atoms such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and isobutanol. Methanol is less desirable in a consumer product due to its toxicity. Isopropanol is a presently preferred co-solvent.

EXAMPLES The following Examples are provided to show various aspects of the present inven- tion without departing from the scope and spirit of the invention. Unless otherwise indicated, all parts and percentages used are by weight.

The following Example shows aerosol spot dry cleaning formulations useful in the present invention.

Example 1 (present invention) The above formulations were prepared by mixing the paraffinic and cycloparaffinic short chain length aliphatic hydrocarbons, isopropanol and fragrance (optional) to- gether in that order with mixing. To this mixture was then added the electrostatic charge limiting substance. The mixture was then mixed thoroughly for some minutes until the electrostatic charge limiting substance had dissolved. To this mixture was then added the solid silica. The mixture was then mixed thoroughly with a rotor/stator mixer to homogenize the mixture and to get a thorough dispersion. This mixture was added to a conventional tin-plated steel aerosol container. Each container was fitted with a conventional aerosol valve which was crimped onto the neck of the container and then the liquefied petroleum gas was added to the container through the valve under pressure to pressurize the container to give a final internal can pressure of from 3.3 to 3.8 x 105 Pascals at 25 °C. A conventional actuator button was then added to the valve stem. The container had to be shaken to redisperse the silica powder before spraying the composition onto a fabric. Each formulation was a single phase homogeneous composition with the silica powder suspended within the com- position after shaking well.

Comparative Example A A sufficient amount of each composition was sprayed onto a fabric stain to saturate the stained area. It was then allowed to dry to a white powder before the powder was removed with a brush. The stains tested were of the greasy type on cotton drill fabrics and then on swatches with fresh stains applied. The specific stains tested were: Ink Lipstick Make-up Italian Dressing Ragu (tomato-based pasta sauce) The performance of each composition was noted for application properties, drying time, stain removal and any other effects such as'haloing'of the original stain. Ex- ample 1 was found to be most equal in performance to the conventional Comparative Example A.

Comparing Example 1 (present invention) with conventional Comparative Example A In a test on blue-dyed polyester/cotton fabric, there was no noticeable difference between any of the compositions tested after the first application of the composition in terms of the residue remaining on the fabric. Formula Comparative Example A Example 1 BUTANE/PROPANE 45. 0 45.00 PROPELLANT PENTANE/HEPTANE BLEND 44. 72 19. 42 SILICA POWDER 7. 2 9. 0 ISOPROPANOL 2. 8 2. 0 OLEYL IMIDAZOLINE 0. 3 0. 5 FRAGRANCE 0.06 0.06 CYCLOPENTANE 0. 0 24. 0 The table below shows the Delta E values for each stain. The lower the value, then the closer the stain is to being completely removed. Readings were taken with a Hunter Miniscan Colorimeter at 25 °C and at standard pressure: STAIN COMPARATIVE EXAMPLE 1 EXAMPLE A Ink 1. 40 1. 19 Lipstick 3. 32 2. 04 Make-up 18. 58 15. 34 Italian Dressing 9. 71 8. 20 Ragu 6. 41 5. 68 For stain removal testing there was a substanial difference in level of performance between Example 1 and Comparative Example A. The readings indicate differences for each formula on different stains of from more than about 10 % up to about 60 %.

Example 1 is further superior to Comparative Example A as key changes have been made to the formula such that the formulated product will not attract (with the excep- tion of the Flame Symbol most commonly seen on self-pressurized aerosol products in the European Union) two additional symbols, i. e. the St Andrew's Cross (representing the hazard classifications : Harmful & Irritant) and the Dead Fish Dead Tree symbol (representing the hazard classification: Dangerous for the Environment).

Those skilled in the art will recognize that the present invention is capable of many modifications and variations without departing from the scope thereof. Accordingly, the detailed description and examples set forth above are meant to be illustrative only and are not intended to limit, in any manner, the scope of the present invention as set forth in the appended claims.