EP1491620A1 - Aerosol composition for spot dry cleaning of fabrics - Google Patents

Aerosol composition for spot dry cleaning of fabrics Download PDF

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Publication number
EP1491620A1
EP1491620A1 EP20030014699 EP03014699A EP1491620A1 EP 1491620 A1 EP1491620 A1 EP 1491620A1 EP 20030014699 EP20030014699 EP 20030014699 EP 03014699 A EP03014699 A EP 03014699A EP 1491620 A1 EP1491620 A1 EP 1491620A1
Authority
EP
European Patent Office
Prior art keywords
aerosol composition
amount
composition
hydrocarbon solvent
present
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP20030014699
Other languages
German (de)
French (fr)
Inventor
Kevan P.R. Dr. Gartland
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SC Johnson and Son Inc
Original Assignee
SC Johnson and Son Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SC Johnson and Son Inc filed Critical SC Johnson and Son Inc
Priority to EP20030014699 priority Critical patent/EP1491620A1/en
Priority to EP04740386A priority patent/EP1639074A1/en
Priority to PCT/EP2004/006988 priority patent/WO2005001017A1/en
Publication of EP1491620A1 publication Critical patent/EP1491620A1/en
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0043For use with aerosol devices
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0013Liquid compositions with insoluble particles in suspension
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50Solvents
    • C11D7/5004Organic solvents
    • C11D7/5027Hydrocarbons
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06LDRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L1/00Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • D06L1/02Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using organic solvents
    • D06L1/04Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using organic solvents combined with specific additives

Definitions

  • This invention relates to a fabric care stain removal preparation deliverable by pressurized aerosol dispenser that utilizes a combination of solvent systems with solid-based absorbent such that the final formula and product is harmless to environment and non-irritating to skin of the consumer.
  • the invention especially relates to a a self-pressurized aerosol composition for spot dry cleaning of fabrics comprising a propellant, a volatile hydrocarbon solvent system for removing stains from the fabrics and a particulate absorbent capable of absorbing stain.
  • 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.
  • aerosol formulations are used so the user can simply spray the composition onto the fabric.
  • 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.
  • 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 dimethyl 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 including propellant.
  • a propellant preferably dimethyl ether (DME)
  • DME dimethyl ether
  • 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 monochlorodifluoromethane 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 fluorinated solvent, unsubstituted aliphatic hydrocarbon, aliphatic alcohol or ketone.
  • the compositions can be used to dry shampoo human hair as well as to spot clean textiles.
  • U.S. Patent No. 3,714,049 (Charle et al.) teaches self-pressurized aerosols composed of a stain removing agent such as a chlorinated hydrocarbon with an isopropanol 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 hydrocarbon or halogenated hydrocarbon where either or both the stain removing agent and the absorbent are microencapsulated.
  • a stain removing agent such as a chlorinated hydrocarbon with an isopropanol diluent or a hydrocarbon
  • a finely divided solid absorbent such as "silicon" powder or talcum powder
  • a propellant such as a saturated lower aliphatic hydrocarbon or halogenated hydrocarbon where either or both the stain removing agent and the absorbent are microencapsulated.
  • 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.
  • a self-pressurized aerosol composition for spot dry cleaning of fabrics
  • the composition containing a combination 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 propane) 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 addition 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 comprising a propellant, a volatile hydrocarbon solvent system for removing stains from a fabric and a particulate absorbent capable of absorbing the stain.
  • the propellant is a blend of liquefied petroleum gases, preferably a blend of liquefied C 3 -C 4 petroleum gases, more preferably a blend of propane, iso-butane and n-butane, especially a butane : propane mixture containing from about 50 to 80, preferably 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 composition;
  • the volatile hydrocarbon solvent system is a mixture of a low molecular weight C 5 -C 7 paraffinic aliphatic hydrocarbon solvent consisting of one or more components, at least one cycloaliphatic C 5 -C 7 hydrocarbon solvent and optionally at least one oxygenated cosolvent;
  • the paraffinic aliphatic hydrocarbon solvent is a blend of aliphatic C 5 -C 7 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
  • 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 preferably 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;
  • 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 C 3 -C 4 liquified petroleum gas, most preferably from about 44 to about 46 wt.%, especially 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 C 5 -C 7 hydrocarbon solvent, most preferably from about 19 to about 20 wt.% of a pentane/heptane/methylcyclohexane (37/52/11) 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
  • the self-pressurized aerosol compositions for spot dry cleaning of woven or nonwoven 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 compositions leave a powder behind which absorbs and removes the stain from the fabric and can then be brushed or vacuumed away from the fabric.
  • the aerosol fabric spot cleaner compositions of the invention not only provide good removal of various oil-based stains or soil, but in addition are formulated so as to avoid the hazard classifications 'IRRITANT' and 'DANGEROUS FOR THE ENVIRONMENT' 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.
  • aerosol compositions of the present invention represent a substantial progress over the prior art aerosol compositions.
  • 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.
  • liquid components other than the propellant are readily made simply by mixing the liquid components other than the propellant 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.
  • a suitable metal aerosol 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 actuator button capable of delivering the desired type or pattern of spray.
  • the liquefied petroleum gas can be added to the composition after the container is sealed by adding it through the valve under pressure.
  • 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 absorbent.
  • 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.
  • 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 compositions 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 invention 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 aerosol container used to dispense the spot dry cleaning compositions of the present invention.
  • cyclopentane Due to its solvent characteristics and less hazardous environmental and human health European Commission hazard classification, cyclopentane presents a significant 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.
  • particulate absorbents are fumed or pyrogenic silica, precipitated silica, surface-treated silica, calcium silicate, calcium carbonate, magnesium 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.
  • 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.
  • fumed or pyrogenic silicas and precipitated silicas are preferred. Fumed or pyrogenic silicas are more preferred where the compositions 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 require 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 hydrocarbons of high volatility and low kinematic viscosity.
  • 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 invention.
  • 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.
  • optional ingredients can be conventional additives such as perfumes, preservatives, 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%, preferably 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 compositions of the present invention. Examples of useful co-solvents are lower alcohols containing 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.
  • Example shows aerosol spot dry cleaning formulations useful in the present invention.
  • the above formulations were prepared by mixing the paraffinic and cycloparaffinic short chain length aliphatic hydrocarbons, isopropanol and fragrance (optional) together 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 10 5 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 composition after shaking well.
  • 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:
  • Example 1 was found to be most equal in performance to the conventional Comparative Example A.
  • Example 1 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 exception 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).

Abstract

A self-pressurized spot dry cleaning composition containing a combination of a propellant, a volatile hydrocarbon solvent blend for removing stains from a fabric and a particulate absorbent capable of absorbing stain. It does not only possess good oil-based stain removal from fabrics such as garments, but in addition is formulated so as to be non-irritant to the consumer and non-dangerous to the environment.

Description

    FIELD OF THE INVENTION
  • This invention relates to a fabric care stain removal preparation deliverable by pressurized aerosol dispenser that utilizes a combination of solvent systems with solid-based absorbent such that the final formula and product is harmless to environment and non-irritating to skin of the consumer. The invention especially relates to a a self-pressurized aerosol composition for spot dry cleaning of fabrics comprising a propellant, a volatile hydrocarbon solvent system for removing stains from the fabrics and a particulate absorbent capable of absorbing stain.
  • 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 dimethyl 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 including 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 monochlorodifluoromethane 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 fluorinated solvent, unsubstituted aliphatic hydrocarbon, aliphatic alcohol or ketone. The compositions can be used to dry shampoo human hair as well as to spot clean textiles.
  • U.S. Patent No. 3,714,049 (Charle et al.) teaches self-pressurized aerosols composed of a stain removing agent such as a chlorinated hydrocarbon with an isopropanol 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 hydrocarbon 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 aerosol composition for spot dry cleaning of fabrics the composition containing a combination 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 propane) 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 addition 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 comprising 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 invention 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, preferably 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 composition;
    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 oxygenated cosolvent;
    the paraffinic aliphatic hydrocarbon solvent is a blend of aliphatic C5-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 cosolvent, if present, is selected from the group consisting of lower alcohols containing 1 to 4 carbon atoms, preferably is isopropanol;
    the cosolvent, 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, pyrogenic 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 µm, preferably from about 10 to about 20 µm, more preferably from about 12 to about 15 µm.
    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 preferably 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.%, especially 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 (37/52/11) 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 cosolvent, 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 substance, 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 particulate 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 nonwoven 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 compositions leave a powder behind which absorbs and removes the stain from the fabric 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 removal of various oil-based stains or soil, but in addition are formulated so as to avoid the hazard classifications 'IRRITANT' and 'DANGEROUS FOR THE ENVIRONMENT' 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 environmental 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 propellant 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 actuator 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 absorbent. 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 compositions 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 invention 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 aerosol 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 significant 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, magnesium 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 compositions 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 require 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 hydrocarbons 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 invention. 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, preservatives, 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%, preferably 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 compositions of the present invention. Examples of useful co-solvents are lower alcohols containing 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 invention 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) together 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 composition 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. Example 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 PROPELLANT 45.0 45.00
    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 A EXAMPLE 1
    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 exception 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.

Claims (23)

  1. A self-pressurised aerosol composition for spot dry cleaning of a fabric comprising:
    a propellant, a volatile hydrocarbon solvent system for removing stains from the fabric and at least one particulate absorbent capable of absorbing stain.
  2. The aerosol composition of claim 1, wherein the propellant is a blend of liquefied C3-C4 petroleum gases, preferably a blend of butane and propane.
  3. The aerosol composition of claim 2, wherein the propellant is a (50-80)/(50-20) mixture, preferably a 70/30 mixture of butane and propane.
  4. The aerosol composition of any of claims 1 to 3, wherein the propellant is present 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 about 45 wt.% of the total composition to give a final internal can pressure of 3.3 - 3.8 x 105 Pascals at 25 °C.
  5. The aerosol composition of any of claims 1 to 4, wherein the volatile hydrocarbon solvent system is a mixture a low molecular weight paraffinic aliphatic C5-C7 hydrocarbon solvent consisting of one or more components, at least one cycloaliphatic C5-C7 hydrocarbon solvent and optionally at least one oxygenated cosolvent.
  6. The aerosol composition of claim 5, wherein the paraffinic aliphatic C5-C7 hydrocarbon solvent is a blend of pentane, heptane and methyl-cyclohexane.
  7. The aerosol composition of claim 6, wherein pentane, heptane and methyl-cyclohexane are present in a weight ratio of from (30-40) : (45-55) : (10-15), preferably in a weight ratio of 37 : 52 : 11.
  8. The aerosol composition of any of claims 1 to 7, wherein the paraffinic aliphatic C5-C7 hydrocarbon solvent is present in an amount of from about 5 to about 20 wt.%, preferably from about 10 to about 20 wt.%, more preferably in an amount of about 19.5 wt.% of the total composition.
  9. The aerosol composition of any of claims 1 to 8, wherein the cycloaliphatic hydrocarbon solvent is at least one cycloaliphatic C5-C7 hydrocarbon, preferably cyclopentane.
  10. The aerosol composition of any of claims 1 to 9, wherein the cycloaliphatic 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.% of the total composition.
  11. The aerosol composition of any of claims 5 to 10, wherein the oxygenated cosolvent, if present, is selected from the group consisting of lower alcohols containing 1 to 4 carbon atoms, preferably is isopropanol.
  12. The aerosol composition of any of claims 5 to 11, wherein the cosolvent is present 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.% of the total composition.
  13. The aerosol composition of any of claims 1 to 12, wherein the particulate absorbent is selected from the group consisting of fumed silicas, pyrogenic silicas, precipitated silicas, surface-treated silicas, calcium silicate, calcium carbonate, magnesium silicate, starch, clays, talc and magnesium oxide and mixtures thereof.
  14. The aerosol composition of any of claims 1 to 13, wherein the particulate absorbent has an average particle size of no more than about 5 to about 30 µm, preferably from about 10 to about 20 µm, more preferably from about 12 to about 15 µm.
  15. The aerosol composition of any of claims 1 to 14, wherein the particulate absorbent is present in an amount of from about 1 to about 20 wt.%, preferably from about 5 to about 12 wt.%, more preferably in an amount of about 7 wt.% of the total composition.
  16. The aerosol composition of any of claims 1 to 15, which additionally comprises at least one electrostatic charge limiting substance.
  17. The aerosol composition of claim 16, wherein the electrostatic charge limiting substance is oleyl imidazoline.
  18. The aerosol composition of any of claims 16 or 17, wherein the electrostatic charge limiting substance is present in an amount of from up to about 2 wt.%, preferably from about 0.1 to about 2.0 wt.%, more preferably in an amount of about 0.1 to about 0.5 wt.% of the total composition.
  19. The aerosol composition of any of claims 1 to 18, which additionally comprises at least one perfume.
  20. The aerosol composition of claim 19, wherein the perfume is present in an amount of from up to about 1.0 wt.%, preferably from about 0.01 to about 1.0 wt.%, more preferably in an amount of about 0.05 wt.% of the total composition.
  21. The aerosol composition of any of claims 1 to 20, containing
    from about 40 to about 60 wt.% of the liquefied C3-C4 petroleum gas,
    from about 5 to about 20 wt.% of the paraffinic aliphatic C5-C7 hydrocarbon solvent,
    from about 15 to about 35 wt.% of the cycloaliphatic C5-C7 hydrocarbon solvent,
    from about 1 to about 10 wt.% of the co-solvent,
    from about 0.1 to about 2.0 wt.% of the electrostatic charge limiting substance,
    from about 0.05 to about 1 wt.% of a perfume and
    from about 1 to about 20 by weight of the particulate absorbent.
  22. The aerosol composition of any of claims 1 to 21, containing
    from about 45 to about 55 wt.% of the liquefied C3-C4 petroleum gas,
    from about 15 to about 20 wt.% of the paraffinic aliphatic C5-C7 hydrocarbon solvent,
    from about 20 to about 30 wt.% of the cycloaliphatic C5-C7 hydrocarbon solvent,
    from about 6 to about 8 wt.% of the co-solvent,
    from about 0.1 to about 0.5 wt.% of the electrostatic charge limiting substance,
    from about 0.05 to about 10 wt.% of a perfume and
    from about 5 to about 12 wt.% of the particulate absorbent.
  23. The aerosol composition of any of claims 1 to 22, containing
    from about 44 to about 46 wt.% of a butane/propane (70/30) mixture,
    from about 19 to about 20 wt.% of a pentane/heptane/methylcyclohexane (37/52/11) mixture,
    from about 22 to about 25 wt.% of cyclopentane,
    from about 0.1 to about 5 wt.% of isopropanol,
    from about 0.1 to about 0.5 wt.% of oleyl imidazoline,
    from about 0.01 to about 0.01 of a perfume, and
    from 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.
EP20030014699 2003-06-27 2003-06-27 Aerosol composition for spot dry cleaning of fabrics Withdrawn EP1491620A1 (en)

Priority Applications (3)

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EP20030014699 EP1491620A1 (en) 2003-06-27 2003-06-27 Aerosol composition for spot dry cleaning of fabrics
EP04740386A EP1639074A1 (en) 2003-06-27 2004-06-28 Aerosol composition for spot dry cleaning of fabrics
PCT/EP2004/006988 WO2005001017A1 (en) 2003-06-27 2004-06-28 Aerosol composition for spot dry cleaning of fabrics

Applications Claiming Priority (1)

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EP20030014699 EP1491620A1 (en) 2003-06-27 2003-06-27 Aerosol composition for spot dry cleaning of fabrics

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2169126A1 (en) 2008-09-29 2010-03-31 Geberit International AG Pneumatic activation device

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015157240A1 (en) * 2014-04-11 2015-10-15 Honeywell International Inc. Solvent vapor phase degreasing and defluxing compositions, methods, devices and systems

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3714049A (en) * 1969-02-04 1973-01-30 Oreal Aerosol stain-removing composition
SU1594232A1 (en) * 1987-07-20 1990-09-23 Омский технологический институт бытового обслуживания Composition for removing hydrophobic dirt
JPH0649494A (en) * 1991-03-01 1994-02-22 Nippon Baazu Kk Detergent composition
EP0890670A2 (en) * 1997-07-11 1999-01-13 S.C. Johnson & Son, Inc. Spot removal compositions for use in aerosol dispensers
WO2001030957A1 (en) * 1999-10-25 2001-05-03 Cps - Chemical Products And Services A/S Textile stain remover composition and a method for removing stains

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3714049A (en) * 1969-02-04 1973-01-30 Oreal Aerosol stain-removing composition
SU1594232A1 (en) * 1987-07-20 1990-09-23 Омский технологический институт бытового обслуживания Composition for removing hydrophobic dirt
JPH0649494A (en) * 1991-03-01 1994-02-22 Nippon Baazu Kk Detergent composition
EP0890670A2 (en) * 1997-07-11 1999-01-13 S.C. Johnson & Son, Inc. Spot removal compositions for use in aerosol dispensers
WO2001030957A1 (en) * 1999-10-25 2001-05-03 Cps - Chemical Products And Services A/S Textile stain remover composition and a method for removing stains

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 199121, Derwent World Patents Index; Class A97, AN 1991-155243, XP002263082 *
DATABASE WPI Section Ch Week 199412, Derwent World Patents Index; Class E15, AN 1994-098087, XP002263083 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2169126A1 (en) 2008-09-29 2010-03-31 Geberit International AG Pneumatic activation device

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WO2005001017A1 (en) 2005-01-06

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