EP1062903A1 - Méthode de nettoyage de tapis utilisant un gant - Google Patents
Méthode de nettoyage de tapis utilisant un gant Download PDFInfo
- Publication number
- EP1062903A1 EP1062903A1 EP99870118A EP99870118A EP1062903A1 EP 1062903 A1 EP1062903 A1 EP 1062903A1 EP 99870118 A EP99870118 A EP 99870118A EP 99870118 A EP99870118 A EP 99870118A EP 1062903 A1 EP1062903 A1 EP 1062903A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- carpet
- cleaning
- glove
- layer
- group
- 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.)
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Classifications
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
- A47L13/00—Implements for cleaning floors, carpets, furniture, walls, or wall coverings
- A47L13/10—Scrubbing; Scouring; Cleaning; Polishing
- A47L13/16—Cloths; Pads; Sponges
- A47L13/18—Gloves; Glove-like cloths
- A47L13/19—Gloves; Glove-like cloths containing cleaning agents
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- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
- A47L13/00—Implements for cleaning floors, carpets, furniture, walls, or wall coverings
- A47L13/10—Scrubbing; Scouring; Cleaning; Polishing
- A47L13/16—Cloths; Pads; Sponges
- A47L13/18—Gloves; Glove-like cloths
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
- A47L25/00—Domestic cleaning devices not provided for in other groups of this subclass
- A47L25/08—Pads or the like for cleaning clothes
Definitions
- the present invention relates to a process of cleaning a carpet with a liquid carpet cleaning composition using a glove. More particularly, the present invention relates to a process of cleaning a carpet comprising the steps of applying a liquid carpet cleaning composition onto the carpet and contacting the carpet with a glove comprising at least two layers.
- Carpets produced from synthetic or natural fibers and mixtures thereof are commonly used in residential and commercial applications as a floor covering.
- fibers can be used in making carpets such as polyamide fibers, polyester fibers as well as wool, cotton or even silk in the case of rugs.
- carpets irrespective of whether they are made from natural or synthetic fibers are all prone to soiling and staining when contacted with many household items.
- Food, grease, oils, beverages in particular such as coffee, tea and soft drinks especially those containing acidic dyes can cause unsightly, often dark stains on carpets.
- fibers may become soiled as a result of dirt particles, clay, dust, i.e., particulate soils in general, coming into contact with and adhering to the fibers of the carpet.
- These stains and soils often appear in the form of localized spots ("spot stains”) and tend to accumulate particularly in the so called "high traffic areas" such as near doors as a result of intensive use of the carpets in such areas.
- Liquid compositions for treating carpets are already known in the art. For example as disclosed in EP-A-0 629 694.
- compositions are not fully satisfactory from a consumer viewpoint.
- the objective of the present invention is to provide a process of cleaning a carpet which provides cleaning performance benefits on various types of spot stains including particulate spot stains, greasy spot stains, bleachable spot stains and/or enzymatic spot stains.
- An advantage of the process of cleaning a carpet according to the present invention is that said process provides an easy and fast way for a user to clean spot stains on a carpet, while providing excellent overall cleaning performance. More advantageously, the process of cleaning carpets according to the present invention provides excellent cleaning performance, when used to clean localized carpet stains, i.e., spot stains.
- Another advantage of the present invention is that said process allows the absorption from the carpet of the liquid cleaning composition including emulsified dirt as well as excess liquid cleaning composition resulting in prevention of carpet resoiling and reduction of drying time.
- the process of the present invention allows to protect the hands of a user performing said process from the liquid cleaning composition that can be irritant to the user's skin.
- a further advantage of the present invention is that the process of cleaning carpets herein is applicable to all carpet types, especially delicate natural fibers.
- the present invention is also suitable to be used to clean hard wearing textiles and fabrics, e.g., upholstery, rugs, curtains.
- compositions used in the present process are safe to all known carpet dyes, even well known particularly sensitive natural dyes.
- US 4,980,943 discloses a cleaning glove which includes a glove base having a side to which there is attached a primary layer of a tufted blended yarn tufted to the glove base and one or more fibrous bristle portions or strips.
- said primary layer is not capable of capillarity.
- CH 682207 discloses a dish washing glove consisting essentially of a sponge material. However, no glove having an impermeable second layer as well as no carpet cleaning application for said dish washing glove is disclosed therein.
- WO 94/24636 discloses a jacket consisting essentially of spongy cloth used for cleaning a carpet. However, no impermeable layer is disclosed therein.
- EP-A-0 753 280 discloses a hard surface cleaning glove. However, no glove having an impermeable second layer as well as no carpet cleaning application for said hard surface cleaning glove is disclosed therein.
- the present invention encompasses a process comprising the steps of applying a liquid carpet cleaning composition onto a carpet and contacting said carpet with a glove comprising at least two layers; the first layer being capable of capillarity and a second layer which is impermeable to said carpet cleaning composition wherein the second layer is located between the first layer and the cavity formed by the glove.
- said liquid carpet cleaning composition comprises an ingredient selected from the group consisting of a peroxygen bleach, a surfactant, a volatile organic compound, an anti-resoiling agent, and a mixture thereof.
- the present invention encompasses a process of cleaning a carpet, said process comprising the steps of applying a liquid carpet cleaning composition onto the carpet and contacting the carpet with a glove as described herein.
- said cleaning composition is directly applied onto said carpet prior to contacting said carpet with said glove, applied onto said glove prior to contacting said carpet with said glove and/or applied onto said glove at the time of manufacture.
- said process comprises the steps of contacting parts of the carpet, more preferably soiled parts of the carpet, more preferably spot stains on the carpet, with said composition
- said process after contacting said carpet with said glove, further comprises the step of imparting mechanical action to the carpet using said glove.
- mechanical action it is meant herein, agitation of the glove on the carpet, as for example rubbing the carpet using the glove.
- said process additionally comprises the step of leaving said composition to substantially dry on the carpet. More preferably said process of cleaning a carpet further comprises the step of removing said composition, even more preferably said process of cleaning a carpet further comprises the step of removing said composition in combination with soil particles.
- a liquid composition according to the present invention is applied onto the carpet and/or onto the glove prior to contacting said carpet with said glove by using a dispensing device, preferably a spray dispenser.
- Said spray dispenser is preferably a container that has at least one aperture through which the composition is dispensed to produce a spray of droplets.
- Such a spray dispenser may comprise a means for delivering the composition by a pump ("pump spray dispenser") or may be operated by any source of pressurised gas such as an aerosol-can or a pressurizer. Pump spray dispensers may be manually operated or electrically operated. Said spray dispensers are particularly preferable if a high amount of product has to be applied onto heavily stained areas of the carpet as they facilitate the ease of use by the consumer. Said spray dispensers ensure that a high amount of product is applied onto said heavily stained areas of the carpet.
- Preferred spray dispensers herein are manually or electrically operated pump spray dispensers.
- Typical manually operated pump spray dispensers include push button operated or trigger operated pump spray dispenser.
- a preferred spray dispenser herein is a container wherein the means for delivering the composition comprises an electrically driven pump and a spray arm. Said spray arm is either extended or extendible and has at least one aperture so that in operation, the composition is pumped by said electrically driven pump from the container, through the spray arm to the aperture from which it is dispensed. It is preferred that the spray arm communicates with the container by means of a flexible connector.
- the spray arm may have at least one aperture located along its length. The spray arm makes it easier to control where the composition is sprayed, thereby increasing the accuracy with which the composition is applied.
- the electrically driven pump may be, for example, a gear pump, an impeller pump, a piston pump, a screw pump, a peristaltic pump, a diaphragm pump, or any other miniature pump.
- the electrically driven pump for use herein is a gear pump with a typical speed between 6000 rpm and 12000 rpm.
- the electrically driven pump is driven by a means which typically produces a torque of between 1 and 20 mN.m such as an electric motor.
- the electric motor must in turn be provided with a power source.
- the power source may be either mains electricity (optionally via transformer), or it may be a throw-away battery or rechargeable battery.
- the spray arm may be rigidly extended. However such a spray arm can be difficult to store, and the spray arm is preferably extensible either by means of telescopic or foldable configuration.
- compositions for the cleaning of carpets according to the present invention applied will depend on the severity of the stain or soil. In the case of stubborn stains more than one application may be required to ensure complete removal of the stain.
- the area to be cleaned by applying the compositions according to the present invention may be of any size. Indeed, parts of the carpets, a complete section and/or the whole carpet may be treated with the composition for treating of a carpet according to the present invention.
- the composition applied to the carpet is left to substantially dry.
- the composition is left to dry on the carpet for less than 2 hours, preferably less than 1 hour, more preferably less than 40 minutes, even more preferably from 1 to 30 minutes and most preferably from 1 to 20 minutes.
- the step of leaving the composition to dry onto the carpet can either be an “active drying step” or a “passive drying step”.
- active drying step it is meant herein, performing an additional action to facilitate the evaporation of the volatile ingredients of the liquid composition as disclosed herein, preferably by heating the carpet and/or the liquid composition applied thereon, preferably heating by means of application of hot air, infrared radiation and the like.
- passive drying step it is meant herein, evaporation of the volatile ingredients of the liquid composition as disclosed herein without performing further action.
- substantially dry it is meant herein the stage where at least 40%, preferably at least 60% of the initial amount of composition dispensed onto the carpet is lost due to evaporation.
- normal temperature conditions it is meant herein, from 15° C to 25° C, preferably from 20° C to 25° C.
- normal humidity conditions it is meant herein, from 40 %RH (%-relative humidity) to 80 %RH, preferably from 50 %RH to 65 %RH.
- said composition may be left to substantially dry until said composition combined with dirt forms substantially dry residues.
- said composition more preferably said substantially dry residues, are then removed from the carpet.
- said substantially dry residues are removed mechanically, as for example by beating, sweeping or brushing, and/or by vacuum cleaning. This may be carried out with the help of any commercially available vacuum cleaners like for instance a standard Hoover® 1300W vacuuming machine.
- the process herein may be used for the removal of stains and soils from carpets or hard wearing textiles and fabrics, e.g., upholstery rugs, curtains.
- the process according to the present invention may be used to hygienise, disinfect and/or exterminate microinsects from carpets or hard wearing textiles and fabrics, e.g., upholstery, rugs, curtains.
- the process according to the present invention requires that a carpet to be cleaned is contacted with a glove.
- glove it is meant herein, a pocket, pouch or mitt having an envelope-type configuration and/or a body intended to be worn on a user's hand and/or over a mechanical device, as for example a brush, broom or the like.
- Said glove may have individual pockets for each finger of the user's hand or have pockets for two or more fingers.
- said glove has an opening for the user's hand or a mechanical device.
- said glove has a basic rectangular shape, preferably with rounded corners, with an opening for the user's hand on one of the short sides.
- said glove has a circular shape with an opening for the user's hand.
- said glove has at least two individual pockets, preferably five individual pockets, for the fingers of a user's hand and an opening for the user's hand.
- Said glove comprises at least two layers, the first layer being capable of capillarity and a second layer impermeable to said carpet cleaning composition wherein the second layer is located between the first layer and the cavity formed by the glove.
- cavity formed by the glove it is meant herein, the inner space provided by the glove's envelope shape to fit a user's hand and/or a mechanical device, as for example a brush, broom or the like.
- capillarity it is meant herein, that the first layer of said glove is capable of the phenomenon commonly known as capillarity.
- This force exerted on said liquid due to the capillarity has to be higher than the sum of other forces acting on said liquid, in order that the liquid be transferred, preferably from the carpet, into the first layer.
- Other forces acting on said liquid may be, for example, gravity force, electrostatic forces and/or capillary forces of carpet fibers. Said other forces tend to act against the capillarity force of the first layer.
- said first layer is made of a material having a low surface energy.
- low surface energy it is meant herein, that the material being capable of capillarity additionally has the capability of being wetted by lipophilic liquids, such as oils, grease and the like.
- lipophilic liquids such as oils, grease and the like.
- the capability of being wetted by lipophilic liquids allows the material to exert a driving force on lipophilic liquids. This means that such lipophilic liquids are particularly well absorbed by said material.
- the material having a low surface energy shows an affinity for greasy/oily substances making up greasy/oily spot stains and hence is particularly suitable to remove grease/oily stains from carpets.
- said material has a water-absorbing capacity of at least 200% of its own weight. More preferably, said material has a water-absorbing capacity of at least 500% of its own weight. More preferably, said material has a water-absorbing capacity of at least 700% of its own weight. Even more preferably, said material has a water-absorbing capacity of at least 1000% of its own weight. Most preferably, said material has a water-absorbing capacity of at least 1200% of its own weight.
- said material has a lipophilic liquid-absorbing capacity of at least 200% of its own weight. More preferably, said material has a lipophilic liquid-absorbing capacity of at least 500% of its own weight. More preferably, said material has a lipophilic liquid-absorbing capacity of at least 700% of its own weight. Even more preferably, said material has a lipophilic liquid-absorbing capacity of at least 1000% of its own weight. Most preferably, said material has a lipophilic liquid-absorbing capacity of at least 1200% of its own weight.
- absorbing capacity it is meant herein, the amount of liquid a material can hold in comparison to its own weight.
- said first layer is made of a spongy cloth.
- said first layer is made of a material selected from the group consisting of synthetic rubber, polyurethane, polyester, polyether, cellulose based material, acrylic-styrene co-polymers and mixtures thereof. More preferably, said first layer is made of synthetic rubber.
- the second layer is impermeable for the carpet cleaning composition employed in the process according to the present invention.
- impermeable it is meant herein, that said composition can not penetrate through said second layer.
- said second layer is made of a material selected from the group consisting of polypropylene, natural rubber, latex and mixtures thereof. More preferably, said second layer is made of polypropylene.
- said first layer may be covered with or replaced by an abrasive layer, a brush, bristle or the like on one of the outer sides of said glove.
- the two sides forming the outer part of the glove are made of two different materials being capable of capillarity.
- said glove further comprises additional layers located on top of the first layer, in between the first and the second layer and/or between the second layer and the cavity formed by the glove.
- Said glove may comprise an additional layer comprising a material protecting the user's hand from the impermeable second layer. This may be necessary due to allergic reaction of the user's hand when coming into contact with the impermeable second layer (e.g., due to a latex allergy).
- said additional layer comprising a material protecting the user's hand is made of cotton, other natural fibers or mixtures thereof.
- said additional layer comprising a material protecting the user's hand is located between the second layer and the cavity formed by the glove. More preferably, said additional layer comprising a material protecting the user's hand is the innermost layer of said glove.
- said process allows the absorption of the liquid cleaning composition including emulsified dirt as well as excess liquid cleaning composition from the carpet into the first layer of said glove resulting in prevention of carpet resoiling and reduction of drying time.
- said first layer being capable of capillarity.
- said first layer preferably made of a spongy cloth, is capable of absorbing the liquid cleaning composition including emulsified dirt as well as excess liquid cleaning composition. This prevents the liquid cleaning composition including emulsified dirt to redeposit on the carpet which would cause carpet resoiling.
- said adsorption allows to take up excess cleaning composition resulting in a faster drying time.
- the chemistry of the cleaning composition employed in the process according to the present invention may by irritant to human skin.
- a peroxygen bleach, when present, a volatile organic compound, when present, and/or a surfactant, when present may cause skin irritation.
- the process of the present invention allows to protect the hands of a user performing said process from the liquid cleaning composition that can be irritant to the user's skin due to the presence of the impermeable layer protecting the user's hand.
- compositions of the present invention are formulated as liquid compositions.
- Preferred compositions herein are aqueous compositions and therefore, preferably comprise water more preferably in an amount of from 60% to 98%, even more preferably of from 80% to 97% and most preferably 85% to 97% by weight of the total composition.
- the pH of the liquid compositions according to the present invention may typically be from 1 to 14.
- the recommended pH range is from 1 to 10, preferably from pH 2 to 8, more preferably from pH 3 to 7, even more preferably from pH 3.5 to 7 and most preferably from 3.5 to 6.5.
- compositions herein may further comprise an acid or base to adjust pH as appropriate.
- Preferred acids herein are organic or inorganic acids or mixtures thereof.
- Preferred organic acids are acetic acid, or citric acid or a mixture thereof.
- Preferred inorganic acids are sulfuric acid or phosphoric acid or a mixture thereof.
- a particularly preferred acid to be used herein is an inorganic acid and most preferred is sulfuric acid.
- Typical levels of such acids when present, are of from 0.01% to 1.0%, preferably from 0.05% to 0.8% and more preferably from 0.1% to 0.5% by weight of the total composition.
- bases to be used herein can be organic or inorganic bases.
- Suitable bases for use herein are the caustic alkalis, such as sodium hydroxide, potassium hydroxide and/or lithium hydroxide, and/or the alkali metal oxides such, as sodium and/or potassium oxide or mixtures thereof.
- a preferred base is a caustic alkali, more preferably sodium hydroxide and/or potassium hydroxide.
- Suitable bases include ammonia, ammonium carbonate and hydrogen carbonate.
- Typical levels of such bases when present, are of from 0.01% to 1.0%, preferably from 0.05% to 0.8% and more preferably from 0.1% to 0.5% by weight of the total composition.
- compositions according to the present invention may comprise a peroxygen bleach.
- Suitable peroxygen bleaches to be used herein are selected from the group consisting of: hydrogen peroxide; water soluble sources of hydrogen peroxide; organic or inorganic peracids; hydroperoxides; diacyl peroxides; and mixtures thereof.
- a hydrogen peroxide source refers to any compound that produces perhydroxyl ions when said compound is in contact with water.
- Suitable water-soluble sources of hydrogen peroxide for use herein are selected from the group consisting of percarbonates, perborates and persilicates and mixtures thereof.
- Suitable diacyl peroxides for use herein are selected from the group consisting of aliphatic, aromatic and aliphatic-aromatic diacyl peroxides, and mixtures thereof.
- Suitable aliphatic diacyl peroxides for use herein are dilauroyl peroxide, didecanoyl peroxide, dimyristoyl peroxide, or mixtures thereof.
- a suitable aromatic diacyl peroxide for use herein is for example benzoyl peroxide.
- a suitable aliphatic-aromatic diacyl peroxide for use herein is for example lauroyl benzoyl peroxide.
- Such diacyl peroxides have the advantage to be particularly safe to carpets and carpet dyes while delivering excellent bleaching performance.
- Suitable organic or inorganic peracids for use herein are selected from the group consisting of : persulphates such as monopersulfate; peroxyacids such as diperoxydodecandioic acid (DPDA); magnesium perphthalic acid; perlauric acid; perbenzoic and alkylperbenzoic acids; and mixtures thereof.
- persulphates such as monopersulfate
- peroxyacids such as diperoxydodecandioic acid (DPDA); magnesium perphthalic acid
- perlauric acid perbenzoic and alkylperbenzoic acids
- Suitable hydroperoxides for use herein are selected from the group consisting of tert-butyl hydroperoxide, cumyl hydroperoxide, 2,4,4-trimethylpentyl-2-hydroperoxide, di-isopropylbenzene-monohydroperoxide, tert-amyl hydroperoxide and 2,5-dimethyl-hexane-2,5-dihydroperoxide and mixtures thereof.
- Such hydroperoxides have the advantage to be particularly safe to carpets and carpet dyes while delivering excellent bleaching performance.
- Preferred peroxygen bleaches herein are selected from the group consisting of : hydrogen peroxide; water soluble sources of hydrogen peroxide; organic or inorganic peracids; hydroperoxides; and diacyl peroxides; and mixtures thereof. More preferred peroxygen bleaches herein are selected from the group consisting of hydrogen peroxide, water soluble sources of hydrogen peroxide and diacyl peroxides and mixtures thereof. Even more preferred peroxygen bleaches herein are selected from the group consisting of hydrogen peroxide, water soluble sources of hydrogen peroxide, aliphatic diacyl peroxides, aromatic diacyl peroxides and aliphatic-aromatic diacyl peroxides and mixtures thereof. Most preferred peroxygen bleaches herein are hydrogen peroxide, water soluble sources of hydrogen peroxide or mixtures thereof.
- the liquid compositions herein comprise from 0.01% to 20%, preferably from 0.5 % to 10%, and more preferably from 1% to 7% by weight of the total composition of a peroxygen bleach, or mixtures thereof.
- a peroxygen bleach in preferred compositions when employed in the process of cleaning a carpet according to the present invention contributes to the excellent cleaning and sanitizing performance on various types of soils including on spot stains like bleachable stains (e.g., coffee, beverage, food) of the compositions of the present invention.
- spot stains like bleachable stains (e.g., coffee, beverage, food) of the compositions of the present invention.
- bleachable stains any soils or stains containing ingredients sensitive to bleach that can be found on any carpet, e.g., coffee or tea.
- compositions according to the present invention typically comprise a surfactant or a mixture thereof.
- compositions herein may comprise up to 50%, preferably from 0.1% to 20%, more preferably from 0.5% to 10% and most preferably from 1% to 5% by weight of the total composition of a surfactant.
- Such surfactants may be selected from those well known in the art including anionic, nonionic, zwitterionic, amphoteric and cationic surfactants and mixtures thereof.
- Particularly suitable surfactants to be used herein are anionic surfactants.
- Said anionic surfactants are preferred herein as they further contribute to the outstanding stain removal performance of the compositions of the present invention on various types of stains. Moreover they do not stick on carpet, thereby reducing resoiling.
- Suitable anionic surfactants include sulfosuccinate surfactants, sulfosuccinamate surfactants, sulfosuccinamide surfactants, alkyl carboxylate surfactants, sarcosinate surfactants, alkyl sulfate surfactants, alkyl sulphonate surfactants, alkyl glycerol sulfate surfactants, alkyl glycerol sulphonate surfactants and mixtures thereof.
- Suitable sulfosuccinate surfactants are according to the formula wherein : R 1 is hydrogen or a hydrocarbon group selected from the group consisting of straight or branched alkyl radicals containing from 6 to 20 carbon atoms, preferably 8 to 18 carbon atoms, more preferably 10 to 16 carbon atoms, and alkyl phenyl radicals containing from 6 to 18 carbon atoms in the alkyl group; R 2 is a hydrocarbon group selected from the group consisting of straight or branched alkyl radicals containing from 6 to 20 carbon atoms, preferably 8 to 18 carbon atoms, more preferably 10 to 16 carbon atoms, and alkyl phenyl radicals containing from 6 to 18 carbon atoms in the alkyl group; and M is hydrogen or a cationic moiety, e.g., an alkali metal cation (e.g., sodium, potassium, lithium, calcium, magnesium and the like) or ammonium or substituted ammonium (e.g.,
- Such sulfosuccinate surfactants are commercially available under the tradenames Aerosol® from Cytec, Anionyx® from Stepan, Arylene® from Hart, Setacin® from Zschimmer & Schwarz, Mackanate® from McIntyre and Monawet® from Mona Industries.
- Suitable alkyl sulphonate surfactants for use herein include water-soluble salts or acids of the formula RSO 3 M wherein R is a C 6 -C 20 linear or branched, saturated or unsaturated alkyl group, preferably a C 8 -C 18 alkyl group and more preferably a C 10 -C 16 alkyl group, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
- R is a C 6 -
- C 14 -C 16 alkyl sulphonate is Hostapur® SAS available from Hoechst.
- Suitable alkyl sulphate surfactants for use herein are according to the formula R 1 SO 4 M wherein R 1 represents a hydrocarbon group selected from the group consisting of straight or branched alkyl radicals containing from 6 to 20, preferably 8 to 18, more preferably 10 to 16, carbon atoms and alkyl phenyl radicals containing from 6 to 18 carbon atoms in the alkyl group.
- M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium, calcium, magnesium and the like) or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
- alkali metal cation e.g., sodium, potassium, lithium, calcium, magnesium and the like
- ammonium or substituted ammonium e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and
- linear alkyl sulphate or sulphonate it is meant herein a non-substituted alkyl sulphate or sulphonate wherein the alkyl chain comprises from 6 to 20 carbon atoms, preferably from 8 to 18 carbon atoms, and more preferably from 10 to 16 carbon atoms, and wherein this alkyl chain is sulphated or sulphonated at one terminus.
- branched sulphonate or sulphate it is meant herein an alkyl chain having from 6 to 20 total carbon atoms, preferably from 8 to 18 total carbon atoms, and more preferably from 10 to 16 total carbon atoms, wherein the main alkyl chain is substituted by at least another alkyl chain, and wherein the alkyl chain is sulphated or sulphonated at one terminus.
- Particularly preferred branched alkyl sulphates to be used herein are those containing from 10 to 14 total carbon atoms like Isalchem 123 AS®.
- Also preferred alkyl sulphates are the alkyl sulphates where the alkyl chain comprises a total of 12 carbon atoms, i.e., sodium 2-butyl octyl sulphate.
- alkyl sulphate is commercially available from Condea under the trade name Isofol® 12S.
- Particularly suitable liner alkyl sulphonates include C12-C16 paraffin sulphonate like Hostapur® SAS commercially available from Hoechst.
- Suitable sulfosuccinamate surfactants for use herein are according to the formula wherein R 1 and R 2 each independently represent a hydrocarbon group selected from the group consisting of straight or branched alkyl radicals containing from 6 to 20, preferably 8 to 18, more preferably 10 to 16, carbon atoms and alkyl phenyl radicals containing from 6 to 18 carbon atoms in the alkyl group.
- M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium, calcium, magnesium and the like) or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
- alkali metal cation e.g., sodium, potassium, lithium, calcium, magnesium and the like
- ammonium or substituted ammonium e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and
- Suitable sulfosuccinamide surfactants for use herein are according to the formula wherein R 1 and R 2 each independently represent a hydrocarbon group selected from the group consisting of straight or branched alkyl radicals containing from 6 to 20, preferably 8 to 18, more preferably 10 to 16, carbon atoms and alkyl phenyl radicals containing from 6 to 18 carbon atoms in the alkyl group.
- M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium, calcium, magnesium and the like) or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
- alkali metal cation e.g., sodium, potassium, lithium, calcium, magnesium and the like
- ammonium or substituted ammonium e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and
- Suitable alkyl carboxylate surfactants for use herein are according to the formula RCO 2 M wherein : R represents a hydrocarbon group selected from the group consisting of straight or branched alkyl radicals containing from 6 to 20, preferably 8 to 18, more preferably 10 to 16, carbon atoms and alkyl phenyl radicals containing from 6 to 18 carbon atoms in the alkyl group.
- M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium, calcium, magnesium and the like) or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
- alkali metal cation e.g., sodium, potassium, lithium, calcium, magnesium and the like
- ammonium or substituted ammonium e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and
- Suitable sarcosinate surfactants to be used herein include acyl sarcosinate or mixtures thereof, in its acid and/or salt form, preferably long chain acyl sarcosinates having the following formula: wherein M is hydrogen or a cationic moiety and wherein R is an alkyl group of from 11 to 15 carbon atoms, preferably of from 11 to 13 carbon atoms. Preferred M are hydrogen and alkali metal salts, especially sodium and potassium.
- Said acyl sarcosinate surfactants are derived from natural fatty acids and the amino-acid sarcosine (N-methyl glycine). They are suitable to be used as aqueous solution of their salt or in their acidic form as powder. Being derivatives of natural fatty acids, said acyl sarcosinates are rapidly and completely biodegradable and have good skin compatibility.
- particularly preferred long chain acyl sarcosinates to be used herein include C 12 acyl sarcosinate, i.e., an acyl sarcosinate according to the above formula wherein M is hydrogen and R is an alkyl group of 11 carbon atom, sodium N-lauroyl sarcosinate, i.e., an acyl sarcosinate according to the above formula wherein M is sodium and R is an alkyl group of 11 carbon atom, and C 14 acyl sarcosinate (i.e., an acyl sarcosinate according to the above formula wherein M is hydrogen and R is an alkyl group of 13 carbon atoms).
- C 12 acyl sarcosinate i.e., an acyl sarcosinate according to the above formula wherein M is hydrogen and R is an alkyl group of 11 carbon atom
- sodium N-lauroyl sarcosinate i.e., an
- sodium N-lauroyl sarcosinate is commercially available, for example, as Hamposyl L-30® supplied by Hampshire or Crodasinic LS30® supplied by Croda.
- C 14 acyl sarcosinate is commercially available, for example, as Hamposyl M-30® supplied by Hampshire or Crodasinic MS30® supplied by Croda.
- Suitable nonionic surfactants include amine oxide surfactants.
- Suitable amine oxide surfactants are according to the formula R 1 R 2 R 3 NO, wherein each of R 1 , R 2 and R 3 is independently a saturated substituted or unsubstituted, linear or branched alkyl groups of from 1 to 30 carbon atoms, preferably of from 1 to 20 carbon atoms, and mixtures thereof.
- Particularly preferred amine oxide surfactants to be used according to the present invention are amine oxide surfactants having the following formula R 1 R 2 R 3 NO wherein R 1 is a saturated linear or branched alkyl group of from 1 to 30 carbon atoms, preferably of from 6 to 20 carbon atoms, more preferably of from 6 to 16 carbon atoms, and wherein R 2 and R 3 are independently substituted or unsubstituted, linear or branched alkyl groups of from 1 to 4 carbon atoms, preferably of from 1 to 3 carbon atoms, and more preferably are methyl groups.
- Preferred amine oxide surfactants used herein are pure-cut amine oxide surfactants, i.e., a pure single amine oxide surfactant, e.g. C 8 N,N-dimethyl amine oxide, as opposed to mixtures of amine oxide surfactants of different chain lengths
- Suitable amine oxide surfactants for use herein are for instance pure cut C 8 amine oxide, pure cut C 10 amine oxide, pure cut C 14 amine oxide, natural blend C 8 -C 10 amine oxides as well as natural blend C 12 -C 16 amine oxides.
- Such amine oxide surfactants may be commercially available from Hoechst or Stephan.
- Suitable nonionic surfactants for use herein also include any ethoxylated C 6 -C 24 fatty alcohol nonionic surfactant, alkyl propoxylates and mixtures thereof, fatty acid C 6 -C 24 alkanolamides, C 6 -C 20 polyethylglycol ethers, polyethylene glycol with molecular weight 1000 to 80000 and glucose amides, alkyl pyrrolidones.
- Suitable cationic surfactants for use herein include quaternary ammonium compounds of the formula R 1 R 2 R 3 R 4 N+ where R 1 ,R 2 and R 3 are methyl groups, and R 4 is a C 12-15 alkyl group, or where R1 is an ethyl or hydroxy ethyl group, R 2 and R 3 are methyl groups and R 4 is a C 12-15 alkyl group.
- Suitable zwitterionic surfactants are zwitterionic betaine surfactants.
- Suitable zwitterionic betaine surfactants for use herein contain both a cationic hydrophilic group, i.e., a quaternary ammonium group, and anionic hydrophilic group on the same molecule at a relatively wide range of pH's.
- the typical anionic hydrophilic groups are carboxylates and sulphonates, although other groups like sulfates, phosphonates, and the like can be used.
- a generic formula for the zwitterionic betaine surfactant to be used herein is : R 1 -N+(R 2 )(R 3 )R 4 X- wherein R 1 is a hydrophobic group; R 2 is hydrogen, C 1 -C 6 alkyl, hydroxy alkyl or other substituted C 1 -C 6 alkyl group; R 3 is C 1 -C 6 alkyl, hydroxy alkyl or other substituted C 1 -C 6 alkyl group which can also be joined to R 2 to form ring structures with the N, or a C 1 -C 6 sulphonate group; R 4 is a moiety joining the cationic nitrogen atom to the hydrophilic group and is typically an alkylene, hydroxy alkylene, or polyalkoxy group containing from 1 to 10 carbon atoms; and X is the hydrophilic group, which is a carboxylate or sulphonate group.
- R 1 are aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chains that can contain linking groups such as amido groups, ester groups. More preferred R 1 is an alkyl group containing from 1 to 24, preferably from 8 to 18, and more preferably from 10 to 16 carbon atoms. These simple alkyl groups are preferred for cost and stability reasons.
- the hydrophobic group R 1 can also be an amido radical of the formula R a -C(O)-NH-(C(R b ) 2 )m, wherein R a is an aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chain, preferably an alkyl group containing from 8 up to 20, preferably up to 18, more preferably up to 16 carbon atoms, R b is selected from the group consisting of hydrogen and hydroxy groups, and m is from 1 to 4, preferably from 2 to 3, more preferably 3, with no more than one hydroxy group in any (C(R b ) 2 ) moiety.
- R a is an aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chain, preferably an alkyl group containing from 8 up to 20, preferably up to 18, more preferably up to 16 carbon atoms
- R b is selected from the group consisting of hydrogen and hydroxy groups
- m is from 1 to 4,
- Preferred R 2 is hydrogen, or a C 1 -C 3 alkyl and more preferably methyl.
- Preferred R3 is C 1 -C 4 sulphonate group, or a C 1 -C 3 alkyl and more preferably methyl.
- Preferred R 4 is (CH 2 ) n wherein n is an integer from 1 to 10, preferably from 1 to 6, more preferably is from 1 to 3.
- betaine/sulphobetaine Some common examples of betaine/sulphobetaine are described in U.S. Pat. Nos. 2,082,275, 2,702,279 and 2,255,082, incorporated herein by reference.
- alkyldimethyl betaines examples include coconut-dimethyl betaine, lauryl dimethyl betaine, decyl dimethyl betaine, 2-(N-decyl-N, N-dimethyl-ammonia)acetate, 2-(N-coco N, N-dimethylammonio) acetate, myristyl dimethyl betaine, palmityl dimethyl betaine, cetyl dimethyl betaine, stearyl dimethyl betaine.
- coconut dimethyl betaine is commercially available from Seppic under the trade name of Amonyl 265®.
- Lauryl betaine is commercially available from Albright & Wilson under the trade name Empigen BB/L®.
- amidobetaines include cocoamidoethylbetaine, cocoamidopropyl betaine or C 10 -C 14 fatty acylamidopropylene(hydropropylene)sulfobetaine.
- C 10 -C 14 fatty acylamidopropylene(hydropropylene)sulfobetaine is commercially available from Sherex Company under the trade name "Varion CAS® sulfobetaine".
- betaine Lauryl-immino-dipropionate commercially available from Rhone-Poulenc under the trade name Mirataine H2C-HA®.
- a preferred surfactant for use herein is an anionic surfactant or a zwitterionic surfactant or a mixture thereof
- a more preferred surfactant is a sulfosuccinate surfactant, sulfosuccinamate surfactant, sulfosuccinamide surfactant, carboxylate surfactant, sarcosinate surfactant, alkyl sulfate surfactant, alkyl sulphonate surfactant, alkyl glycerol sulfate surfactant and alkyl glycerol sulphonate surfactant or a zwitterionic betaine surfactant and mixtures thereof.
- a preferred surfactant for use herein is a sarcosinate surfactant, an alkyl sulphonate surfactant, an alkyl sulphate surfactant, or a zwitterionic betaine surfactant and mixtures thereof, and the most preferred surfactant herein is an alkyl sarcosinate surfactant.
- a preferred surfactant for use herein is a mixture of a sulfosuccinate surfactant and a second anionic surfactant. More preferably, said surfactant is a mixture of a sulfosuccinate surfactant and a sulphate surfactant. Most preferably, said surfactant is a sulfosuccinate surfactant.
- a surfactant in preferred compositions when employed in the process of cleaning a carpet according to the present invention contributes to the excellent cleaning performance on various types of soils including diffuse soils (e.g., particulate and/or greasy soils) that tend to accumulate in the so called "high traffic areas" but also in delivering good cleaning performance on other types of stains or soils, i.e., enzymatic stains like blood.
- diffuse soils e.g., particulate and/or greasy soils
- high traffic areas areas with an intensive use of the carpets in such areas as for example near doors.
- pill stains any soils or stains of particulate nature that can be found on any carpet, e.g. clay, dirt, dust, mud, concrete and the like.
- greasy/oily stains any soils or stains of greasy/oily nature that can be found on any carpet, e.g., make-up, lipstick, dirty motor oil and mineral oil, greasy food like mayonnaise and spaghetti sauce.
- enzymatic stains any soils or stains of enzymatic nature that can be found on any carpet, e.g., grass.
- the cleaning performance of a given composition on a soiled carpet may be evaluated by the following test method : A liquid composition according to the present invention is first applied, preferably sprayed, onto the stained portion of a carpet, left to act thereon from 1 to 60 minutes, preferably 30 minutes, after which the carpet is vacuum cleaned using any commercially available vacuum cleaners like for instance a standard Hoover® 1300W vacuuming machine.
- the soils used in this test may be particulate stains, greasy/oily stains or enzymatic stain as described above.
- the cleaning performance may be evaluated by visual using panel score units to rate the cleaning performance.
- compositions as disclosed herein may comprise as a highly preferred optional ingredient an anti-resoiling agent.
- Suitable anti-resoiling agents include anti-resoiling polymers.
- Suitable poly (vinyl methyl ether / maleic acid) copolymers are according to the general formula : wherein n (degree of polymerisation) is an integer of from 50 to 1600, preferably from 100 to 800, and more preferably from 200 to 400.
- suitable poly (vinyl methyl ether / maleic acid) copolymers for use herein have an average molecular weight of from 1'000 to 10'000'000, preferably 10'000 to 1'000'000, more preferably from 10'000 to 500'000, and most preferably from 50'000 to 100'000.
- Suitable poly (vinyl methyl ether / maleic acid) copolymers are commercially available, for instance, from ISP Corporation, New York, NY and Montreal, Canada under the product names Gantrez AN Copolymer® (AN-119 copolymer, average molecular weight of 20'000; AN-139 copolymer, average molecular weight of 41'000; AN-149 copolymer, average molecular weight of 50'000; AN-169 copolymer, average molecular weight of 67'000; AN-179 copolymer, average molecular weight of 80'000), Gantrez S® (Gantrez S97®, average molecular weight of 70'000), and Gantrez ES® (ES-225, ES-335, ES-425, ES-435), Gantrez V® (V-215, V-225, V-425).
- Gantrez AN Copolymer® AN-119 copolymer, average molecular weight of 20'000; AN-139
- the poly (vinyl methyl ether / maleic acid) copolymers are either crosslinked or not crosslinked, i.e., linear. More preferably the poly (vinyl methyl ether / maleic acid) copolymers are not crosslinked.
- Suitable anti-resoiling polymers include soil suspending polyamine polymers. Any soil suspending polyamine polymer known to those skilled in the art may also be used herein. Particularly suitable polyamine polymers for use herein are alkoxylated polyamines. Such materials can conveniently be represented as molecules of the empirical structures with repeating units : and wherein R is a hydrocarbyl group, usually of 2-6 carbon atoms; R 1 may be a C 1 -C 20 hydrocarbon; the alkoxy groups are ethoxy, propoxy, and the like, and y is from 2 to 30, most preferably from 7 to 20; n is an integer of at least 2, preferably from 2 to 40, most preferably from 2 to 5; and X- is an anion such as halide or methylsulfate, resulting from the quaternization reaction.
- the most highly preferred polyamines for use herein are the so-called ethoxylated polyethylene amines, i.e., the polymerized reaction product of ethylene oxide with ethyleneimine, having the general formula : wherein y is from 2 to 50, preferably from 5 to 30, and n is from 1 to 40, preferably from 2 to 40.
- Suitable anti-resoiling polymers also include polyamine N-oxide polymers.
- Suitable polyamine N-oxide polymers for use herein are according to the following formula : R-A x -P; containing at least one N-oxide group (N-O group);
- N-O group it is meant one of the following general structures: wherein R 1 , R 2 , R 3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group can be attached or form part of any of the aforementioned groups.
- Any polymerizable unit P can be used as long as the amine oxide polymer formed is water-soluble and provides the carpet cleaning composition with carpet cleaning and/or carpet anti-resoiling benefits.
- Preferred polymerizable unit P are vinyl, alkylenes, esters, ethers, amides, imides, acrylates and mixtures thereof.
- a more preferred polymerizable unit P is vinyl.
- Preferred polyamine N-oxide polymers are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, or a derivative thereof, to which the nitrogen of the N-O group can be attached or the N-O group is part of these groups. Most preferred polyamine N-oxide polymers are those wherein R is a pyridine.
- the polyamine N-oxide polymer can be obtained in almost any degree of polymerization.
- the average molecular weight is within the range of 1,000 to 100,000; more preferred 5,000 to 100,000; most preferred 5,000 to 25,000.
- Suitable poly vinyl pyridine-N-oxide polymers are commercially available from Hoechst under the trade name of Hoe S 4268®, and from Reilly Industries Inc. under the trade name of PVNO.
- suitable anti-resoiling polymers include N-vinyl polymer.
- Suitable N-vinyl polymers include polyvinyl pyrrolidone polymers, co-polymers of N-vinylpyrrolidone and N-vinylimidazole, co-polymers of N-vinylpyrrolidone and acrylic acid, and mixtures thereof.
- Suitable co-polymers of N-vinylpyrrolidone and N-vinylimidazole polymers are according to the formula : in which n is between 50 and 500 and preferably between 80 and 200 and m is between 50 and 500 and preferably between 80 and 200.
- the PVPVI has an average molecular weight range from 1,000 to 100,000, more preferably from 5,000 to 100,000, and most preferably from 5,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al., Chemical Analysis, Vol 113. "Modern Methods of Polymer Characterization", the disclosures of which are incorporated herein by reference.)
- the PVPVI co-polymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These co-polymers can be either linear or branched.
- Suitable co-polymers of N-vinylpyrrolidone and N-vinylimidazole are commercially available from BASF, under the trade name of Sokalan® PG55.
- Suitable polyvinylpyrrolidone (“PVP”) for use herein are homopolymers of N-vinylpyrrolidone having the following repeating monomer:
- Preferred vinylpyrrolidone homopolymers for use herein have an average molecular weight of from 1,000 to 100,000, preferably from 5,000 to 100,000, and more preferably from 5,000 to 20,000.
- Suitable vinylpyrrolidone homopolymers are commercially available from BASF under the trade names Luviskol® K15 (viscosity molecular weight of 10,000), Luviskol® K25 (viscosity molecular weight of 24,000), Luviskol® K30 (viscosity molecular weight of 40,000), and other vinylpyrrolidone homopolymers known to persons skilled in the detergent field (see for example EP-A-262,897 and EP-A-256,696).
- Suitable co-polymers of N-vinylpyrrolidone and acrylic acid are according to the formula : in which n is between 50 and 1000 and preferably between 100 and 200 and m is between 150 and 3000 and preferably between 300 and 600.
- the PV/AA have an average molecular weight range from 1,000 to 100,000, more preferably from 5,000 to 100,000, and most preferably from 5,000 to 25,000.
- Suitable co-polymers of N-vinylpyrrolidone and acrylic acid are commercially available from BASF under the trade name Sokalan® PG 310.
- N-vinyl polymers are polyvinyl pyrrolidone polymers, co-polymers of N-vinylpyrrolidone and N-vinylimidazole, co-polymers of N-vinylpyrrolidone and acrylic acid, and mixtures thereof, even more preferred are polyvinyl pyrrolidone polymers.
- Suitable anti-resoiling polymers also include soil suspending polycarboxylate polymers.
- any soil suspending polycarboxylate polymer known to those skilled in the art can be used according to the present invention such as homo- or co-polymeric polycarboxylic acids or their salts including polyacrylates and copolymers of maleic anhydride or/and acrylic acid and the like.
- soil suspending polycarboxylate polymers can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form.
- Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
- the presence in the polymeric polycarboxylates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than 40% by weight.
- Particularly suitable polymeric polycarboxylates to be used herein can be derived from acrylic acid.
- acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid.
- the average molecular weight of such polymers in the acid form preferably ranges from 2,000 to 10,000, more preferably from 4,000 to 7,000 and most preferably from 4,000 to 5,000.
- Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued March 7, 1967.
- Acrylic/maleic-based copolymers may also be used as a preferred soil suspending polycarboxylic polymer.
- Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid.
- the average molecular weight of such copolymers in the acid form preferably ranges from 2,000 to 100,000, more preferably from 5,000 to 75,000, most preferably from 7,000 to 65,000.
- the ratio of acrylate to maleate segments in such copolymers will generally range from 30:1 to 1:1, more preferably from 10:1 to 2:1.
- Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts.
- Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982. Particularly preferred is a copolymer of maleic / acrylic acid with an average molecular weight of 70,000. Such copolymers are commercially available from BASF under the trade name SOKALAN® CP5.
- suitable anti-resoiling polymers include those anti-resoiling polymers having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to about 30 oxypropylene units wherein said mixture contains a sufficient amount of oxyethylene units such that the hydrophile component has hydrophilicity great enough to increase the hydrophilicity of conventional polyester synthetic fiber surfaces upon deposit of the soil release agent on such surface, said hydrophile segments preferably comprising at least about 25% oxyethylene units and more preferably, especially for such components having about 20 to 30 oxypropylene units, at least about 50%
- the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from about 1 to about 200, although higher levels can be used, preferably from 3 to about 150, more preferably from 6 to about 100.
- Suitable oxy C 4 -C 6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as MO 3 S(CH 2 ) n OCH 2 CH 2 O-, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink.
- Anti-resoiling polymers useful in the present invention also include cellulosic derivatives such as hydroxyether cellulosic polymers, co-polymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like.
- Such anti-resoiling polymers are commercially available and include hydroxyethers of cellulose such as METHOCEL® (Dow).
- Cellulosic anti-resoiling polymers for use herein also include those selected from the group consisting of C 1 -C 4 alkyl and C 4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al.
- Anti-resoiling polymers characterised by poly(vinyl ester) hydrophobe segments include graft co-polymers of poly(vinyl ester), e.g., C 1 -C 6 vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones. See European Patent Application 0 219 048, published April 22, 1987 by Kud, et al. Commercially available anti-resoiling polymers of this kind include the SOKALAN® type of material, e.g., SOKALAN HP-22®, available from BASF.
- One type of preferred anti-resoiling polymers is a co-polymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate.
- the molecular weight of these anti-resoiling polymers is in the range of from about 25,000 to about 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur issued July 8, 1975.
- Another preferred anti-resoiling polymers is a polyester with repeat units of ethylene terephthalate units which contains 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000.
- this polymer include the commercially available material ZELCON 5126® (from Dupont) and MILEASE T® (from ICI). See also U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
- Another preferred anti-resoiling polymers agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone.
- These anti-resoiling polymers are fully described in U.S. Patent 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink.
- Other suitable anti-resoiling polymers include the terephthalate polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
- Preferred anti-resoiling polymers also include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al, which discloses anionic, especially sulfoaroyl, end-capped terephthalate esters.
- Still another preferred anti-resoiling agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1,2-propylene units.
- the repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end-caps.
- a particularly preferred anti-resoiling agent of this type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of from about 1.7 to about 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-ethanesulfonate.
- Said anti-resoiling agent also comprises from about 0.5% to about 20%, by weight of the oligomer, of a crystalline-reducing stabilizer, preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
- a crystalline-reducing stabilizer preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
- the liquid compositions may comprise from 0.01% to 10%, preferably from 0.01% to 5%, and more preferably from 0.05% to 2% by weight of the total composition of a further anti-resoiling agent.
- a preferred anti-resoiling agent is an anti-resoiling polymer.
- a more preferred anti-resoiling agent is a poly (vinyl methyl ether / maleic acid) copolymer, a soil suspending polyamine polymer, a poly vinyl pyridine-N-oxide polymer or a mixture thereof.
- An even more preferred anti-resoiling agent is a poly (vinyl methyl ether / maleic acid) copolymer, an alkoxylated polyamine polymer, a poly vinyl pyridine-N-oxide polymer or a mixture thereof.
- compositions according to the present invention may comprise a volatile organic compound (VOC) or a mixture thereof.
- VOC volatile organic compound
- compositions herein may comprise up to 90%, preferably from 0.1% to 20%, more preferably from 0.5% to 10% and most preferably from 1% to 5% by weight of the total composition of a volatile organic compound or a mixture thereof.
- Suitable volatile organic compounds for use herein are selected from the group consisting of : an aliphatic and/or aromatic alcohol; a glycol ether and/or a derivative thereof; a polyol; and a mixture thereof.
- Suitable aromatic alcohols to be used herein are according to the formula R 1 -OH wherein R 1 is an alkyl substituted or non-alkyl substituted aryl group of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to 10.
- R 1 is an alkyl substituted or non-alkyl substituted aryl group of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to 10.
- a suitable aromatic alcohol to be used herein is benzyl alcohol.
- Suitable aliphatic alcohols to be used herein are according to the formula R 2 -OH wherein R 2 is a linear or branched saturated or unsaturated hydrocarbon chain of from 1 to 20 carbon atoms, preferably from 1 to 10 and more preferably from 2 to 6. Highly preferred herein are aliphatic alcohols with 2 to 4 carbon atoms and most preferably 4 carbon atoms, or mixtures thereof. Suitable aliphatic alcohols to be used herein include linear alcohol like 2-octanol, decanol, isopropyl alcohol, propyl alcohol, ethanol and/or methanol. Highly preferred herein are ethanol, isopropyl alcohol or a mixture thereof.
- Ethanol may be commercially available from Eridania Italia under its chemical name.
- Isopropanol may be commercially available from Merck/BDH Italia under its chemical name.
- Suitable glycol ethers and/or derivatives thereof to be used herein include monoglycol ethers and/or derivatives thereof, polyglycol ethers and/or derivatives thereof and mixtures thereof.
- Suitable monoglycol ethers and derivatives thereof to be used herein include n-buthoxypropanol (n-BP), water-soluble CELLOSOLVE® solvents or mixtures thereof.
- Preferred Cellosolve® solvents include propoxy ethyl acetate salt (i.e., Propyl Cellosolve acetate salt®), ethanol-2-butoxy phosphate salt (i.e., Butyl Cellosolve phosphate salt®), 2-(Hexyloxy)ethanol (i.e., 2-hexyl Cellosolve®), 2-ethoxy ethanol (i.e., 2-ethyl Cellosolve®), 2-butoxyethanol (i.e., 2-buthyl Cellosolve®) or mixtures thereof.
- Suitable polyglycol ethers and derivatives thereof to be used herein include n-butoxypropoxypropanol (n-BPP), butyl triglycol ether (BTGE), butyl diglycol ether (BDGE), water-soluble CARBITOL® solvents or mixtures thereof.
- Preferred water-soluble CARBITOL® solvents are compounds of the 2-(2-alkoxyethoxy)ethanol class, 2-(2-alkoxyethoxy)propanol class and/or 2-(2-alkoxyethoxy)butanol class wherein the alkoxy group is derived from ethyl, propyl or butyl.
- a preferred water-soluble carbitol is 2-(2-butoxyethoxy)ethanol also known as butyl carbitol®.
- Preferred glycol ethers and/or derivatives thereof are 2-ethoxyethanol, 2-butoxyethanol, n-butoxypropoxypropanol, butyl carbitol® or mixtures thereof.
- Suitable polyol solvents to be used herein are the polyols having at least 2 hydroxyl groups (-OH) like diols.
- Suitable diols to be used herein include 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, methyl-2,4 pentanediol or mixture thereof.
- volatile organic compounds when present, further contribute to the excellent overall cleaning performance of the present invention. Additionally, their addition in the compositions herein also enhances the sanitising properties of the compositions.
- compositions herein may further comprise conventional carpet cleaning ingredients.
- the compositions herein may comprises a number of additional compounds selected from the group consisting of stabilising agents, chelating agents, builder systems, radical scavengers, perfumes, dyes, suds suppressing agents, enzymes, photobleaching agents, bleach activators and other minors and mixtures thereof.
- compositions herein may further comprises a number of additional compounds selected from the group consisting of stabilising agents, chelating agents, builder systems, radical scavengers, perfumes, dyes, suds suppressing agents, enzymes, photobleaching agents, bleach activators and other minors and mixtures thereof.
- compositions of the present invention may further comprise a stabilizing agent selected from the group consisting of hydroxy pyridine N-oxides or derivatives thereof and mixtures thereof.
- Suitable hydroxy pyridine N-oxides or derivatives thereof are according to the following formula: wherein X is nitrogen, Y is one of the following groups oxygen, -CHO, -OH, -(CH 2 )n-COOH, wherein n is an integer of from 0 to 20, preferably of from 0 to 10 and more preferably is 0, and wherein Y is preferably oxygen. Accordingly particularly preferred hydroxy pyridine N-oxides or derivatives thereof to be used herein is 2-hydroxy pyridine N-oxide.
- Hydroxy pyridine N-oxides or derivatives thereof may be commercially available from Sigma.
- compositions herein may comprise up to 2%, preferably from 0.001% to 1% and more preferably from 0.001% to 0.5% by weight of the total composition of a hydroxy pyridine N-oxide or derivatives thereof or mixtures thereof.
- compositions of the present invention may further comprise a chelating agent.
- Suitable chelating agents are those known to those skilled in the art. Particularly suitable chelating agents include for examples phosphonate chelating agents, polyfunctionally-substituted aromatic chelating agents, amino carboxylate chelating agents, other chelating agents like ethylene diamine N,N'-disuccinic acid and mixtures thereof.
- compositions herein may comprise up to 4%, preferably from 0.001% to 1%, and more preferably from 0.001% to 0.5% by weight of the total composition of a chelating agent.
- Suitable phosphonate chelating agents to be used herein may include ethydronic acid, alkali metal ethane 1-hydroxy diphosphonates as well as amino phosphonate compounds, including amino alkylene poly (alkylene phosphonate), alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates, and diethylene triamine penta methylene phosphonates.
- the phosphonate compounds may be present either in their acid form or as salts of different cations on some or all of their acid functionalities.
- Preferred phosphonate chelating agents to be used herein are diethylene triamine penta methylene phosphonates (DETPMP). Such phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST®.
- Polyfunctionally-substituted aromatic chelating agents may also be useful in the compositions herein. See U.S. patent 3,812,044, issued May 21, 1974, to Connor et al.
- Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy -3,5-disulfobenzene.
- a preferred biodegradable chelating agent for use herein is ethylene diamine N,N'- disuccinic acid, or alkali metal, or alkaline earth, ammonium or substitutes ammonium salts thereof or mixtures thereof.
- Ethylenediamine N,N'- disuccinic acids especially the (S,S) isomer, have been extensively described in US patent 4, 704, 233, November 3, 1987. to Hartman and Perkins.
- Ethylenediamine N,N'- disuccinic acid is, for instance, commercially available under the tradename ssEDDS® from Palmer Research Laboratories.
- Suitable amino carboxylate chelating agents to be used herein include ethylene diamine tetra acetates, diethylene triamine pentaacetates, diethylene triamine pentaacetate (DTPA), N-hydroxyethylethylenediamine triacetates, nitrilotriacetates, ethylenediamine tetrapropionates, triethylenetetraaminehexaacetates, ethanoldiglycines, propylene diamine tetracetic acid (PDTA) and methyl glycine di-acetic acid (MGDA), both in their acid form, or in their alkali metal, ammonium, and substituted ammonium salt forms.
- a particularly suitable amino carboxylate to be used herein is diethylene triamine penta acetic acid (DTPA).
- Suitable chelating agents to be used herein include salicylic acid or derivatives thereof, or mixtures thereof according to the following formula: wherein X is carbon, Y is one of the following groups -CHO, -OH, -(CH2)n-COOH, and preferably is -(CH2)n-COOH, and wherein n is an integer of from 0 to 20, preferably of from 0 to 10 and more preferably is 0.
- Salicylic acid and derivatives thereof may be used herein either in their acid form or in their salts form as for example sodium salts.
- Salicylic acid is particularly preferred herein and may be commercially available from Rhone Poulenc.
- compositions herein comprise a peroxygen bleach, preferably hydrogen peroxide
- said compositions may further comprise a bleach activator, as an optional inaredient.
- bleach activator it is meant herein a compound which reacts with the peroxygen bleach, preferably hydrogen peroxide, to form a peracid.
- the peracid thus formed constitutes the activated bleach.
- Suitable bleach activators to be used herein include those belonging to the class of esters, amides, imides, or anhydrides. Examples of suitable compounds of this type are disclosed in British Patent GB 1 586 769 and GB 2 143 231 and a method for their formation into a prilled form is described in European Published Patent Application EP-A-62 523.
- Suitable examples of such compounds to be used herein are tetracetyl ethylene diamine (TAED), sodium 3,5,5 trimethyl hexanoyloxybenzene sulphonate, diperoxy dodecanoic acid as described for instance in US 4 818 425 and nonylamide of peroxyadipic acid as described for instance in US 4 259 201 and n-nonanoyloxybenzenesulphonate (NOBS).
- TAED tetracetyl ethylene diamine
- NOBS n-nonanoyloxybenzenesulphonate
- N-acyl caprolactam selected from the group consisting of substituted or unsubstituted benzoyl caprolactam, octanoyl caprolactam, nonanoyl caprolactam, hexanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, formyl caprolactam, acetyl caprolactam, propanoyl caprolactam, butanoyl caprolactam pentanoyl caprolactam or mixtures thereof.
- a particular family of bleach activators of interest was disclosed in EP 624 154, and particularly preferred in that family is acetyl triethyl citrate (ATC).
- Acetyl triethyl citrate has the advantage that it is environmentally friendly as it eventually degrades into citric acid and alcohol. Furthermore, acetyl triethyl citrate has a good hydrolytical stability in the composition upon storage and it is an efficient bleach activator.
- compositions according to the present invention may comprise up to 30%, preferably from 1% to 20%, and more preferably from 2% to 10% by weight of the total composition of a bleach activator.
- compositions according to the present invention may further comprise a builder system.
- a builder system Any conventional builder system known in the art is suitable for use herein.
- Suitable builders for use herein include derivatives of succinic acid of the formula R-CH(COOH)CH 2 (COOH) wherein R is C 10-20 alkyl or alkenyl, preferably C 12-16 alkyl or alkenyl, or wherein R can be substituted with hydroxyl, sulpho sulphoxyl or sulphone substituents.
- Specific examples include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenylsuccinate, 2-tetradecenyl succinate.
- Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.
- Suitable builders are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US 4,663,071.
- fatty acid builders including saturated or unsaturated C 10-18 fatty acids, as well as the corresponding soaps.
- Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain.
- the preferred unsaturated fatty acid is oleic acid.
- compositions herein may comprise up to 10%, preferably from 1% to 7% by weight of the total composition of a builder system.
- compositions herein may comprise a radical scavenger as another optional ingredient.
- Suitable radical scavengers for use herein include the well-known substituted mono and di hydroxy benzenes and derivatives thereof, alkyl- and aryl carboxylates and mixtures thereof.
- Preferred radical scavengers for use herein include di-tert-butyl hydroxy toluene (BHT), p-hydroxy-toluene, hydroquinone (HQ), di-tert-butyl hydroquinone (DTBHQ), mono-tert-butyl hydroquinone (MTBHQ), tert-butyl-hydroxy anysole (BHA), p-hydroxy-anysol, benzoic acid, 2,5-dihydroxy benzoic acid, 2,5-dihydroxyterephtalic acid, toluic acid, catechol, t-butyl catechol, 4-allyl-catechol, 4-acetyl catechol, 2-methoxyphenol, 2-ethoxy-phenol, 2-methoxy-4-(2-propenyl)phenol, 3,4-dihydroxy benzaldehyde, 2,3-dihydroxy benzaldehyde, benzylamine, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl
- di-tert-butyl hydroxy toluene which is for example commercially available from SHELL under the trade name IONOL CP® and/or tert-butyl-hydroxy anysole and/or propyl gallate.
- IONOL CP® tert-butyl-hydroxy anysole and/or propyl gallate.
- compositions according to the present invention may comprise up to 5%, preferably from 0.002% to 1.5% by weight and more preferably from 0.002% to 0.5% by weight of the total composition of a radical scavenger.
Landscapes
- Detergent Compositions (AREA)
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP99870118A EP1062903A1 (fr) | 1999-06-07 | 1999-06-07 | Méthode de nettoyage de tapis utilisant un gant |
AU60483/00A AU6048300A (en) | 1999-06-07 | 2000-06-06 | Process of cleaning a carpet with a glove |
PCT/US2000/015584 WO2000074550A1 (fr) | 1999-06-07 | 2000-06-06 | Méthode de nettoyage de moquette au moyen d'un gant |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP99870118A EP1062903A1 (fr) | 1999-06-07 | 1999-06-07 | Méthode de nettoyage de tapis utilisant un gant |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1062903A1 true EP1062903A1 (fr) | 2000-12-27 |
Family
ID=8243847
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99870118A Withdrawn EP1062903A1 (fr) | 1999-06-07 | 1999-06-07 | Méthode de nettoyage de tapis utilisant un gant |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP1062903A1 (fr) |
AU (1) | AU6048300A (fr) |
WO (1) | WO2000074550A1 (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006136440A1 (fr) * | 2005-06-23 | 2006-12-28 | Tex-A-Tec Ag | Moyens et articles pour le traitement de surfaces |
CZ298323B6 (cs) * | 2001-05-11 | 2007-08-29 | Vrstvená uterka |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7584519B2 (en) | 2003-06-05 | 2009-09-08 | The Clorox Company | Disposable mitt or glove containing treatment composition |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2061709A (en) * | 1979-10-30 | 1981-05-20 | Beecham Walters J E | Pad |
US4980943A (en) * | 1989-05-18 | 1991-01-01 | Stockwell Group, Inc. | Cleaning glove |
EP0546426A1 (fr) * | 1991-12-07 | 1993-06-16 | Margarete Burkhardt | Article de nettoyage et polissage de surfaces |
CH682207A5 (en) * | 1991-07-15 | 1993-08-13 | Zohreh Tahmourpour | Cleaning glove for vegetables, fish, body care etc. - is made of sponge material capable of suction and has scraping or scrubbing layer |
WO1994023636A1 (fr) * | 1993-04-16 | 1994-10-27 | Henkel-Ecolab Gmbh & Co. Ohg | Manchon enfichable sur le support d'un appareil de nettoyage destine en particulier au nettoyage de tapis |
EP0629694A1 (fr) * | 1993-06-09 | 1994-12-21 | The Procter & Gamble Company | Procédé de nettoyage de tapis |
EP0753280A2 (fr) * | 1995-07-13 | 1997-01-15 | MELITTA HAUSHALTSPRODUKTE GmbH & Co. Kommanditgesellschaft | Gant de nettoyage |
JPH09122057A (ja) * | 1995-11-06 | 1997-05-13 | Matsuo Sonoda | 3層手袋状掃除具 |
-
1999
- 1999-06-07 EP EP99870118A patent/EP1062903A1/fr not_active Withdrawn
-
2000
- 2000-06-06 AU AU60483/00A patent/AU6048300A/en not_active Abandoned
- 2000-06-06 WO PCT/US2000/015584 patent/WO2000074550A1/fr active Application Filing
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2061709A (en) * | 1979-10-30 | 1981-05-20 | Beecham Walters J E | Pad |
US4980943A (en) * | 1989-05-18 | 1991-01-01 | Stockwell Group, Inc. | Cleaning glove |
CH682207A5 (en) * | 1991-07-15 | 1993-08-13 | Zohreh Tahmourpour | Cleaning glove for vegetables, fish, body care etc. - is made of sponge material capable of suction and has scraping or scrubbing layer |
EP0546426A1 (fr) * | 1991-12-07 | 1993-06-16 | Margarete Burkhardt | Article de nettoyage et polissage de surfaces |
WO1994023636A1 (fr) * | 1993-04-16 | 1994-10-27 | Henkel-Ecolab Gmbh & Co. Ohg | Manchon enfichable sur le support d'un appareil de nettoyage destine en particulier au nettoyage de tapis |
EP0629694A1 (fr) * | 1993-06-09 | 1994-12-21 | The Procter & Gamble Company | Procédé de nettoyage de tapis |
EP0753280A2 (fr) * | 1995-07-13 | 1997-01-15 | MELITTA HAUSHALTSPRODUKTE GmbH & Co. Kommanditgesellschaft | Gant de nettoyage |
JPH09122057A (ja) * | 1995-11-06 | 1997-05-13 | Matsuo Sonoda | 3層手袋状掃除具 |
Non-Patent Citations (1)
Title |
---|
PATENT ABSTRACTS OF JAPAN vol. 1997, no. 09 30 September 1997 (1997-09-30) * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CZ298323B6 (cs) * | 2001-05-11 | 2007-08-29 | Vrstvená uterka | |
WO2006136440A1 (fr) * | 2005-06-23 | 2006-12-28 | Tex-A-Tec Ag | Moyens et articles pour le traitement de surfaces |
Also Published As
Publication number | Publication date |
---|---|
AU6048300A (en) | 2000-12-28 |
WO2000074550A1 (fr) | 2000-12-14 |
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