WO2004057096A1 - Procede de nettoyage a sec - Google Patents

Procede de nettoyage a sec Download PDF

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Publication number
WO2004057096A1
WO2004057096A1 PCT/EP2003/013827 EP0313827W WO2004057096A1 WO 2004057096 A1 WO2004057096 A1 WO 2004057096A1 EP 0313827 W EP0313827 W EP 0313827W WO 2004057096 A1 WO2004057096 A1 WO 2004057096A1
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WO
WIPO (PCT)
Prior art keywords
dry cleaning
surfactant
water
solvent
composition
Prior art date
Application number
PCT/EP2003/013827
Other languages
English (en)
Inventor
Johannes Maria Wilhelmus Evers
Machiel Goedhart
Freddie Kerpels
Cornelis Gerhard Van Kralingen
Pieter Everhardus Maria Overdevest
Hank Robert Reinhoudt
Karin Vrieswijk
Original Assignee
Unilever N.V.
Unilever Plc
Hindustan Lever Limited
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 Unilever N.V., Unilever Plc, Hindustan Lever Limited filed Critical Unilever N.V.
Priority to AU2003289973A priority Critical patent/AU2003289973A1/en
Publication of WO2004057096A1 publication Critical patent/WO2004057096A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • D06L1/22—Processes involving successive treatments with aqueous and organic agents
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • D06L1/12—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents

Definitions

  • the present invention relates to a dry cleaning process, in particular for cleaning articles, especially laundry articles.
  • Laundry articles can be cleaned using water as the primary medium with surfactants and other cleaning agents. However, not all laundry articles can be cleaned using water. These articles are cleaned in a dry cleaning process wherein an organic dry cleaning solvent is used as the primary medium. In dry cleaning usually the laundry articles are immersed in or washed with solvent liquids. Applications involving one or more stages of immersion, rinsing and/or drying are known. Solvents can be used at ambient temperature or at elevated temperatures up to the boiling point of the solvent.
  • Liquid carbondioxide is one example, but the high pressure equipment needed for this inorganic dry cleaning solvent makes it unpractical and prohibitively expensive.
  • a novel and more promising class of dry cleaning solvents are the so called non-flammable, non-chlorine containing organic dry cleaning solvents. Examples may include hydrofluoroethers such as nonafluoromethoxybutane and nonafluoroethoxybutane or hydrofluorocarbons as decafluoropentane.
  • Hydrofluoroethers are relatively low in toxicity, are claimed to have zero ozone depletion potential, have relatively short atmospheric lifetimes, and can have very low global warming potentials relative to chlorofluorocarbons and many chlorofluorocarbon substitutes. Furthermore, HFEs are listed as non-volatile organic compounds by the EPA, and as such are not considered as smog precursors .
  • WO 00/36206 discloses a dry cleaning composition comprising hydrofluoroether, 1-30 wt.% of a nonionic fluorosurfactant and less than 1 wt.% water.
  • JP 11140499 discloses a dry cleaning composition comprising hydrofluoroether, 0 percent water and 10 and up to 90 wt.% of salt of a fluoralkyl phosphate surfactant.
  • US 6 127 430 discloses a composition comprising from 0.1 to 99 parts by weight of hydrofluoroether and from 99.9 to 1 parts by weight of water, the sum of a and b equalling 100 parts, and certain fluorinated surfactants.
  • WO 97/22683 (3M) discloses a dry cleaning composition comprising hydrofluoroether and 0.1 wt.% of a nonionic surfactant like fluoralkyl sulphon amide.
  • US 5 610 128 discloses compositions with perfluoroalkylamine salts of octylphenyl acid phosphate.
  • particulate soil is a common domestic stain that is difficult to clean using dry cleaning only without extensive manual pretreatment . Redeposition of soil often represents another problem in dry cleaning. Other common domestic stains such as kitchen grease are also difficult to remove with fluorinated solvents .
  • the dry cleaning process according to this aspect of the invention delivers effective cleaning and/or surprisingly good garment care including a reduction in shrinkage and/or in the formation of wrinkles.
  • Garment care including minimising or avoiding wrinkles is a significant benefit since this would reduce the need for time and energy consuming ironing of the laundry articles.
  • the present invention is particularly suitable for an in-home dry cleaning application because it is possible to use very low volumes of organic dry cleaning solvent (liquid to cloth ratio) and still obtain effective cleaning and/or garment care. Because low volumes of organic dry cleaning solvent are used, the dry cleaning process is highly suitable for non-industrial application since it can be carried out in a relatively small and cost effective dry cleaning apparatus .
  • dry cleaning process used herein is intended to mean any process wherein laundry articles are contacted with a dry cleaning composition within a closable vessel. However, as used herein this term does not include any process comprising steps wherein the laundry articles are also immersed and rinsed in an aqueous cleaning composition comprising more than 80 wt.% water because this would damage garments that can only be dry cleaned.
  • dry cleaning composition as used herein is intended to mean the composition used in the dry cleaning process including the dry cleaning solvent, any surfactant, cleaning agents but excluding the laundry articles that are to be cleaned.
  • organic dry cleaning solvent as used herein is intended to mean any non-aqueous solvent that preferably has a liquid phase at 20°C and standard pressure.
  • organic has its usual meaning, i.e., a compound with at least one carbon hydrogen bond.
  • weight of the cloth When referring to the "weight of the cloth”, it is intended to mean the weight of the cloth of the laundry article after the cloth has been equilibrated at 20°C, a relative humidity of 55% and standard pressure. Except in the case of determining the water in cloth ratio, then the weight of the cloth is the dry weight of the cloth (see test below) .
  • the term "laundry article” as used herein is typically a garment but may include any textile article. Textile articles include - but are not limited to - those made from natural fibres such as cotton, wool, linen, hemp, silk and man made fibres such as nylon, viscose, acetate, polyester, polyamide, polypropylene elastomer, natural or synthetic leather, natural or synthetic fur and mixtures thereof.
  • liquid to cloth ratio (w/w) (LCR) as used herein is intended to mean the ratio of the weight of the total amount of dry cleaning composition to the weight of the cloth as defined above .
  • immerse as used herein is intended to mean that the laundry article is contacted with a cleaning effective amount of dry cleaning composition in a step of the dry cleaning process to wet the laundry article which is usually a LCR of greater than 0.5 or more preferably a LCR as given below.
  • cleaning effective amount as defined herein is intended to mean an amount effective to obtain the desired cleaning.
  • in-home as defined herein is intended to mean that the LCR of the dry cleaning step is at most 20. Although, the in-home dry cleaning is especially suitable for domestic homes, in some cases these small appliances may also be used in hotels, airports on a non-industrial scale.
  • the water content refers to water purposefully added to the laundry articles, for example as part of the dry cleaning composition as such or a pretreat ent composition, including hydrated water as part of ingredients making up these compositions. It is not intended to include the moisture of the untreated wash load e.g., a wet towel.
  • a dry cleaning process comprising a low-aqueous dry cleaning step of contacting a laundry article with a low-aqueous dry cleaning said composition comprising: a) a non-flammable, non-chlorine containing organic dry cleaning solvent, b) a surfactant; and c) water whereby the amounts of surfactant, water and cloth are such that the water in cloth ratio (w/w) (WIC) after said step is less than 0.25.
  • WIC water in cloth ratio
  • this WIC preferably applies to all steps in the dry cleaning process, especially when the dry cleaning composition comprises water and solvent. However, the WIC may or may not differ for each step. It is also preferred that this WIC applies to each step in the dry cleaning process wherein the LCR is more than 1.
  • the dry cleaning composition may comprise water to aid in the cleaning. After removal of the dry cleaning composition by for example draining and/or spinning, the laundry article probably still comprises minor amounts of the dry cleaning composition including water when used.
  • the WIC can be simply measured by any known method in the art. Alternatively, the amount of water in the dry cleaning composition before and after the dry cleaning step can be used to determine the WIC.
  • the WIC may differ for different types of fabric but is preferably measured for cotton since cotton is often relatively sensitive to wrinkling.
  • the WIC is determined as follows,
  • the desired WIC of less than 0.25 can be simply obtained by, for example, decreasing the amount of water in the dry cleaning composition or by increasing the amount of surfactant in respect of the amount of water.
  • the dry cleaning process is carried out in a closable vessel, usually part of an automated dry cleaning apparatus with means to recycle a specific solvent or class of solvents. Generally, the skilled person will start from a situation wherein the amount of solvent and cloth are dictated by the dimension of the dry cleaning apparatus.
  • One particular advantage of the present invention is that it is also possible to use relatively high levels of water in the dry cleaning composition which are needed to remove for example hydrophilic composite stains, while maintaining good garment care. This can be easily achieved by the skilled person by raising the amount of surfactant so the desired WIC of less than 0.25 is obtained.
  • the water to surfactant ratio (w/w) is at most 150, more preferably at most 100, more preferably at most 25 but preferably at least 0.75, more preferably at least 2 and most preferably at least 3.
  • one preferred dry cleaning process further comprises a non-aqueous dry cleaning step wherein the laundry article contacted with a non- aqueous dry cleaning composition, said non-aqueous dry cleaning composition comprising 0.001 to 10 wt.% of a surfactant; 0 to 0.01 wt.% of water; 0 to 50 wt.% of a cosolvent and a non-flammable, non-chlorine containing organic dry cleaning solvent.
  • a sequential dry cleaning process comprising: a) a non-aqueous dry cleaning step, wherein said articles are contacted with a non-aqueous dry cleaning composition said non-aqueous dry cleaning composition comprising 0.001 to 10 wt.% of a surfactant;
  • the low aqueous and non- aqueous compositions may be used in any order. However, in some cases it will be preferred to contact the articles with a non- aqueous composition prior to a low aqueous dry cleaning composition. In fact, the low aqueous dry cleaning step may be followed or preceded with various other steps such as a regeneration, garment care treatment and/or rinsing step, and, in fact, any other step known to the person skilled in the art.
  • the dry cleaning process preferably comprises the step of contacting a laundry article with a dry cleaning composition whereby the laundry article is stained with domestic stain material selected from kitchen grease, particulate soil and mixtures thereof.
  • Typical particulate soil stains comprise any particulate matter which is capable of staining garments, such as dirt, mud, sand, charcoal, make up, deodorant, toothpaste but also corroded iron particles and mixtures thereof.
  • Kitchen grease usually comprises edible fats and oils of animal or vegetable origin such as lard, sunflower oil, soy oil, olive oil, palm oil, peanut oil, rapeseed oil and mixtures thereof.
  • articles such as clothing are cleaned by contacting a cleaning effective amount of the dry cleaning composition according to one aspect of the invention with the articles for an effective period of time to clean the articles or otherwise remove stains.
  • the laundry article is immersed in the dry cleaning composition.
  • the amount of dry cleaning composition used and the amount of time the composition contacts the article can vary based on equipment and the number of articles being cleaned.
  • the dry cleaning process will comprise at least one step of contacting the article with dry cleaning composition according to the first aspect of the invention and at least one step of rinsing the article with a fresh load of dry cleaning solvent.
  • the rinse composition will usually comprise of mainly solvent but cleaning agents may be added as desired.
  • the amount of dry cleaning composition used to clean a certain amount of laundry articles in a step of the dry cleaning process can be important.
  • these amounts are expressed as the liquid to cloth ratio or LCR.
  • the LCR is at most 20, more preferably at most 10, even more preferably at most 7 and preferably greater than 0.5, more preferably greater than 0.7, even more preferably greater than 1 and most preferably greater than 2.5.
  • the same LCR may be used wherein the "liquid" refers to the rinse composition which usually comprises only organic dry cleaning solvent with optionally some cleaning agents.
  • the LCR of each step may be different or the same.
  • the LCR of each step is as described above.
  • the dry cleaning process may comprise different steps in any order depending on the desired outcome.
  • the number and length of steps for e.g., cleaning, rinsing, conditioning steps may depend on the desired outcome.
  • Each step may preferably last from at least 0.1 min, or preferably at least 0.5 min or more preferably at least 1 min or even 5 min, and at most 2 hrs, preferably at most 30 min, even more preferably at most 20 min and in some instances at most 5 min. In some cases longer times may be desired for example overnight.
  • each step comprises contacting the laundry article with a composition tailored for that step, e.g. a dry cleaning composition for a cleaning step, a rinsing composition for a rinsing step, a conditioning composition for a conditioning step.
  • the last rinsing step may also be a conditioning step when the composition comprises conditioning agents while it also rinses off any unwanted residues e.g. soil or surfactants.
  • a step will normally comprise contacting the laundry article with a composition, agitating the laundry article in the composition, removing the composition from the laundry article. The removal may be carried out by any means known in the art such draining, spinning or when appropriate evaporating the composition, or any combination thereof.
  • the laundry articles in need of treatment are placed inside a closable vessel.
  • the vessel is a rotatable drum as part of an automated dry cleaning machine that is closed or sealed in such a way that the dry cleaning solvent can be contained within the machine if needed.
  • the laundry articles are then contacted with the dry cleaning composition. This may be done in any way known in the art such as spraying or even using a mist.
  • the dry cleaning composition in situ in the drum by contacting the different ingredients of the dry cleaning composition separately with the laundry articles.
  • the dry cleaning composition comprises dry cleaning solvent, water and surfactant - first water, then surfactant followed by the dry cleaning solvent. Or first the dry cleaning solvent, followed by the surfactant and then water. Or any other order.
  • ingredients may be premixed before they are contacted with the laundry articles.
  • water and surfactant may be premixed and this premix is then contacted with the laundry followed by the dry cleaning solvent.
  • dry cleaning solvent and surfactant may be premixed and this premix is then contacted with the laundry followed by water.
  • in situ formulation of the dry cleaning composition may also be provided by incorporating one or more ingredients of the dry cleaning composition into a pretreatment composition, pretreating the laundry articles with the pretreatment composition, contacting the laundry articles with the remaining ingredients of the dry cleaning composition thereby formulating the dry cleaning composition in situ.
  • This pretreatment may take place manually outside the drum or mechanically inside the drum as part of a pretreatment step.
  • the pretreatment step per se need not be immersive, i.e., it may be limited to treating the stained areas only provided that when the laundry articles are contacted with all the ingredients making up the final dry cleaning composition, the laundry articles are immersed in said dry cleaning composition.
  • the dry cleaning composition comprises of dry cleaning solvent
  • water and surfactant - stained areas of the laundry articles may be pre-treated with a premix of water and surfactant manually or by an automated process.
  • the laundry articles may be contacted in the drum with the remaining ingredients such as in this case, the dry cleaning solvent (and optionally the remaining amounts of water and cleaning agent) to result in situ in the dry cleaning composition according to this aspect of the invention.
  • the pretreatment time will be at least 5 sec but could be less than 1 day, preferably less than 1 hr, more preferably less than 30 min.
  • the pretreatment composition may be formulated to treat specific stains. For example cleaning effective amounts of protease and other enzymes may be included to treat proteinacious stains.
  • the complete dry cleaning composition is premixed in a separate premix compartment.
  • the dry cleaning composition comprises dry cleaning solvent, surfactant and water
  • these may be premixed in a separate compartment before the dry cleaning composition is contacted with the laundry article.
  • a premix is in the form of an emulsion or microemulsion.
  • Forming a premix of for example a water-in-oil emulsion can be brought about by any number of suitable procedures.
  • the aqueous phase containing a cleaning effective amount of surfactant package can be contacted with the solvent phase by metered injection just prior to a suitable mixing device. Metering is preferably maintained such that the desired solvent/water ratio remains relatively constant.
  • Mixing devices such as pump assemblies or in-line static mixers, a centrifugal pump or other type of pump, a colloid mill or other type of mill, a rotary mixer, an ultrasonic mixer and other means of dispersing one liquid in another, non-miscible liquid can be used to provide effective agitation to cause emulsification.
  • static mixers are devices through which the emulsion is passed at high speed and in which said emulsion experiences sudden changes in direction and/or in the diameter of the channels which make up the interior of the mixers. This results in a pressure loss, which is a factor in obtaining a correct emulsion in terms of droplet size and stability.
  • the mixing steps are for example sequential.
  • the procedure consists in mixing the solvent and emulsifier in a first stage, the premix being mixed and emulsified with the water in a second stage.
  • the premix may take place at room temperature, which is also the temperature of the fluids and raw materials used.
  • a batch process such as an overhead mixer or a continuous process such as a two fluid co-extrusion nozzle, an in-line injector, an in-line mixer or an in-line screen can be used to make the emulsion.
  • the size of the emulsion composition in the final composition can be manipulated by changing the mixing speed, mixing time, the mixing device and the viscosity of the aqueous solution. In general, by reducing the mixing speed, decreasing the mixing time, lowering the viscosity of the aqueous solution or using a mixing device that produces less shear force during mixing, one can produce an emulsion of a larger droplet size.
  • ultrasonic mixers are especially preferred.
  • composition may be in the form of a micro-emulsion but usually will be in the form of a macro-emulsion, which is generally accepted to be thermodynamically unstable.
  • a suitable process and appliance for dry cleaning is described in US 6 045 588.
  • the solvent will preferably be filtered and recycled in the same appliance.
  • the laundry articles will be agitated in the dry cleaning process by tumbling, rotating, ultrasonics or any suitable type of mechanical energy (see US 6
  • the dry cleaning solvent is usually a non-flammable, non- chlorine containing organic dry cleaning solvent.
  • dry cleaning solvent is used in the singular, it should be noted that a mixture of solvents may also be used. Thus, the singular should be taken to encompass the plural, and vice versa .
  • the solvent preferably does not contain Cl atoms.
  • the solvent should not be flammable such as most petroleum or mineral spirits having typical flash points as low as 20°C or even lower.
  • nonflammable is intended to describe dry cleaning solvents with a flash point of at least 37.8°C, more preferably at least 45°C, most preferably at least 50°C.
  • the limit of a flashpoint of at least 37.8°C for non-flammable liquids is defined in NFPA 30, the Flammable and Combustible Liquids Code as issued by
  • NFPA30 One preferable class of solvents is a fluorinated organic dry cleaning solvent including hydrofluorocarbon (HFC) and hydrofluoroether (HFE) .
  • HFC hydrofluorocarbon
  • HFE hydrofluoroether
  • non flammable non-halogenated solvents such as siloxanes (see below) . It should be noted that mixtures of different dry cleaning solvents may also be used.
  • the ozone depleting potential is the ratio of the impact on ozone of a chemical compared to the impact of a similar mass of CFC- 11.
  • the ODP of CFC-11 is defined to be 1.0.
  • One preferred hydrofluorocarbon solvent is represented by the formula C x H y F ( 2x+2 . y ) , wherein x is from 3 to 8, y is from 1 to 6, the mole ratio of F/H in the hydrofluorocarbon solvent is greater than 1.6.
  • x is from 4 to 6 and most preferred x is 5 and y is 2.
  • hydrofluorocarbon solvents selected from isomers of decafluoropentane and mixtures thereof.
  • isomers of decafluoropentane and mixtures thereof are particularly useful.
  • 1, 1, 1, 2, 2, 3, 4, 5, 5, 5-decafluoropentane is particularly useful.
  • the E.I. Du Pont De Nemours and Company markets this compound under the name Vertrel XFTM.
  • Hydrofluoroethers are particularly suitable.
  • Hydrofluoroethers suitable for use in the present invention are generally low polarity chemical compounds minimally containing carbon, fluorine, hydrogen, and catenary (that is, in-chain) oxygen atoms. HFEs can optionally contain additional catenary heteroatoms, such as nitrogen and sulphur. HFEs have molecular structures which can be linear, branched, or cyclic, or a combination thereof (such as alkylcycloaliphatic) , and are preferably free of ethylenic unsaturation, having a total of about 4 to about 20 carbon atoms. Such HFEs are known and are readily available, either as essentially pure compounds or as mixtures.
  • Preferred hydrofluoroethers can have a boiling point in the range from about 40 °C to about 275 °C, preferably from about 50 °C to about 200 °C, even more preferably from about 50 °C to about 121 °C. It is very desirable that the hydrofluoroether has no flashpoint. In general, when a HFE has a flash point, decreasing the F/H ratio or decreasing the number of carbon- carbon bonds each decreases the flash point of the HFE (see WO/00 26206) .
  • Useful hydrofluoroethers include two varieties: segregated hydrofluoroethers and omega-hydrofluoroalkylethers .
  • the segregated hydrofluoroethers comprise at least one mono-, di-, or trialkoxy-substituted perfluoroalkane, perfluorocycloalkane, perfluorocycloalkyl-containing perfluoroalkane, or perfluorocycloalkylene-containing perfluoroalkane compound.
  • HFEs suitable for use in the processes of the invention include the following compounds: C 4 F 9 OC 2 F 4 H
  • Preferred HFEs are according to the formula
  • X and Y are each independently F or H provided that at least one F is present.
  • a suitable dry cleaning composition may comprise a mixture of at least one HFE together with at least one siloxane.
  • suitable HFEs include nonafluoromethoxybutane (C4F90CH3) isomers such as 1, 1, 1, 2, 2, 3, 3, , 4-nonafluoro-4- methoxy-butane (CH30CF2CF2CF2CF3) , 1, 1, 1, 2, 3, 3-hexafluoro-2-
  • siloxane solvents may also be used advantageously in the present invention.
  • the siloxane may be linear, branched, cyclic, or a combination thereof.
  • One preferred branched siloxane is tris (trimethylsiloxyl) silane.
  • Also preferred are linear and cyclic oligo dimethylsiloxanes.
  • One preferred class of siloxane solvents is an alkylsiloxane represented by the formula
  • each R is independently chosen from an alkyl group having form 1 to 10 carbon atoms and w is an integer from 1 to 30.
  • R is methyl and w is 1-4 or even more preferably w is 3 or 4.
  • cyclic siloxane octamethyl cyclotetrasiloxane and decamethyl cyclopentasiloxane are particularly effective.
  • Very useful siloxanes are selected from the group consisting of decamethyl tetrasiloxane, dodecamethyl pentasiloxane and mixtures thereof.
  • the organic dry cleaning solvent is not a terpene or isoparaffinic solvent.
  • the dry cleaning composition comprises a terpene or an isoparaffinic solvent (as defined above) then the dry cleaning composition comprises less than 50 wt.% more preferably less than 10 wt.%, even more preferably less than 1 wt.% of a terpene and/or isoparaffinic solvent by weight of the total dry cleaning composition.
  • Especially suitable organic dry cleaning solvents include those selected from the group consisting of the isomers of nonafluoromethoxybutane, nonafluoroethoxybutane and decafluoropentane, octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, decamethyl tetrasiloxane, dodecamethyl pentasiloxane and mixtures thereof.
  • Even more preferred organic dry cleaning solvents include those selected from the group consisting of octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, decamethyl tetrasiloxane, dodecamethyl pentasiloxane and mixtures thereof.
  • the dry cleaning compositions of the invention generally contain greater than about 50 percent by weight of organic dry cleaning solvent, preferably greater than about 75 weight percent, more preferably greater than about 80 weight percent, more preferably greater than about 85 weight percent, even more preferably greater than about 95 weight percent, but preferably less than 100 weight percent of organic dry cleaning solvent by weight of the total dry cleaning composition. Such amounts aid in improved drying times and maintain a high flashpoint or no flashpoint at all.
  • the dry cleaning compositions may even comprise of at least 99 weight percent of organic dry cleaning solvent by weight of the total dry cleaning composition and sometimes even 100 weight percent of organic dry cleaning solvent.
  • water may be used in the dry cleaning process and the amount of water is important.
  • the amount of water present in any step of the dry cleaning process is at such a level that laundry articles can be safely cleaned. This includes laundry articles that can only be dry cleaned.
  • the amount of water present in the low aqueous dry cleaning composition is preferably from 0.01 to 50 wt.% water more preferably from 0.01 to 10 wt.%, even more preferably from 0.01 to 0.9 wt.% water by weight of the dry cleaning composition or more preferably, 0.05 to 0.8 wt.% or most preferable 0.1 to 0.7 wt.%.
  • the amount of water present in the non-aqueous dry cleaning composition is preferably from 0 to 0.1 wt.% water by weight of the dry cleaning composition or more preferably, 0 to 0.01 wt.% or even more preferable 0 to 0.001 wt.% and most preferable 0 wt.%.
  • compositions of the invention may contain one or more cosolvents.
  • the purpose of a cosolvent in the dry cleaning compositions of the invention is often to increase the solvency of the dry cleaning composition for a variety of soils.
  • the cosolvent also enables the formation of a homogeneous solution containing a cosolvent, a dry cleaning solvent, and the soil; or a cosolvent, a dry cleaning solvent and an optional cleaning agent.
  • a "homogeneous composition” is a single phased composition or a composition that appears to have only a single phase, for example, a macro-emulsion, a micro-emulsion or an azeotrope.
  • the dry cleaning composition is preferably a non-azeotrope as azeotropes may be less robust.
  • Useful cosolvents of the invention are soluble in the dry cleaning solvent or water, are compatible with typical cleaning agents, and can enhance the solubilisation of hydrophilic composite stains and oils typically found in stains on clothing, such as vegetable, mineral, or animal oils. Any cosolvent or mixtures of cosolvents meeting the above criteria may be used.
  • Useful cosolvents include alcohols, ethers, glycol ethers, alkanes, alkenes, linear and cyclic amides, perfluorinated tertiary amines, perfluoroethers, cycloalkanes, esters, ketones, aromatics, the fully or partly halogenated derivatives thereof and mixtures thereof.
  • the cosolvent is selected from the group consisting of alcohols, alkanes, alkenes, cycloalkanes, ethers, esters, cyclic amides, aromatics, ketones, the fully or partly halogenated derivatives thereof and mixtures thereof.
  • cosolvents which can be used in the dry cleaning compositions of the invention include methanol, ethanol, isopropanol, t- butyl alcohol, trifluoroethanol, pentafluoropropanol, hexafluoro-2-propanol, methyl t-butyl ether, methyl t-amyl ether, propylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, propylene glycol methyl ether, ethylene glycol monobutyl ether, trans-1, 2-dichloroethylene, decalin, methyl decanoate, t-butyl acetate, ethyl acetate, glycol methyl ether acetate, ethyl lactate, diethyl phthalate, 2-butanone, N-alkyl pyrrolidone (such as N-methyl pyrrolidone,
  • the cosolvent is present in the compositions of the invention in an effective amount by weight to form a homogeneous composition with the other dry cleaning solvent (s) such as HFE.
  • the effective amount of cosolvent will vary depending upon which cosolvent or cosolvent blends are used and the other dry cleaning solvent (s) used in the composition.
  • the preferred maximum amount of any particular cosolvent present in a dry cleaning composition should be low enough to keep the dry cleaning composition non-flammable as defined above.
  • cosolvent may be present in the compositions of the invention in an amount of from about 1 to 50 percent by weight, preferably from about 5 to about 40 percent by weight, and more preferably from about 10 to about 25 percent by weight. In some exceptional cases the cosolvent may be present amounts of from about 0.01 percent by weight of the total dry cleaning composition.
  • the dry cleaning compositions of the invention can utilise many types of cyclic, linear or branched surfactants known in the art, both fluorinated and non-fluorinated.
  • Preferred solvent compatible surfactants include nonionic, anionic, cationic and zwitterionic surfactants having at least 4 carbon atoms, but preferably less than 200 carbon atoms or more preferably less than 90 carbon atoms as described below.
  • Solvent compatible surfactants usually have a solvent-philic part that increases the solubility of the surfactant in the dry cleaning solvent/composition.
  • Effective surfactants may comprise of one or more polar hydrophilic groups and one or more dry cleaning solvent-philic parts having at least 4 carbon atoms so that the surfactant is soluble in said dry cleaning solvent/composition. It is preferred that the surfactant is soluble in the dry cleaning composition, i.e., to at least the amount of surfactant used in the dry cleaning composition at 20 °C.
  • the composition may comprise one or a mixture of surfactants depending on the desired cleaning and garment care.
  • One preferred surfactant is an anionic surfactant.
  • Another preferred surfactant is a cationic surfactant.
  • Preferred surfactants are compounds that act as interfacial tension modifiers for a particular solvent-water combination.
  • Interfacial tension modifiers are defined herein as surfactants which lower the solvent-water interfacial tension to less than 10 mN/m, preferably less than 3 mN/m, more preferably less than 1 mN/m.
  • the determination of interfacial tension is a standard laboratory method.
  • Preferred methods to determine the interfacial tension include the spinning and the pendant drop method. Suitable devices are for example the SITE04 Spinning drop Tensiometer and the DSA-10 Drop shape analyser for the pendant drop method (both ex Kruss) .
  • the surfactant should preferably be used in a concentration higher than the critical micelle concentration such as in a concentration of 3 wt.% by weight of the total composition.
  • Particularly preferred surfactants are those that are more soluble in the solvent than in water.
  • the solubility can be easily tested by comparing the amount of surfactant that still dissolves in 100 ml of a solvent to the amount that dissolves in 100 ml water at 20 °C.
  • the surfactant is assumed to dissolve when it results in a transparent or translucent solution.
  • Water-in-solvent emulsifying surfactants which are effective in stabilising water-in-solvent emulsions.
  • Water-in-solvent emulsifying surfactants for the present purpose are those surfactants which form stable water-in- solvent emulsions of 1 wt.% water at 5 wt.% surfactant after 60 sec of high shear agitation with an ultra-turrax (Polytron PT3100 with stirrer probe PT-DA3012/2S, ex Kinematica) at 27000 rpm, whereby the formed emulsions remain stable for at least 15 min at 20°C.
  • the surfactant has an HLB of less than 13; and preferably, less than about 12; and most preferably, less than about 10.
  • Typical examples include surfactants having a bulky hydrophobic moiety and a smaller hydrophilic moiety such as for example low
  • EO/PO surfactants multiple tail surfactants such as a sulfosuccinate with two hydrocarbon tails and Crodafos 810A (ex Croda) , which is a mixture of phosphate esters with one or two
  • the polar hydrophilic group, Z can be nonionic, ionic (that is, anionic, cationic, or amphoteric) , or a combination thereof.
  • Typical nonionic moieties include polyoxyethylene and polyoxypropylene moieties.
  • Typical anionic moieties include carboxylate, sulfonate, sulfate, or phosphate moieties.
  • Typical cationic moieties include quaternary ammonium, protonated ammonium, imidazolines, amines, diamines, sulfonium, and phosphonium moieties.
  • amphoteric moieties include betaine, sulfobetaine, aminocarboxyl, amine oxide, and various other combinations of anionic and cationic moieties.
  • suitable surfactants comprise at least one polar hydrophilic group Z which is an anionic moiety whereby the counterion may be as described below.
  • the polar hydrophilic group Z is preferably selected from the group comprising -S0 4 M, -S0 3 M, -P0M 2 , -P0 3 M 2 , -C0 2 M and mixtures thereof wherein each M can be independently selected from the group including H, NR 4 , Na, K and Li, wherein each R is independently selected from H and C 1 -. 4 alkyl radical but preferably H.
  • M is H but in some cases salts may also be used.
  • the surfactant is fluorinated or more preferably a fluorinated acid. Suitable fluorosurfactants are in most cases those according to the formula (I) :
  • Xf fluorinated radicals
  • Z polar hydrophilic groups
  • Y suitable linking groups
  • n and p are integers independently selected from 1 to 4 and m is selected from 0 to 4.
  • the surfactant comprises more than one Xf, Y or Z group, then each of Xf, Y and Z may be the same or different.
  • the polar hydrophilic group is connected by a covalent bond to Y, or in absence of Y, to Xf.
  • the fluorinated radical, Xf can generally be a linear or cyclic, saturated or unsaturated, aromatic or non-aromatic, radical preferably having at least 3 carbon atoms.
  • the carbon chain may be linear or branched and may include hetero atoms such as oxygen or sulphur, but preferably not nitrogen.
  • Xf is an aliphatic and saturated.
  • a fully fluorinated Xf radical is preferred, but hydrogen or chlorine may be present as substituents provided that not more than one atom of either is present for every two carbon atoms, and, preferably, the radical contains at least a terminal perfluoromethyl group. Radicals containing no more than about 20 carbon atoms are preferred because larger radicals usually represent a less efficient utilisation of fluorine.
  • Xf groups can be based on perfluorinated carbon: C n F 2n+ ⁇ - wherein n is from 1-40, preferably 2 to 26, most preferably 2 to 18 or can be based on oligomers of hexafluoropropyleneoxide: [CF(CF 3 ) - CF 2 - 0] n wherein n is from
  • KrytoxTM 157 especially, KrytoxTM 157 FSL.
  • Fluoroaliphatic radicals containing about 2 to 14 carbon atoms are more preferred.
  • the linking group, Y is selected from groups such as alkyl, alkylene, alkylene oxide, arylene, carbonyl, ester, amide, ether oxygen, secondary or tertiary amine, sulfonamidoalkylene, carboxamidoalkylene, alkylenesulfonamidoalkylene, alkyleneoxyalkylene, or alkylenethioalkylene or mixtures thereof.
  • Y is (CH 2 ) t or (CH 2 )tO wherein t is 1 to 10, preferably 1 to 6, most preferably 2 to 4.
  • Y may be absent, in which case Xf and Z are directly connected by a covalent bond.
  • a particularly useful class of fluoroaliphatic surfactants useful in this invention are those wherein Xf, Y, and Z are as defined, and n is 1 or 2, m is 0 to 2, and p is 1 or 2.
  • n 1 to 4
  • p 1 to 4
  • Z is as defined and
  • R 1 is a perfluoroalkyl group having 1 to 40 carbon atoms
  • R 2 is an alkyl or an alkylene oxide group having 2 to 6 carbon atoms
  • v is 0-10
  • the surfactant is according to the formula [R 1 -R 2 v ] w PO ( OH) 3 _
  • R 1 is a perfluoroalkyl group having 1 to 26 carbon atoms
  • R 2 is an alkyl or an alkylene oxide group having 2 to 6 carbon atoms
  • v is 0-10 and w is 1-2.
  • R 1 is a perfluoroalkyl group having 2 to 16 carbon atoms
  • R 2 is an alkyl or an alkylene oxide group having 2 to 6 carbon atoms
  • v is 1 and w is 1 or 2.
  • R 1 is a perfluoroalkyl group having 2 to 14 carbon atoms
  • R 2 is ethylene oxide
  • Non-fluorinated surfactant One other suitable class of surfactants are non-fluorinated surfactants according the formula (II) :
  • Xh is a non-fluorinated radical and(Y), (Z),n, m and p are as described above for formula (I) .
  • Xh may be a linear, branched or cyclic, saturated or unsaturated, aromatic or non-aromatic, radical preferably having at least 4 carbon atoms.
  • Xh preferably includes hydrocarbon radicals.
  • the carbon chain may be linear, branched or cyclic and may include hetero atoms such as oxygen, nitrogen or sulphur, although in some cases nitrogen is not preferred.
  • Xh is aliphatic and saturated. Radicals containing no more than about 24 carbon atoms are preferred.
  • One preferred surfactant is an acid surfactant.
  • Preferred surfactants include anionic surfactants.
  • Anionic surfactants are generally known in the art and include, for example, alkyl aryl sulfonates (such as, for example, alkylbenzenesulfonates) , alkyl aryl sulfonic acids (such as, for example, sodium and ammonium salts of toluene-, xylene- and isopropylbenzenesulfonic acids) , sulfonated amines and sulfonated amides (such as, for example, amidosulfonates) , carboxylated alcohols and carboxylated alkylphenol ethoxylates, diphenyl sulfonates, fatty esters, isethionates, lignin-based surfactants, olefin sulfonates (such as, for example,
  • RCH-CHS0 3 Na where R is C ⁇ o-C ⁇ 6 ) , phosphorous-based surfactants, protein based surfactants, sarcosine-based surfactants (such as, for example, N- acylsarcosinates such as sodium N- lauroylsarcosinate) , sulfates and sulfonates of oils and/or fatty acids, sulfates and sulfonates of ethoxylated alkylphenols, sulfates of alcohols, sulfates of ethoxylated alcohols, sulfates of fatty esters, sulfates of aromatic or fluoro containing compounds, sulfosuccinnamates, sulfosuccinates (such as, for example, diamyl-, dioctyl- and diisobutylsulfosuccinates) , taurates, and sulfonic acids.
  • Nonionic surfactants include, but are not limited to nonionic and cationic surfactants.
  • Compounds suitable for use as the nonionic surfactant of the present invention are those that carry no discrete charge when dissolved in aqueous media.
  • Nonionic surfactants are generally known in the art and include, for example, alkanol amides (such as, for example, coco, lauric, oleic and stearic monoethanolamides, diethanolamides and monoisopropanolamides) , amine oxides (such as, for example, polyoxyethylene ethanolamides and polyoxyethylene propanolamides), polyalkylene oxide block copolymers (such as, for example, poly (oxyethylene- co-oxypropylene) ) , ethoxylated alcohols, (such as, for example, isostearyl polyoxyethylene alcohol, lauryl, cetyl, stearyl, oleyl, tridecyl, trimethylnonyl, iso
  • fatty esters such as, for example, glycerol monostearate, glycerol monolaurate, glycerol dilaurate, glycerol monoricinoleate, and glycerol oleate
  • glycol esters such as, for example, propylene glycol monostearate, ethylene glycol monostearate, ethylene glycol distearate, diethylene glycol monolaurate, diethylene glycol monolaurate, diethylene glycol monooleate, and diethylene glycol stearate
  • lanolin-based surfactants such as, for example, propylene glycol monostearate, ethylene glycol monostearate, ethylene glycol distearate, diethylene glycol monolaurate, diethylene glycol monolaurate, diethylene glycol monooleate, and diethylene glycol stearate
  • lanolin-based surfactants such as, for example, propylene glycol monostearate, ethylene glycol monostearate,
  • one component of the present invention comprises one or more nonionic surfactants according to one or more of the structural formulas III and IV:
  • R 9 is a monovalent hydrocarbon group of from 1 to 30 carbons that may be linear, cyclic, branched, unsaturated, aromatic or fluoro containing;
  • R 10 is hydrogen or a monovalent hydrocarbon group of 1 to 30 carbons that may be linear, cyclic, branched, unsaturated, aromatic or fluoro containing; and n is from about 1 to about 100, more preferably from about 1 to about 40.
  • R 9 contains from 2 to about 24 carbons, even more preferably from 8 to 24 carbons, R 10 is H and n is from about 2 to about 20.
  • Examples include: didodecyldimethyl ammonium bromide (DDAB) , dihexadecyldimethyl ammonium chloride, dihexadecyldimethyl ammonium bromide, dioctadecyldimethyl ammonium chloride, dieicosyldimethyl ammonium chloride, didocosyldimethyl ammonium chloride, dicoconutdimethyl ammonium chloride, ditallowdimethyl ammonium bromide (DTAB) .
  • DDAB didodecyldimethyl ammonium bromide
  • DTAB didodecyldimethyl ammonium bromide
  • silicone surfactants including, but not limited to the polyalkyleneoxide polydimethylsiloxanes having a polydimethylsiloxane hydrophobic moiety and one or more hydrophilic polyalkyleneoxide side chains and have the general formula:
  • a + b are from about 1 to about 50, preferably from about 3 to about 30, more preferably from about 10 to about 25, and each R 1 is the same or different and is selected from the group consisting of methyl and a poly (ethyleneoxide/propyleneoxide) copolymer group having the general formula:
  • R 1 being a poly (ethyleneoxide/propyleneoxide) copolymer group, and wherein n is 3 or 4, preferably 3; total c (for all polyalkyleneoxide side groups) has a value of from 0 to about 100, preferably from about 6 to about 100; total d is from 0 to about 14, preferably from 0 to about 3; and more preferably d is 0; total c+d has a value of from about 5 to about 150, preferably from about 9 to about 100 and each R 2 is the same or different and is selected from the group consisting of hydrogen, an alkyl having 1 to 4 carbon atoms, and an acetyl group, preferably hydrogen and methyl group. Examples of these surfactants may be found in
  • the molecular weight of the polyalkyleneoxide group (R 1 ) is less than or equal to about 10,000.
  • the molecular weight of the polyalkyleneoxide group is less than or equal to about 8,000, and most preferably ranges from about 300 to about 5,000.
  • the values of c and d can be those numbers which provide molecular weights within these ranges.
  • the number of ethyleneoxide units (-C 2 H 4 0) in the polyether chain (R 1 ) must be sufficient to render the polyalkyleneoxide polysiloxane water dispersible or water soluble. If propyleneoxide groups are present in the polyalkyleneoxide chain, they can be distributed randomly in the chain or exist as blocks.
  • SilwetTM surfactants are L-7600, L-7602, L-7604, L-7605, L-7657, and mixtures thereof.
  • polyalkyleneoxide polydimethylsiloxane surfactants can also provide other benefits, such as anti-static benefits, and softness to fabrics.
  • polyalkyleneoxide polydimetylsiloxanes are well known in the art.
  • Polyalkyleneoxide polydimethylsiloxanes of the present invention can be prepared according to the procedure set forth in U.S. Pat. No. 3,299,112, incorporated herein by reference.
  • Another suitable silicone surfactant is SF-1488, which is available from GE silicone fluids.
  • Especially preferred silicone surfactants include TegoprenTM 7008 and 7009 (ex
  • the surfactant or mixture of surfactants is present in a cleaning effective amount.
  • a cleaning effective amount is the amount needed for the desired cleaning. This will, for example, depend on the number of articles, level of soiling and volume of dry cleaning composition used. However, surprisingly effective cleaning was observed when the surfactant was present from at least 0.001 wt.% to 10 wt.% by weight of the dry cleaning composition. More preferably, the surfactant is present from 0.01 to 3 wt.% or even more preferably from 0.05 to 0.9 wt.% by weight of the dry cleaning composition. More preferably, the surfactant is present from 0.1 to 0.8 wt.% or even more preferably from 0.3 to 0.7 wt.% by weight of the dry cleaning composition.
  • the surfactant to cloth ratio (w/w) was important in many cases to obtain an effective cleaning while maintaining a good garment care.
  • the SCR is at most 0.25, more preferably at most 0.12, more preferably at most 0.08, more preferably at most 0.04, but preferably at least 0.0001, more preferably at least 0.0003, more preferably at least 0.001 and most preferably at least 0.002.
  • the dry cleaning compositions may contain one or more optional cleaning agents.
  • Cleaning agents include any agent suitable for enhancing the cleaning, appearance, condition and/or garment care.
  • the cleaning agent may be present in the compositions of the invention in an amount of about 0 to 20 wt.%, preferably 0.001 wt.% to 10 wt.%, more preferably 0.01 wt.% to 2 wt.% by weight of the total dry cleaning composition.
  • cleaning agents include, but are not limited to, builders, enzymes, bleach activators, bleach catalysts, bleach boosters, bleaches, alkalinity sources, antibacterial agents, colorants, perfumes, pro-perfumes, finishing aids, lime soap dispersants, composition malodour control agents, odour neutralisers, polymeric dye transfer inhibiting agents, crystal growth inhibitors, photobleaches, heavy metal ion sequestrants, anti-tarnishing agents, anti-microbial agents, anti-oxidants, anti-redeposition agents, soil release polymers, electrolytes, pH modifiers, thickeners, abrasives, divalent or trivalent ions, metal ion salts, enzyme stabilisers, corrosion inhibitors, diamines or polyamines and/or their alkoxylates, suds stabilising polymers, process aids, fabric softening agents, optical brighteners, hydrotropes, suds or foam suppressors, suds or foam boosters, fabric softeners, antistatic agents, dye fixatives,
  • Example 1 In one container two pieces of woven cotton (20x20cm) (Cotton cretonne bleached (150 gm/m 2 ) ex Centre For Testmaterials, The Netherlands) were contacted and agitated (50 rpm) for 15 minutes at 20°C with one of the compositions in table I (LCR of 10) .
  • the pieces of cotton were transferred to a second bottle with clean solvent which was agitated (50 rpm) for 5 min to mimic a rinse cycle.
  • the pieces of cotton were then removed from the second bottle with tweezers and shaken lightly for 5 sec to remove excess solvent.
  • the pieces of cotton were dried on a flat surface (parchment paper ex. Fischer code 949ZQ92902) using a table fan (ex Ferm type TV-200) . After drying the maximum wrinkle height was measured.
  • the WIC was determined as described above.
  • composition B The pieces of cotton dry cleaned with composition A showed large wrinkles.
  • composition C the amount of surfactant

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
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  • Accessory Of Washing/Drying Machine, Commercial Washing/Drying Machine, Other Washing/Drying Machine (AREA)

Abstract

L'invention concerne un procédé de nettoyage à sec comprenant une étape de nettoyage à sec faiblement aqueuse qui consiste à mettre en contact un vêtement avec une composition de nettoyage à sec faiblement aqueuse. Cette composition comprend: a) un solvant de nettoyage à sec organique ne contenant pas de chlore et ininflammable; b) un tensioactif; et c) de l'eau. Les quantités de tensioactif, d'eau et de vêtement sont telles que le rapport «eau dans vêtement» (WIC) (en poids) après la première étape est inférieur à 0,25.
PCT/EP2003/013827 2002-12-19 2003-12-03 Procede de nettoyage a sec WO2004057096A1 (fr)

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WO2006084208A2 (fr) * 2005-02-04 2006-08-10 The Procter & Gamble Company Utilisation de structurants aqueux pour fournir des avantages d'entretien de tissu dans un systeme de traitement de tissu non aqueux

Citations (8)

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Publication number Priority date Publication date Assignee Title
US3689211A (en) * 1969-04-24 1972-09-05 Dow Chemical Co Dry cleaning method
DE3739711A1 (de) * 1987-11-24 1989-06-08 Kreussler Chem Fab Verwendung von polydialkylcyclosiloxanen als loesemittel fuer die chemischreinigung
WO2000035571A1 (fr) * 1998-12-16 2000-06-22 3M Innovative Properties Company Microemulsions contenant de l'eau et des hydrofluoroethers
WO2000036206A1 (fr) * 1998-12-16 2000-06-22 3M Innovative Properties Company Compositions de nettoyage a sec contenant un hydrofluoroether
WO2001094684A1 (fr) * 2000-06-05 2001-12-13 The Procter & Gamble Company Proprietes visuelles ameliorees pour procede de lavage
WO2002046517A1 (fr) * 2000-12-06 2002-06-13 General Electric Company Composition de nettoyage a sec a base de siloxane et procede associe
WO2002050366A1 (fr) * 2000-12-20 2002-06-27 General Electric Company Procede et composition de nettoyage a sec au siloxane
WO2002053824A1 (fr) * 2000-12-29 2002-07-11 Unilever N.V. Compositions de nettoyage a sec et leur utilisation

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0882124B1 (fr) * 1995-12-15 2002-04-10 Minnesota Mining And Manufacturing Company Procede et composition de nettoyage

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3689211A (en) * 1969-04-24 1972-09-05 Dow Chemical Co Dry cleaning method
DE3739711A1 (de) * 1987-11-24 1989-06-08 Kreussler Chem Fab Verwendung von polydialkylcyclosiloxanen als loesemittel fuer die chemischreinigung
WO2000035571A1 (fr) * 1998-12-16 2000-06-22 3M Innovative Properties Company Microemulsions contenant de l'eau et des hydrofluoroethers
WO2000036206A1 (fr) * 1998-12-16 2000-06-22 3M Innovative Properties Company Compositions de nettoyage a sec contenant un hydrofluoroether
WO2001094684A1 (fr) * 2000-06-05 2001-12-13 The Procter & Gamble Company Proprietes visuelles ameliorees pour procede de lavage
WO2002046517A1 (fr) * 2000-12-06 2002-06-13 General Electric Company Composition de nettoyage a sec a base de siloxane et procede associe
WO2002050366A1 (fr) * 2000-12-20 2002-06-27 General Electric Company Procede et composition de nettoyage a sec au siloxane
WO2002053824A1 (fr) * 2000-12-29 2002-07-11 Unilever N.V. Compositions de nettoyage a sec et leur utilisation

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