EP0871808B1 - Composition pour traiter des taches sur des textiles a laver et procede de traitement - Google Patents

Composition pour traiter des taches sur des textiles a laver et procede de traitement Download PDF

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Publication number
EP0871808B1
EP0871808B1 EP96930883A EP96930883A EP0871808B1 EP 0871808 B1 EP0871808 B1 EP 0871808B1 EP 96930883 A EP96930883 A EP 96930883A EP 96930883 A EP96930883 A EP 96930883A EP 0871808 B1 EP0871808 B1 EP 0871808B1
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EP
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Prior art keywords
cleaning composition
stain
spot
composition according
water
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EP96930883A
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German (de)
English (en)
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EP0871808A4 (fr
EP0871808A1 (fr
Inventor
Eric Tcheou
Jose Luis Vega
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Procter and Gamble Co
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Procter and Gamble Co
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/18—Hydrocarbons
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0017—Multi-phase liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
    • D06F43/00—Dry-cleaning apparatus or methods using volatile solvents
    • D06F43/002—Spotting apparatus
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/40—Specific cleaning or washing processes
    • C11D2111/44—Multi-step processes

Definitions

  • the present invention relates to compositions for treating stains on laundry items.
  • Laundry items can be treated either before or after a conventional laundering process by application of the composition in the region of the stain so that the stain is at least partially released and removal of the stain is made easier.
  • Emulsions of solvent-aqueous systems are known to be effective as spot pretreating compositions on both hydrophobic and hydrophilic stains.
  • GB-A-2 194 547 published on 9th March 1988, discloses mixtures of n-dodecane with both short-chain (Neodol 91-6) and long chain (Neodol 45-1) nonionics.
  • the compositions are in the form of liquid solutions; water-in-oil or oil-in-water microemulsions, or gels. However this application does not disclose compositions which comprise alkali material.
  • EP-A-0 216 355 discloses emulsions comprising a solt, as well as a mixture of surfactants and a solvent.
  • the present invention relates to a cleaning composition which is an oil-in-water or water-in-oil emulsion comprising non-aqueous hydrophobic solvent; first anionic or nonionic surfactant having an alkyl chain, the length of the alkyl chain being C 11 or less; and second anionic or nonionic surfactant having an alkyl chain, the length of the alkyl chain being C 12 or more.
  • Another object of the present invention is to improve the removal of bleachable stains through the application of the composition of the present invention and the application of a bleaching compound, preferably a peroxide compound.
  • the objective of the present invention is achieved by providing a cleaning composition which has a pH greater than 8, thereby enhancing cleaning performance for both fatty stains and bleachable stains.
  • a cleaning composition which has a pH greater than 8, thereby enhancing cleaning performance for both fatty stains and bleachable stains.
  • the pH is greater than 9, and more preferably greater than 10.
  • the cleaning composition preferably comprises water from 5% to 95% by weight of the composition.
  • the invention also relates to a method for treating a spot or stain on a textile fabric using the cleaning compositions of the invention.
  • Hydrophobic solvents are an essential feature of the compositions of the present invention.
  • Preferred hydrophobic solvents are defined in terms of Hansen parameters.
  • a hydrophobic solvent as defined herein is considered to be a solvent having Hansen hydrogen bonding cohesion parameter dH below 18 (Joule/cm 3 ) 0.5 .
  • Preferred hydrophobic solvents have a Hansen hydrogen bonding cohesion parameter dH below 12 (Joule/cm 3 ) 0.5 and a Hansen polar parameter dP below 8 (Joule/cm 3 ) 0.5 .
  • Preferred solvents for use comprise mixtures of hydrocarbons with a flash point no lower than 70°C, an initial boiling point no lower than 130°C, preferably no lower than 145°C, and a solidification point not above 20°C and aliphatic fatty acid esters. More preferred solvents would be alkanes or alkenes with a chain length above C7, and particularly alkanes and alkenes with an average of C8 to C20 atoms. Particularly preferred hydrophobic solvents are deodorised kerosine; solvent naphta; chlorinated hydrocarbons; and terpenes.
  • paraffins Even more preferred are paraffins; isoparaffins; naphthenes; aromatics; olefins; 1,1,1-trichloroethane perchloroethylene; methylene chloride; Shellsol SS® mixture (C8-C11 isoparaffin + 5% aliphatic C7 ester); D-Limonene; and Glidsafe® supplied by Glidsol.
  • Solvents are used in the detergent compositions of the present invention preferably at a level of from 3% to 90%, more preferably from 4% to 45%, and most preferably from 5% to 25% by weight of the detergent composition.
  • solvents having a Hansen parameter of dH less than 18 (Joule/cm 3 ) 0.5 include glycol ethers, more preferably glycol ethers based upon ethylene oxide, propylene oxide, or mixtures thereof. Particularly preferred are ethylene glycol monoethyl ether; Propylene glycol monomethyl ether; 2-butoxy ethanol; butyl diethylene glycol ether ethanol; butoxytriglycol; butylene glycol; hexylene glycol; and propyl propanol. Such solvents are used in combination with mixtures of short chain surfactants and long chain surfactants.
  • short-chain what is meant herein is surfactants which comprise a C 6 -C 11 alkyl chain as their hydrophobic portion. Such short-chain surfactants are accordingly those conventionally used in this field, but with a shorter alkyl chain, and can be of any type.
  • suitable short chain surfactants for use herein include C 6 -C 11 alkyl sulfates (C 6 -C 11 SO 4 ), alkyl ether sulfates (C 6 -C 11 (OCH 2 CH 2 )eSO 4 ), alkyl sulfonates (C 6 -C 11 SO 3 ), alkyl succinates (C 6 -C 11 OOCCH 2 CH 2 COOZ), alkyl carboxylates (C 6 -C 11 COOM), alkyl ether carboxylates (C 6 -C 11 (OCH 2 CH 2 )eCOOM), alkyl sarcosinates (C 6 -C 11 CON(CH 3 )R), alkyl sulfo succinates (C 6 -C 11 OOCCH(SO 3 M)CH 2 COOZ), amine oxides (C 6 -C 11 RR'NO), glucose amides (C 6 -C 11 CONR''X), alkylpyrrolidone
  • e and p are independently from 0 to 20 and e+p>0
  • Z is M or R
  • M is H or any counterion such as those known in the art, including Na, K,Li, NH 4 , amine
  • X is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof
  • R, R' and R'' are C 1 -C 5 alkyl groups, possibly functionalized with hydroxyl groups
  • R and R' are preferably C 1 -C 3 , most preferably methyl
  • R'' is preferably 2-hydroxyethyl or 2 hydroxypropyl
  • G is saccharide, preferably glucose, and g is of from 1.5 to 8.
  • compositions according to the present invention may comprise any of the above surfactants alone, or any combination thereof.
  • Preferred short chain nonionic surfactants for use herein are alkyl alkoxylates according to the formula C 6 -C 11 (OCH 2 CH 2 ) e (OCH 2 CH 2 CH 2 ) p OH, where e and p representing respectively the degree of ethoxylation and propoxylation, are independently of from 0 to 20, and that e+p>0.
  • Most preferred short chain nonionic surfactants for use herein are those where e and p are such that e+p is from 3 to 10, particularly those where p is 0 and e is 3 to 8.
  • most preferred short chain nonionic surfactants for use herein are those where said short chain is a hydrocarbon chain comprising from 7 to 11 carbon atoms.
  • Said preferred short chain nonionic surfactants for use herein can be manufactured by the processes well known to the man skilled in the art, such as condensation of the corresponding alcohol and alkylene oxide, but such short chain surfactants are more conveniently commercially available for instance from Sidobre under the trade name Mergital ® C 4 (C8EO4), from Kolb under the trade names Imbentin® AG/810/050 and AG/810/080 (respectively C8-10EO5 and C8-10EO8); from Shell under the trade name Dobanol 91-2.5 (C 9 -C 11 E02.5), Dobanol 91-6 (C 9 -C 11 EO6), Dobanol 91-4-6; from Vista Chemicals Vista 1012-52, from EXXON Asopol 91-4.6.
  • Another preferred class of short chain nonionic surfactants are secondary alcohol ethoxylates according to the formula wherein (X+Y) is from 2 to 10 and the number of ethoxylate groups n is from 1 to 7.
  • Example of commercially available surfactants of this type include the Tergitol S series from Union Carbide.
  • Preferred short chain anionic surfactants for use herein are C 6 -C 11 alkyl sulfates and C 6 -C 11 alkyl sulfonates, C 6 -C 11 betaines, C 6 -C 11 amine oxides and mixtures thereof. Most preferred are the C 6 -C 8 alkyl sulfates and sulfonates.
  • Such short chain anionic surfactants can be made by well known sulphation or sulphonation processes followed by neutralization, but said anionic short chain surfactants are more conveniently commercially available, for instance from Rhone Poulenc under the trade name Rhodapon ® OLS, or from Witco under the trade name Witconate®.
  • any alkaline materials is suitable for use in the present invention.
  • Preferred alkaline materials are selected from the group consisting of potassium hydroxide, sodium hydroxide, ammonium hydroxide, ammonium silicate, sodium bicarbonate, borax, monoethanolamine borate, monoethanolamine triethanolamine, and mixtures thereof.
  • the spot treating composition comprises from 0.1% to 10%, preferably 0.5% to 3% by weight of the alkaline material.
  • the pH is greater than 8, more preferably greater than 9, and most preferably greater than 10. pH of the neat compositions was measured by means of a portable pH meter from Knick (Portamess 752).
  • long-chain is surfactants having an alkyl chain, the alkyl chain comprising 12, or more than 12 carbon atoms.
  • long-chain surfactants useful herein include the conventional C 12 -C 18 alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C 12 -C 20 alkyl sulfates ("AS"), the C 1 -C 18 secondary (2,3) alkyl sulfates of the fomula CH 3 (CH 2 ) x (CHOSO 3 - M + ) CH 3 and CH 3 (CH 2 ) y (CHOSO 3 - M + )CH 2 CH 3 where x and (y+1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C 12 -C 18 alkyl alkoxy sulfates ("AE
  • the conventional nonionic and amphoteric surfactants such as the C 12 -C 18 alkyl ethoxylates ("AE") particulary preferred are C 12 -C 16 fatty alcohol polyglycol ethers or ethoxylated primary alcohols with EO 2-7 (especially ethoxylates and mixed ethoxy/propoxy), C 12 -C 18 betaines and sulfobetaines ("sultaines"), C 12 -C 18 amine oxides, and the like, can also be included in the overall compositions.
  • the C 12 -C 18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C 12 -C 18 N-methylglucamides. See WO 9,206,154.
  • sugar-derived surfactants include the N-alkoxy polyhhydroxy fatty acid amides, such as C 12 -C 18 N-(3-methoxypropyl) glucamide.
  • the N-propyl through N-hexyl C 12 -C 18 glucamides can be used for low sudsing.
  • C 12 -C 20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C 12 -C 16 soaps may be used.
  • Mixtures of anionic and nonionic surfactants are espicially useful. Other conventional useful surfactants are listed in standard texts.
  • a particularly preferred composition according to the present invention comprises from 5% to 50% by weight of a mixed nonionic system comprising first, short-chain nonionic surfactant and second, long-chain nonionic surfactant. More preferably the composition comprises from 10% to 40% by weight of the mixed nonionic surfactant, and most preferably from 15% to 30%.
  • the nonionic system preferably has an overall HLB value of from 2 to 16, more preferably from 8 to 14, most preferably from 9 to 10. Furthermore it is preferred that the ratio of first surfactant to second surfactant is from 1:10 to 10:1, more preferably from 1:3 to 3:1, and most preferably about 1:1.
  • Bleaching agents may also be useful in the method of the present invention for treating bleachable stains.
  • the bleaching agents may be incorporated into the compositions described above, or may be added as separate bleaching compositions. Peroxide bleaching agents are most preferred.
  • the detergent composition of the present invention is useful in various known and conventional cleaning methods.
  • a preferred cleaning method comprises the steps of applying the detergent composition to the spot or stain; placing an absorbent layer adjacent to the textile fabric in the region of the spot or stain; and applying heat, pressure, or heat and pressure to the textile fabric in the region of the spot or stain; so that some or all of the spot or stain is absorbed into the absorbent layer.
  • a still more preferred cleaning method comprises the steps of :
  • An alternative device for applying heat or pressure is a heated roller or any other heated applicator.
  • the roller or applicator may also be provided with a supply of the detergent composition.
  • Suitable applicators include a steam iron with suction brush attachment, such as that disclosed in EP-A-0 493 348, and a thermoelectric applicator, such as that disclosed in EP-A-0 552 397. Also suitable is a steam iron with atomiser, such as that disclose in EP-A-0 629 736 wherein the detergent composition may optionally be stored in the iron and delivered directly onto the textile fabrics by means of the atomiser.
  • hydrophobic stains are first rendered hydrophilic by applying a detergent composition, optionally with a gentle rubbing action.
  • Greasy stains which contain hydroxyl groups are deprotoneated at high pH and are thus rendered more easy to solubilize in the detergent solution. Higher pH can also induce soll peptization on some food stains. The stains are in effect broken down, and rendered easier to remove.
  • the benefits of high pH can be particularly observed when before or after application of the detergent composition, another composition containing a bleaching species is applied on the stain. Indeed, conventional peroxide bleaching technologies have an increased reactivity with pH. Water is then applied to the stain, again, optionally with a gentle rubbing action. The stain is removed by laying the stained fabric adjacent to an absorbent layer. The stain, which has been rendered more hydrophilic by the treatment, is transferred to the absorbent layer.
  • Textile fabrics are any materials made from cloth, including garments such as shirts, blouses, socks, skirts, trousers, jackets, underwear etc, and also including tablecloths, towels, curtains etc.
  • the definition of textile fabrics as used herein does not include carpets and similar floor coverings.
  • Textile fabrics which are to be used in the present invention are commonly made by weaving or knitting. Many different fibres may be used to produce woven, knitted or other types of textile fabric including synthetic fibres (such as polyester, polyamide, etc.) and natural fibres from plants (such as cotton, hemp) and from animals (such as wool, angora, silk). Blends of different fibres are also commonly used.
  • synthetic fibres such as polyester, polyamide, etc.
  • natural fibres such as cotton, hemp
  • animals such as wool, angora, silk
  • Example 1 Example 2 Example 3 Example 4 Shellsol ® 20 20 20 20 Dobanol 25EO3 ® 5 5 5 - Alkyl sulphate C8AS 5 - 5 5 Dehydol C8EO4 ® - 5 - 5 Sodium hydroxide 1 1 - - Monoethanolamine - - 3 3 Water 69 69 67 67
  • Shellsol ® is a mixture of C 8 -C 11 isoparaffins with 5% aliphatic C 7 ester.
  • Dehydol ® is a fatty alcohol polyglycol ether octyl with an average of 4EO, supplied by Henkel.
  • Dobanol ® is a ethoxylated primary alcohol with an average of 3EO, supplied by Shell.
  • Alkyl sulphate, C8AS has an average of 8 carbon atoms in the alkyl chain.
  • emulsions were prepared by mixing the components in the following order : Dobanol 25E3 was first mixed with the Shellsol solvent. The short-chain surfactant (alkyl sulphate or Dehydol) was then added followed by an aqueous solution of sodium hydroxide. Mixing was continued until a stable oil-in-water emulsion was formed.
  • the short-chain surfactant alkyl sulphate or Dehydol
  • Example 5 Example 6
  • Example 7 Limonene 18.3 18.3 23.5 HLAS 10.5 - - Dehydol C8EO4 ® 6 16.5 - Alkyl Sulphate C8A5 - - 7.8 Monoethanolamine 3 3 5.8 Butyl carbitol 10 10 11.7 Oleic acid - - 6 Water balance balance balance
  • Example 8 Example 9
  • Example 10 Example 11 Dodecane 22 48.2 - - Hexadecane - - 10 - Tridecane - - - 20 C14-15EO1 5.5 14.8 10 - C12-15EO3 - - - 5 C9-11EO6 22 34.2 7.5 - C8EO4 - - 5 Sodium hydroxide 1 1 1 1 Butyl carbitol - 0.8 - - Water balance balance balance balance balance balance balance balance balance balance balance balance balance balance balance balance balance balance balance balance balance balance balance balance balance balance balance balance balance balance balance balance balance balance balance balance balance balance balance balance balance balance balance balance balance balance
  • DTPMP is diethylene triamine penta methylene phosphonic acid from Monsanto, Dequest 2060.
  • a set of polycotton swatches (50mm square) were soiled with make-up, chocolate sauce and tomato sauce. The stain was left to age for a day, in the dark, at normal room temperature (c.a. 20°C, 60%RH). Each soiled swatch was cleaned by the following method:

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Treatment Of Fiber Materials (AREA)

Abstract

Cette invention se rapporte à une composition de nettoyage qui est une émulsion d'huile dans l'eau ou d'eau dans l'huile ou une solution comprenant un solvant hydrophobe non aqueux, un premier tensioactif anionique ou non ionique ayant une chaîne alkyle, dont la longueur est de C11 ou moins, et un second tensioactif anionique ou non ionique ayant une chaîne alkyle, dont la longueur est de C12 ou plus. Cette composition de nettoyage possède un pH supérieur à 8. Cette invention se rapporte également à un procédé pour traiter des taches sur un tissu textile au moyen de ladite composition de nettoyage.

Claims (13)

  1. Composition de nettoyage ayant un pH d'au moins 8, la composition de nettoyage comprenant
    (i) un solvant hydrophobe non aqueux ; et
    (ii), (iii) un mélange de tensioactifs
       caractérisée en ce que le mélange de tensioactifs comprend :
    (ii) un premier tensioactif anionique ou non ionique ayant une chaíne alkyle, la longueur de la chaíne alkyle étant en C11 ou moins ; et
    (iii) un second tensioactif anionique ou non ionique ayant une chaíne alkyle, la longueur de la chaíne alkyle étant en C12 ou plus,
    la composition de nettoyage étant en outre caractérisée en ce qu'elle est une émulsion, soit huile-dans-l'eau soit eau-dans-l'huile.
  2. Composition de nettoyage selon la revendication 1, comprenant 0,1 à 10% en poids d'un matériau alcalin, dans laquelle le matériau alcalin est choisi dans le groupe constitué par l'hydroxyde de potassium, l'hydroxyde de sodium, l'hydroxyde d'ammonium, le silicate d'ammonium, le bicarbonate de sodium, le borax, le borate de monoéthanolamine, la monoéthanolamine, la triéthanolamine, et leurs mélanges.
  3. Composition de nettoyage selon la revendication 1, comprenant en outre 5 à 95% en poids d'eau.
  4. Composition de nettoyage selon la revendication 1, dans laquelle le pH d'une solution à 1% dans l'eau distillée est d'au moins 9, et de préférence d'au moins 10.
  5. Composition de nettoyage selon la revendication 1 comprenant 3% à 90% en poids d'un solvant hydrophobe non aqueux ayant un paramètre dH de cohésion de liaison hydrogène Hansen inférieur à 18 (joule/cm3)0,5 et un paramètre polaire Hansen dP inférieur à 8 (joule/cm3)0,5.
  6. Composition de nettoyage selon la revendication 5, dans laquelle le solvant comprend des hydrocarbures ayant un point éclair non inférieur à 70°C, un point d'ébullition initial supérieur à 145°C, et un point de solidification inférieur à 20°C.
  7. Composition de nettoyage selon la revendication 6, dans laquelle le solvant est choisi dans le groupe constitué par des alcanes linéaires ou ramifiés en C10-C18, les terpènes, et leurs mélanges.
  8. Composition de nettoyage selon la revendication 1, dans laquelle le second tensioactif est choisi dans le groupe constitué par des éthers de polyglycol d'alcool gras en C12-C16 ou des alcools primaires éthoxylés avec 2 à 7 éthoxylations.
  9. Composition de nettoyage selon la revendication 8, comprenant 5% à 50% en poids d'un système tensioactif non ionique mixte comprenant les premier et second tensioactifs, le système tensioactif non ionique mixte ayant une valeur HLB globale de 2 à 16.
  10. Composition de nettoyage selon la revendication 9, dans laquelle le rapport molaire du premier tensioactif au second tensioactif est de 1 : 10 à 10 : 1.
  11. Procédé de traitement d'une tache ou d'une salissure sur un article textile comprenant les étapes consistant à :
    (a) appliquer la composition de nettoyage selon l'une quelconque des revendications précédentes sur la tache ou la salissure ;
    (b) placer une couche absorbante en position adjacente à l'article textile dans la région de la tache ou la salissure ; et
    (c) appliquer chaleur, pression, ou chaleur et pression, à l'article textile dans la région de la tache ou la salissure de manière qu'une partie ou la totalité de la tache ou la salissure soit absorbée dans la couche absorbante.
  12. Procédé selon la revendication 11, comprenant en outre les étapes consistant à :
    (d) appliquer un solvant hydrophile ou de l'eau à l'article textile dans la région de la tache ou la salissure ; et
    (e) appliquer un second moyen pour transférer une partie ou la totalité de la tache ou salissure dans la couche absorbante.
  13. Procédé selon la revendication 12, dans lequel le second moyen pour transférer une partie ou la totalité de la tache ou salissure dans la couche absorbante comprend l'étape consistant à appliquer de la chaleur à l'article textile dans la région de la tache ou salissure en utilisant un fer à repasser manuel.
EP96930883A 1995-11-27 1996-09-16 Composition pour traiter des taches sur des textiles a laver et procede de traitement Expired - Lifetime EP0871808B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP96930883A EP0871808B1 (fr) 1995-11-27 1996-09-16 Composition pour traiter des taches sur des textiles a laver et procede de traitement

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP95118617 1995-11-27
EP95118617 1995-11-27
EP96930883A EP0871808B1 (fr) 1995-11-27 1996-09-16 Composition pour traiter des taches sur des textiles a laver et procede de traitement
PCT/US1996/014766 WO1997020094A1 (fr) 1995-11-27 1996-09-16 Composition pour traiter des taches sur des textiles a laver et procede de traitement

Publications (3)

Publication Number Publication Date
EP0871808A1 EP0871808A1 (fr) 1998-10-21
EP0871808A4 EP0871808A4 (fr) 1999-04-28
EP0871808B1 true EP0871808B1 (fr) 2003-02-19

Family

ID=8219839

Family Applications (2)

Application Number Title Priority Date Filing Date
EP96932226A Withdrawn EP0866893A4 (fr) 1995-11-27 1996-09-16 Composition pour traiter des taches sur des textiles a laver et procedes de traitement
EP96930883A Expired - Lifetime EP0871808B1 (fr) 1995-11-27 1996-09-16 Composition pour traiter des taches sur des textiles a laver et procede de traitement

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP96932226A Withdrawn EP0866893A4 (fr) 1995-11-27 1996-09-16 Composition pour traiter des taches sur des textiles a laver et procedes de traitement

Country Status (14)

Country Link
EP (2) EP0866893A4 (fr)
JP (2) JP3085986B2 (fr)
AR (3) AR004772A1 (fr)
AT (2) ATE232919T1 (fr)
AU (4) AU6978796A (fr)
BR (3) BR9612283A (fr)
CA (2) CA2238482C (fr)
DE (1) DE69626311T2 (fr)
EG (1) EG20922A (fr)
ES (1) ES2188785T3 (fr)
MX (3) MX9804177A (fr)
NO (2) NO982359L (fr)
WO (3) WO1997020094A1 (fr)
ZA (2) ZA969921B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7757340B2 (en) 2005-03-25 2010-07-20 S.C. Johnson & Son, Inc. Soft-surface remediation device and method of using same

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5891197A (en) * 1996-08-02 1999-04-06 The Proctor & Gamble Company Stain receiver for dry cleaning process
US6855172B2 (en) 1998-10-13 2005-02-15 Dry, Inc. Dry-cleaning article, composition and methods
JP4005092B2 (ja) 2004-08-20 2007-11-07 東京応化工業株式会社 洗浄除去用溶剤
TWI400330B (zh) * 2005-12-28 2013-07-01 Kao Corp Liquid detergent
EP2404988B1 (fr) 2010-07-07 2018-01-24 Dalli-Werke GmbH & Co. KG Composition d'application locale en pré-traitement de taches sur du linge
JP5544256B2 (ja) * 2010-09-21 2014-07-09 花王株式会社 硬質表面の洗浄方法
GB201021822D0 (en) * 2010-12-23 2011-02-02 Reckitt & Colman Overseas Cleaning composition and method
JP2012131949A (ja) * 2010-12-24 2012-07-12 Idemitsu Kosan Co Ltd イソパラフィン含有エマルジョン組成物
EP2535401B1 (fr) 2011-06-17 2017-01-25 Dalli-Werke GmbH & Co. KG Composition de détergent comportant des polymères de libération des saletés de stabilité de stockage améliorée
RU2690000C2 (ru) * 2013-09-06 2019-05-30 Дзе Проктер Энд Гэмбл Компани Капсулы, содержащие водорастворимые волокнистые материалы стенок, и способы их изготовления
FR3047488B1 (fr) * 2016-02-05 2020-02-28 Laboratoires Anios Compositions detergentes pour le nettoyage dans l'industrie cosmetique et pharmaceutique.
RU2751765C2 (ru) * 2018-12-21 2021-07-16 Светлана Борисовна Узенькова Способ чистки изделий из натуральной и искусственной кожи, натурального и искусственного меха и подкладочной ткани изделий
JP7332286B2 (ja) * 2018-12-26 2023-08-23 花王株式会社 繊維製品の処理方法

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US495428A (en) * 1893-04-11 Furnace-mouth feed-water heater
GB1384896A (en) * 1971-02-03 1975-02-26 Boulus P A Cleaning covering textile materials
US3748268A (en) * 1972-03-27 1973-07-24 Minnesota Mining & Mfg Spot and stain removing composition
GB1518676A (en) * 1975-10-30 1978-07-19 Procter & Gamble Ltd Detergent compositions
US4199482A (en) * 1977-03-31 1980-04-22 Colgate-Palmolive Company Laundry pre-spotter composition and method of using same
DE2903061A1 (de) * 1979-01-26 1980-08-07 Heliotronic Gmbh Verfahren zur herstellung grosskristalliner vorzugsorientierter siliciumfolien
DE2939810A1 (de) * 1979-10-01 1981-04-16 Henkel KGaA, 4000 Düsseldorf Zur textilbehandlung geeignetes spruehreinigungsmittel
US4336024A (en) * 1980-02-22 1982-06-22 Airwick Industries, Inc. Process for cleaning clothes at home
US4412934A (en) * 1982-06-30 1983-11-01 The Procter & Gamble Company Bleaching compositions
DE3465334D1 (en) * 1983-04-14 1987-09-17 Interox Chemicals Ltd Peroxygen compounds
US4634551A (en) * 1985-06-03 1987-01-06 Procter & Gamble Company Bleaching compounds and compositions comprising fatty peroxyacids salts thereof and precursors therefor having amide moieties in the fatty chain
US4749516A (en) * 1985-09-24 1988-06-07 S. C. Johnson & Son, Inc. Anionic emulsion pre-spotting composition
MY101656A (en) * 1986-09-02 1991-12-31 Colgate Palmolive Co Laundry pre-spotter composition providing improved oily soil removal.
US4915854A (en) * 1986-11-14 1990-04-10 The Procter & Gamble Company Ion-pair complex conditioning agent and compositions containing same
US5002684A (en) * 1987-04-08 1991-03-26 Harris Research, Inc. Composition and method for removal of stains from fibers
US5205960A (en) * 1987-12-09 1993-04-27 S. C. Johnson & Son, Inc. Method of making clear, stable prespotter laundry detergent
US4954286A (en) * 1988-04-14 1990-09-04 Lever Brothers Company Fabric pretreatment cleaning compositions
DE4303454A1 (de) * 1993-02-05 1994-08-11 Nouvelle Cosmetic Gmbh Verfahren zum Entfernen von Flecken und Fleckentfernungsset
DE69326757T2 (de) * 1993-07-12 2000-05-31 The Procter & Gamble Co., Cincinnati Stabile, wässrige Emulsionen aus nichtionischen oberflächenaktiven Mitteln mit einem viskositätskontrollierendem Mittel
EP0779357A1 (fr) * 1995-12-16 1997-06-18 The Procter & Gamble Company Emulsions stables contenant un ingrédient hydrophobe liquide

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7757340B2 (en) 2005-03-25 2010-07-20 S.C. Johnson & Son, Inc. Soft-surface remediation device and method of using same

Also Published As

Publication number Publication date
BR9611771A (pt) 1999-02-23
EP0866893A1 (fr) 1998-09-30
ATE241691T1 (de) 2003-06-15
ZA969925B (en) 1997-08-19
ES2188785T3 (es) 2003-07-01
NO982360D0 (no) 1998-05-25
AR004773A1 (es) 1999-03-10
WO1997020094A1 (fr) 1997-06-05
AU6978796A (en) 1997-06-19
MX9804177A (es) 1998-09-30
EP0871808A4 (fr) 1999-04-28
AU1276697A (en) 1997-06-19
CA2238482C (fr) 2005-04-12
BR9612283A (pt) 1999-07-13
MX9804179A (es) 1998-09-30
EP0866893A4 (fr) 1999-04-14
NO982359D0 (no) 1998-05-25
WO1997020095A1 (fr) 1997-06-05
AR004772A1 (es) 1999-03-10
DE69626311D1 (de) 2003-03-27
MX9804178A (es) 1998-09-30
CA2238482A1 (fr) 1997-06-05
CA2238620C (fr) 2002-01-22
ZA969921B (en) 1997-06-17
ATE232919T1 (de) 2003-03-15
AU7109896A (en) 1997-06-19
AU6978396A (en) 1997-06-19
EG20922A (en) 2000-06-28
JP3085986B2 (ja) 2000-09-11
EP0871808A1 (fr) 1998-10-21
JPH11501354A (ja) 1999-02-02
JP2002509558A (ja) 2002-03-26
NO982359L (no) 1998-05-25
AR004771A1 (es) 1999-03-10
NO982360L (no) 1998-05-25
BR9611791A (pt) 1999-07-13
WO1997020098A1 (fr) 1997-06-05
DE69626311T2 (de) 2003-12-11
JP3412111B2 (ja) 2003-06-03
CA2238620A1 (fr) 1997-06-05

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