WO2001081530A1 - Packaging for unit dose of detergent and method of its use - Google Patents
Packaging for unit dose of detergent and method of its use Download PDFInfo
- Publication number
- WO2001081530A1 WO2001081530A1 PCT/US2001/013456 US0113456W WO0181530A1 WO 2001081530 A1 WO2001081530 A1 WO 2001081530A1 US 0113456 W US0113456 W US 0113456W WO 0181530 A1 WO0181530 A1 WO 0181530A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- package
- substrate
- detergent
- fabric
- fabrics
- Prior art date
Links
- 239000003599 detergent Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000004806 packaging method and process Methods 0.000 title description 2
- 239000000203 mixture Substances 0.000 claims abstract description 84
- 239000004744 fabric Substances 0.000 claims abstract description 68
- 239000000758 substrate Substances 0.000 claims abstract description 40
- 239000000126 substance Substances 0.000 claims abstract description 33
- 238000011282 treatment Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 polyethylene Polymers 0.000 claims description 53
- 239000002904 solvent Substances 0.000 claims description 16
- 239000004743 Polypropylene Substances 0.000 claims description 12
- 229920001155 polypropylene Polymers 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 12
- 239000004615 ingredient Substances 0.000 claims description 10
- 239000004902 Softening Agent Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 3
- 238000010412 laundry washing Methods 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims 1
- 239000004800 polyvinyl chloride Substances 0.000 claims 1
- 239000004753 textile Substances 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 description 29
- 150000001875 compounds Chemical class 0.000 description 24
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- 125000001165 hydrophobic group Chemical group 0.000 description 12
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- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 5
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- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical class O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 5
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- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- 239000003093 cationic surfactant Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
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- 238000002844 melting Methods 0.000 description 4
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- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
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- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 3
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- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 2
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- SWZDQOUHBYYPJD-UHFFFAOYSA-N tridodecylamine Chemical compound CCCCCCCCCCCCN(CCCCCCCCCCCC)CCCCCCCCCCCC SWZDQOUHBYYPJD-UHFFFAOYSA-N 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
- C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
- C11D17/045—Multi-compartment
-
- 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
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
- C11D17/046—Insoluble free body dispenser
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
- B65D81/32—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents for packaging two or more different materials which must be maintained separate prior to use in admixture
- B65D81/3261—Flexible containers having several compartments
- B65D81/3272—Flexible containers having several compartments formed by arranging one flexible container within another
-
- 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
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
-
- 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/001—Softening compositions
-
- 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
- D06L1/01—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using only solid or pasty agents
-
- 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
Definitions
- the present invention further relates to a method of use of the package.
- Laundry detergents have long been known in the form of tablets (i.e. a unit dose) packaged into a polymeric film.
- An early commercial of this was Procter & Gamble's Salvo® tablets which were sold in the United States in the 1960's. In one commercially marketed execution, four Salvo® tablets were sealed within a polyethylene film. More recently automatic dish washing tablets have been presented to the consumer in a similar package.
- Laundry detergent tablets have also been presented commercially, for example in pairs, wrapped and sealed within a flow-wrap which is discarded after the package has been opened for use.
- the present invention avoids this wastefulness by providing a package which comprises a substrate and one or more fabric treatment chemicals, wherein the fabric treatment chemicals are released from the substrate through the action of temperature, friction and/or contact with water.
- the package may then be used to apply the fabric treatment chemicals either directly to fabrics, or via the wash liquor, or in the dryer; wherein the fabric treatment chemicals are active during the laundry washing and/or drying processes and/or provide a residue on laundered fabrics.
- Preferred chemicals for use in the package of the present invention are a) a surfactant and/or solvent for stain pre-treatment; or b) a fabric softening agent; or c) a fabric integrity ingredient.
- the present invention also provides a method for treating fabrics, the method comprising the step of opening a package, the package containing at least one unit dose of detergent, and subsequently dissolving and/or dispersing the detergent composition to provide a wash liquor, and wherein the package comprises an insoluble substrate and one or more fabric treatment chemicals, the chemical-containing substrate being used to directly or indirectly apply the fabric treatment chemicals to the fabrics.
- the method of the present invention comprises one of the steps of: a) pretreating stains on the fabrics with the chemical-containing substrate, before washing the fabrics with the wash liquor comprising the detergent composition; b) adding the chemical-containing substrate to the wash liquor, the wash liquor comprising the detergent composition; or c) adding the chemical-containing substrate to the dryer, after washing the fabrics with the wash liquor comprising the detergent composition.
- the detergent composition useful in the present invention may comprise any chemical components which are useful in laundry, especially but not exclusively domestic laundry; as well as process aids and other auxiliaries known in the laundry field.
- unit dose it is meant herein a predetermined amount of detergent composition, preferably in the tablet form.
- the substrate is insoluble, by which it is meant herein that at least 50% by weight of the substrate does not dissolve in water at 20°C and pH 7 for a period of at least 24 hours.
- the insoluble substrate may be formed from a sheet of flexible material.
- Materials suitable for use as a flexible sheet include mono-layer, co-extruded or laminated films.
- Such films may comprise various components, such as polyethylene, polypropylene, polystyrene, polyethylene-terephtalate.
- the insoluble substrate comprises, or consists essentially of, a polyethylene and bi-oriented-polypropylene co-extruded film with an MVTR of less than 5 g/day/m 2 .
- the package is preferably sealed around the at least one unit dose of the detergent composition so that the package is substantially impermeable to moisture so that the MVTR of the package is preferably of less than 10 g/day/m 2 , more preferably of less than 5 g/day/m 2 , even more preferably of less than 1 g/day/m 2 .
- the film may have various thicknesses. The thickness should typically be between 10 and 150 ⁇ m, preferably between 15 and 120 ⁇ m, more preferably between 20 and 100 ⁇ m, even more preferably between 25 and 80 ⁇ m and most preferably between 30 and 40 ⁇ m.
- Alternative insoluble substrates may also be formed from cellulosic or other polymeric material by methods such as wet-laying, air-laying or hydroentangling.
- the insoluble substrate preferably comprises a barrier layer typically found with packaging materials having a low oxygen transmission rate, typically of less than 300 cm 3 /m 2 /day, preferably of less than 150 cm 3 /m 2 /day, more preferably of less than 100 cm 3 /m 2 /day, even more preferably of less than 50 cm 3 /m 2 /day and most preferably of less than 10 cm 3 /m 2 /day.
- Typical materials having such barrier properties include bi-oriented polypropylene, polyethylene terephthalate, polyamide, poly(ethylene vinyl alcohol) , or laminated materials comprising one of these, as well as SiOx (Silicium oxides), or metallic foils such as aluminium foils for example.
- Such packaging material may have a beneficial influence on the stability of the product during storage for example.
- Another suitable type of substrate is those that are adapted to soften fabrics in an automatic laundry dryer, of the types disclosed in U.S. Pat. Nos. 3,989,631 , Marsan, issued Nov. 2, 1976; 4,055,248, Marsan, issued Oct. 25, 1977;
- the fabric treatment compositions are provided as an article of manufacture in combination with a dispensing means such as a flexible substrate which effectively releases the composition in an automatic laundry (clothes) dryer.
- a dispensing means such as a flexible substrate which effectively releases the composition in an automatic laundry (clothes) dryer.
- Such dispensing means can be designed for single usage or for multiple uses.
- the dispensing means can also be a "carrier material" that releases the fabric softener composition and then is dispersed and/or exhausted from the dryer.
- the dispensing means will normally carry an effective amount of fabric treatment composition.
- Such effective amount typically provides sufficient fabric conditioning/antistatic agent and/or anionic polymeric soil release agent for at least one treatment of a minimum load in an automatic laundry dryer.
- Typical amounts for a single article can vary from about 0.25 g to about 100 g, preferably from about 0.5 g to about 20 g, most preferably from about 1 g to about 10 g.
- each unit dose comprises between 10g and 100g of active components, more preferably between 30g and 60 g.
- the consumer may be guided by usage instructions to use two unit doses for an averagely soiled laundry load, to use three unit doses for a heavily soiled load.
- One unit dose may be used for a very lightly soiled load or for a half load.
- the primary package for example a cardboard box or carton
- One solution to this problem is to wrap N unit doses in a plurality, A+B, of secondary packages, so that a predetermined number of unit doses are packed in pairs, to give A packages comprising pairs of unit doses, and to wrap a predetermined number of unit doses in threes, to give B packages each comprising three unit doses, and finally to pack these secondary packages into the primary package.
- the values for "A" and "B" can be predetermined according to known consumer habits.
- N (A x n ⁇ ) + (B x n 2 ) + ...
- N, A, B, n ⁇ , n 2 ... are each integers and wherein ni ⁇ n 2 .
- n-i, n 2 ... are each 2, or greater.
- a primary package containing 32 unit doses may comprise 10 flow- wrapped secondary packages each containing 2 unit doses and 4 flow-wrapped secondary packages each containing 3 unit doses.
- a longitudinal seal is provided, which may be a fin seal or an overlapping seal, after which a first end of the package is closed with a first end seal, followed by closure of the second end with a second end seal.
- the package further comprises a means for opening the sealed package.
- the package may optionally comprise re-closing means as described in WO92/20593.
- a cold seal or an adhesive is particularly suited.
- a band of cold seal or a band of adhesive may be applied to a surface of the package at a position adjacent to the second end of the package, so that this band may provide both the initial seal and re-closure of the package.
- the adhesive or cold seal band may correspond to a region having a cohesive surface, i.e. a surface which will adhere only to another cohesive surface.
- Such re-closing means may also comprise spacers which will prevent unwanted adhesion.
- spacers are described in WO95/13225, published on 18 th May 1995.
- the main requirement is that the communication between the exterior and the interior of the package should be minimal, even after first opening of the package.
- a cold seal may be used, and in particular a grid of cold seal, whereby the cold seal is adapted so as to facilitate opening of the package.
- the chemicals preferred for use in the present invention in combination with the insoluble substrate include: a) a surfactant and/or solvent for stain pre-treatment; b) a fabric softening agent, including cationic surfactants and nonionic surfactants; c) a fabric integrity ingredient, including carboxymethyl celluloses;
- a highly preferred component of the detergent composition present on the substrate for use herein is a solvent. More preferred 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 ) 05 , and a Hansen polar parameter dP below 8 (Joule/cm 3 ) 0 5 .
- Preferred solvents for use comprise mixture of hydrocarbons with a flash point no lower than 70°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 a chain length above C12.
- Particularly preferred hydrophobic solvents are terpenes, paraffins; isoparaffins; naphtenes; aromatics; and olefins.
- 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 ) 05 include glycol ethers, more preferably glycol ethers based upon ethylene oxide, propylene oxide, or mixtures thereof. Such solvents may, and preferably are, used in combination with either short chain surfactants, long chain surfactants, or mixtures thereof.
- the hydrophobic solvents defined above are used in combination with mixtures of short chain and long chain surfactants having preferably and overall HLB value of from 2 to 16, and more preferably from 8 to 14.
- Preferred molar ratio of short-chain to long chain ratios are from 1 :10 to 10:1 , more preferably between 1 :3 and 3:1 , most preferably about 1 :1.
- Surfactants are preferably present at a level of from 1 to 50%, more preferably 10 to 40% and most preferably 15 to 30% by weight of the detergent composition.
- Short chain surfactants are surfactants which compromise a C6-C10 alkyl chain as their hydrophobic portion.
- Preferred short-chain surfactants for use are the C4-C8 fatty alcohol polyglycol ethers with 2-5 EO.
- C6-C8 alkyl sulphonates, C6- C8 alkyl sulphates, C6-C8 alkyl ethoxy sulphates, C6-C10 betaines or C6-C10 amine oxides could also be useful.
- Water-soluble nonionic surfactants are also useful as surfactants in the compositions of the invention. Indeed, preferred processes use anionic/nonionic blends.
- Such nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
- Suitable nonionic surfactants include the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 16 carbon atoms, in either a straight chain or chain configuration, with from about 4 to 25 moles of ethylene oxide per mole of alkyl phenol.
- Preferred nonionics are the water-soluble condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with from 1 to 25 moles of ethylene oxide per mole of alcohol, especially 2 to 7 moles of ethylene oxide per mole of alcohol.
- Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 9 to 15 carbon atoms; and condensation products of propylene glycol with ethylene oxide.
- polyhydroxy fatty acid amides which my be prepared by reacting a fatty acid ester and an N-alkyl polyhydroxy amine.
- the preferred amine for use in the present invention is N-(R1 )-CH2(CH2OH)4-CH2- OH and the preferred ester is a C12-C20 fatty acid methyl ester.
- Most preferred is the reaction product of N-methyl glucamine (which may be derived from glucose) with C12-C20 fatty acid methyl ester.
- Semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl moiety of from about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the groups consisting of alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon atoms.
- the fabric softening agent comprises from about 5% to about 95% preferably from about 15% to about 90%, more preferably from about 25% to about 85%, and even more preferably from about 25% to about 55%, of biodegradable cationic surfactant, preferably an ester quaternary ammonium compound (EQA).
- EQA ester quaternary ammonium compound
- the EQA of the present invention is selected from Formulas I, II, III, and mixtures thereof.
- Formula I comprises:
- Tallow is a convenient and inexpensive source of long chain alkyl and alkenyl materials. It will be understood that substituents R and R 2 of Formula I can optionally be substituted with various groups such as alkoxyl or hydroxyl groups.
- the preferred compounds can be considered to be diester (DEQA) variations of ditallow dimethyl ammonium methyl sulfate (DTDMAMS), which is a widely used fabric softener. At least 80% of the DEQA is in the diester form, and from 0% to about 20%, preferably less than about 10%, more preferably less than about 5%, can be EQA monoester (e.g., only one -Y--R 2 group).
- biodegradable Formula I compounds suitable for use in the fabric softening agents herein are: N-methyl-N,N-di-(2-C14 -C18 -acyloxy ethyl), N-2-hydroxyethyl ammonium methylsulfate; [HO--CH(CH3)CH2 ][CH3 ]+ N[CH2 CH2 OC(O)C15 H31 ]2 Br- ; [HO--CH(CH3)CH2 ][CH3 ]+ N[CH2 CH2
- a preferred compound is N-methyl, N,N-di-(2-oleyloxyethyl) N-2- hydroxyethyl ammonium methylsulfate.
- compositions and articles of the present invention comprise EQA compounds of Formula II:
- a specific example of a biodegradable Formula II EQA compound suitable for use in the aqueous fabric softening compositions herein is: 1 ,2-bis(tallowyl oxy)-3- trimethyl ammoniopropane methylsulfate (DTTMAPMS).
- Formula II EQA compounds of this invention are obtained by, e.g., replacing "tallowyl” in the above compounds with, for example, cocoyl, lauryl, oleyl, stearyl, palmityl, or the like; replacing "methyl” in the above compounds with ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, or the hydroxy substituted analogs of these radicals; replacing "methylsulfate” in the above compounds with chloride, ethylsulfate, bromide, formate, sulfate, lactate, nitrate, and the like, but methylsulfate is preferred.
- Fabric conditioning agent useful in the present invention can also comprise Formula III compounds:
- An example of this compound is methyl bis (oleyl amidoethyl) 2- hydroxyethyl ammonium methyl sulfate.
- the cationic surfactants herein can be prepared by standard esterification and quatemization reactions, using readily available starting materials. General methods for preparation are disclosed in U.S. Pat. No. 4,137,180, incorporated herein by reference.
- the diester quat when specified, it will include the monoester quat that is normally present.
- the percentage of monoester quat should be as low as possible, preferably less than about 20%.
- the level of monoester quat present can be controlled in the manufacturing of the EQA.
- EQA compounds prepared with fully saturated acyl groups are rapidly biodegradable and excellent softeners.
- compounds prepared with at least partially unsaturated acyl groups have advantages (i.e., antistatic benefits) and are highly acceptable for consumer products when certain conditions are met.
- IV Iodine Value
- Antistatic effects are especially important where the fabrics are dried in a tumble dryer, and/or where synthetic materials which generate static are used. As the IV is raised, there is a potential for odor problems.
- Such sources must be deodorized, e.g., by absorption, distillation (including stripping such as steam stripping), etc., as is well known in the art.
- the polyunsaturation content of the touch hardened fatty acid should be less than about 5%, preferably less than about 1 %.
- the cis/trans isomer weight ratios are controlled by methods known in the art such as by optimal mixing, using specific catalysts, providing high H 2 availability, etc.
- the fabric conditioning agent optionally further comprises ethoxylated and/or propoxylated sugar derivative containing a "sugar” moiety, e.g., a moiety derived from, e.g., a polyhydroxy sugar, or sugar alcohol, that contains from about 4 to about 12 hydroxy groups.
- This sugar moiety is substituted by at least one long hydrophobic group, containing from about 8 to about 30 carbon atoms, preferably from about 16 to about 18 carbon atoms.
- the hydrophobic group can contain more carbon atoms, e.g., 20-22, and/or there can be more than one hydrophobic group, preferably two or, less preferably, three.
- the hydrophobic group is supplied by esterifying one of the hydroxy groups with a fatty acid.
- the hydrophobic group can be supplied by connecting the hydrophobic group to the sugar moiety by an ether linkage, and/or a moiety containing a carboxy group esterified with a fatty alcohol can be attached to the sugar moiety to provide the desired hydrophobic group.
- Sugar moieties include sucrose, galactose, mannose, glucose, fructose, sorbitan, sorbitol, mannitol, inositol, etc., and/or their derivatives such as glucosides, galactosides, etc.
- Other "sugar” types of moieties containing multiple hydroxy groups can also be used including starch fractions and polymers such as polyglycerols.
- the sugar moiety can be any polyhydroxy group that provides the requisite number/density of hydroxy groups approximating that of conventional sugar moieties.
- the hydrophobic group can be provided by attachment with an ester, ether, or other linkage that provides a stable compound.
- the hydrophobic group is preferably primarily straight chain, and preferably contains some unsaturation to provide additional antistatic benefits.
- Such hydrophobic groups and their sources are well known, and are described hereinafter with respect to the more conventional types of softening agents.
- the polyalkoxy chain can be all ethoxy groups, and/or can contain other groups such as propoxy, glyceryl ether, etc., groups.
- polyethoxy groups are preferred, but for improved properties such as biodegradability, glyceryl ether groups can be inserted.
- R is a hydrophobic group containing from about 8 to about 30, preferably from about 12 to about 22, more preferably from about 16 to about 18 carbon atoms;
- sugar refers to a polyhydroxy group, preferably derived from a sugar, sugar alcohol, or similar polyhydroxy compound;
- R1 is an alkylene group, preferably ethylene or propylene, more preferably ethylene;
- m is a number from 1 to about 4, preferably 2;
- n is a number from about 4 to about 100, preferably from about 10 to about 40. (R1 0)n can be attached to a sugar moiety or link a sugar moiety and R.
- Preferred compounds of this type are polyethoxylated sorbitan monostearate and polyethoxylated sorbitan tristearate, e.g., Glycosperse S-20 and Glycosperse TS-20, respectively, from Lonza, each of which contain about 20 ethoxylate moieties per molecule, and mixtures thereof.
- the level of the polyethoxy sugar derivative is typically at least about 2%, preferably at least about 10%.
- Preferably the maximum level is no more than about 90%, more preferably no more than about 75%.
- the polyethoxy sugar derivative provides improved antistatic properties to the compositions and can provide equivalent antistatic properties to conventional dryer added compositions, and/or articles, even with less, or no, quaternary ammonium softener materials present. It is possible to prepare a dryer-added composition, or article, that is entirely nonionic.
- Fabric softening agents employed herein optionally contain, as a preferred component, at a level of from 0% to about 95%, preferably from about 10% to about 75%, more preferably from about 20% to about 60%, carboxylic acid salt of a tertiary amine which has the formula:
- R5 is a long chain aliphatic group containing from about 8 to about 30 carbon atoms
- R6 and R7 are the same or different from each other and are selected from the group consisting of aliphatic groups containing from about 1 to about 30 carbon atoms, hydroxyalkyl groups of the Formula R4 OH wherein R4 is an alkylene group of from about 2 to about 30 carbon atoms, and alkyl ether groups of the formula R9 (OCn H2n)m wherein R9 is alkyl and alkenyl of from about 1 to about 30 carbon atoms and hydrogen, each n is 2 or 3, and m is from about 1 to about 30, and wherein R8 is selected from the group consisting of unsubstituted alkyl, alkenyl, aryl, alkaryl and aralkyl of about 1 to about 30 carbon atoms, and substituted alkyl, alkenyl, aryl, alkaryl, and aralkyl of from about 1 to about 30 carbon atoms
- This component can provide the following benefits: superior odor, a decrease in paint softening of the dryer drum, and/or improved fabric softening performance, compared to similar articles without this component.
- Either R5, R6, R7, and/or R8 chains can contain unsaturation for improved antistatic benefits.
- Tertiary amine salts of carboxylic acids have superior chemical stability, compared to primary and secondary amine carboxylate salts.
- primary and secondary amine carboxylates tend to form amides when heated, e.g., during processing or use in the dryer. Also, they absorb carbon dioxide, thereby forming high melting carbamates which build up as an undesirable residue on treated fabrics.
- R5 is an aliphatic chain containing from about 12 to about 30 carbon atoms
- R6 is an aliphatic chain of from about 1 to about 30 carbon atoms
- R7 is an aliphatic chain of from about 1 to about 30 carbon atoms.
- Particularly preferred tertiary amines for static control performance are those containing unsaturation; e.g., oleyldimethylamine and/or soft tallowalkyldimethylamine.
- Examples of preferred tertiary amines as starting material for the reaction between the amine and carboxylic acid to form the tertiary amine salts are: lauryldimethylamine, myristyldimethylamine, stearyldimethylamine, tallowalkyldimethylamine, coconutalkyldimethylamine, dilaurylmethylamine, distearylmethylamine, ditallowalkylmethylamine, oleyldimethylamine, dioleyl methylamine, lauryldi(3-hydroxypropyl)amine, stearyldi(2-hydroxyethyl)amine, trilaurylamine, laurylethylmethylamine, and C18 H37 N[(OC2 H4)10 OH]2.
- Preferred fatty acids are those wherein R8 is a long chain, unsubstituted alkyl or alkenyl group of from about 8 to about 30 carbon atoms, more preferably from about 11 to about 17 carbon atoms.
- Examples of specific carboxylic acids as a starting material are: formic acid, acetic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, oxalic acid, adipic acid, 12-hydroxystearic acid, benzoic acid, 4-hydroxybenzoic acid, 3- chlorobenzoic acid, 4-nitrobenzoic acid, 4-ethylbenzoic acid, 4-(2- chloroethyl)benzoic acid, phenylacetic acid, (4-chlorophenyl)acetic acid, (4- hydroxyphenyl)acetic acid, and phthalic acid.
- Preferred carboxylic acids are stearic, oleic, lauric, myristic, palmitic, and mixtures thereof.
- Preferred amine salts for use herein are those wherein the amine moiety is a C8 - C30 alkyl or alkenyl dimethyl amine or a di-C8 -C30 alkyl or alkenyl methyl amine, and the acid moiety is a C8 -C30 alkyl or alkenyl monocarboxylic acid.
- the amine and the acid, respectively, used to form the amine salt will often be of mixed chain lengths rather than single chain lengths, since these materials are normally derived from natural fats and oils, or synthetic processed which produce a mixture of chain lengths. Also, it is often desirable to utilize mixtures of different chain lengths in order to modify the physical or performance characteristics of the softening composition.
- Specific preferred amine salts for use in the present invention are oleyldimethylamine stearate, stearyldimethylamine stearate, stearyldimethylamine tallowate, stearyldimethylamine myristate, stearyldimethylamine palmitate, distearylmethylamine palmitate, distearylmethylamine laurate, and mixtures thereof.
- a particularly preferred mixture is oleyldimethylamine stearate and distearylmethylamine myristate, in a ratio of 1 :10 to 10:1 , preferably about 1 :1.
- Fabric conditioning agents useful in the present invention optionally further comprise unsaturated fatty acid.
- the unsaturated fatty acid is preferably present in the fabric conditioning agents herein at a level of from about 1 % to about 15%, preferably from about 3% to about 12%.
- Preferred fatty acids are those containing a long chain, unsubstituted alkenyl group of from about 8 to about 30 carbon atoms, more preferably from about 11 to about 17 carbon atoms.
- Examples of specific carboxylic acids are: oleic acid, linoleic acid, and mixtures thereof. These unsaturated fatty acids can be used in combination with saturated fatty acids like stearic, palmitic, and/or lauric acids.
- Preferred carboxylic acids are oleic, linoleic, tallow fatty acids, and mixtures thereof.
- a highly preferred optional ingredient is a nonionic fabric softening agent material other than those disclosed hereinbefore.
- nonionic fabric softener materials typically have an HLB of from about 2 to about 9, more typically from about 3 to about 7.
- the materials selected should be relatively crystalline, higher melting (e.g., >25° C). These materials can then improve processability of the composition.
- the level of optional nonionic softener in the solid composition is typically from about 10% to about 50%, preferably from about 15% to about 40%.
- Preferred nonionic softeners are fatty acid partial esters of polyhydric alcohols, or anhydrides thereof, wherein the alcohol, or anhydride, contains from about 2 to about 18, preferably from about 2 to about 8, carbon atoms, and each fatty acid moiety contains from about 8 to about 30, preferably from about 16 to about 20, carbon atoms.
- Typical examples of said fatty acids being lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and behenic acid.
- such softeners contain from about 1 to about 4, preferably about 2 fatty acid groups per molecule.
- the polyhydric alcohol portion of the ester can be ethylene glycol, polyethylene glycol, (e.g., tetraethylene glycol), glycerol, poly (e.g., di-, tri-, tetra, penta-, and/or hexa-) glycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol or sorbitan.
- These nonionic fabric softening materials do not include the ethoxylated sugar derivatives disclosed hereinbefore. They typically contain no more than about 4 ethoxy groups per molecule.
- Highly preferred optional nonionic softening agents for use in the present invention are C10 -C26 acyl sorbitan esters and polyglycerol monostearate.
- Sorbitan esters are esterified dehydration products of sorbitol.
- the preferred sorbitan ester comprises a member selected from the group consisting of C10- C26 acyl sorbitan monoesters and C10 -C26 acyl sorbitan diesters and ethoxylates of said esters wherein one or more of the unesterified hydroxyl groups in said esters contain from 1 to about 4 oxyethylene units, and mixtures thereof.
- sorbitan esters containing unsaturation e.g., sorbitan monooleate
- sorbitan complex mixtures of anhydrides of sorbitol are collectively referred to herein as "sorbitan”. It will be recognized that this "sorbitan" mixture will also contain some free, uncyclized sorbitol.
- ester mixture having from 20-50% mono-ester, 25-50% di-ester and 10-35% of tri-and tetra-esters are preferred.
- sorbitan mono-ester e.g., monostearate
- sorbitan mono-ester does in fact contain significant amounts of di- and tri-esters and a typical analysis of commercial sorbitan monostearate indicates that it comprises about 27% mono-, 32% di- and 30% tri- and tetra-esters.
- sorbitan monostearate therefore is a preferred material.
- Mixtures of sorbitan stearate and sorbitan palmitate having stea rate/pa Imitate weight ratios varying between 10:1 and 1 :10, and 1 ,5-sorbitan esters are useful. Both the 1 ,4- and 1 ,5-sorbitan esters are useful herein.
- alkyl sorbitan esters for use in the softening compositions herein include sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monobehenate, sorbitan monooleate, sorbitan dilaurate, sorbitan dimyristate, sorbitan dipalmitate, sorbitan distearate, sorbitan dibehenate, sorbitan dioleate, sorbitan tristearate, and mixtures thereof, and mixed tallowalkyl sorbitan mono-, di-, and tri-esters.
- the preferred sorbitan esters employed herein can contain up to about 15% by weight of esters of the C20-C26, and higher, fatty acids, as well as minor amounts of C8, and lower, fatty esters.
- Glycerol and polyglycerol esters especially glycerol, diglycerol, triglycerol, and polyglycerol mono- and/or di- esters, preferably mono-, are also preferred herein (e.g., polyglycerol monostearate with a trade name of Radiasurf 7248).
- Useful glycerol and polyglycerol esters include mono-esters with stearic, oleic palmitic, lauric, isostearic, myristic, and/or behenic acids and the diesters of stearic, oleic, palmitic, lauric, isostearic, behenic, and/or myristic acids. It is understood that the typical mono-ester contains some di- and tri-ester, etc.
- glycol esters also include the polyglycerol, e.g., diglycerol through octaglycerol esters.
- Cyclodextrin/perfume complexes and free perfume can also be used in the present invention in combination with the insoluble substrate.
- the package herein can also contain from about 0.5% to about 60%, preferably from about 1 % to about 50%, cyclodextrin/perfume inclusion complexes, as disclosed in U.S. Pat. Nos. 5,139,687, Botcher et al., issued Aug. 18, 1992; and 5,234,610, Gardlik et al., issued Aug. 10, 1993, which are incorporated herein by reference.
- Perfumes are highly desirable, can usually benefit from protection, and can be complexed with cyclodextrin.
- Fabric softening products typically contain perfume to provide an olfactory aesthetic benefit and/or to serve as a signal that the product is effective.
- perfume ingredients and compositions of this invention are the conventional ones known in the art. Selection of any perfume component, or amount of perfume, is based solely on aesthetic considerations. Suitable perfume compounds and compositions can be found in the art including U.S. Pat. Nos. 4,145,184, Brain and Cummins, issued Mar. 20, 1979; 4,209,417, Whyte, issued Jun. 24, 1980; 4,515,705, Moeddel, issued May 7, 1985; and 4,152,272, Young, issued May 1 , 1979, all of said patents being incorporated herein by reference. Many of the art recognized perfume compositions are relatively substantive, as described hereinafter, to maximize their odor effect on substrates. However, it is a special advantage of perfume delivery via the perfume/ cyclodextrin complexes that nonsubstantive perfumes are also effective. The volatility and substantivity of perfumes is disclosed in U.S. Pat. No. 5,234,610, supra.
- Solid, dryer-activated fabric conditioning compositions are a uniquely desirable way to apply the cyclodext ns, since they are applied at the very end of a fabric treatment regimen when the fabric is clean and when there are almost no additional treatments that can remove the cyclodextrin.
- the unit dose detergent composition may comprise any ingredients which are useful for laundry purposes such as surfactants (anionic, nonionic, cationic, amphoteric, zwittenonic); builders (including phosphates, zeolites); polymers (including acrylic and maleic polymers and copolymers, carboxymethyl cellulose); bleach (such as perborate, percarbonate, and various bleach precursors); bleach activators (such as TAED); clay (such as bentonite); chelating agents; optical brightener; suds suppressor; enzymes; perfume.
- Various salts are also commonly used in detergent compositions for various purposes, some are builders in their own right, others are used as pH buffers or as fillers. The most common salts are carbonates, silicates (including SKS-6®), citrates and sulphates.
- the various components are prepared in powdered or granular form and then mixed prior to being formed into tablets.
- the tablet is most commonly formed by compression of the powders and granules in a tablet mold.
- the tablets may be formed with the aid of tabletting aids, such as binders, disintegrants etc. Binders and disintegrants are described in Handbook of Pharmaceutical Excipients (1986).
- the tablets may also comprise a coating, such as a dicarboxylic acid.
- each unit dose comprises between 10g and 100g of active components, more preferably between 30g and 60 g.
- a detergent powder of composition A (see table 1 ) was prepared as follows: all the particulate materials of composition A were mixed together in a mixing drum to form a homogenous particulate mixture. During the mixing the binder was sprayed on.
- Neodol AE7® A mix of 80% of nonionic surfactant Neodol AE7® and 20% of Lutensit KHD 96® was prepared, by heating the mix to 50°C. 0.74g of this hot melt was applied to a sheet of polypropylene film of a thickness of 30 ⁇ m and of a dimension of 14.5x16cm. The sheet was left to cool down for 24 hours, at ambient conditions. This treated sheet of polypropylene film can be used to wrap two of the tablets prepared in ii).
- a detergent powder of composition B (see table 1 ) was prepared as described in step i) of example 1.
- Anionic agglomerates 1 comprises 40% AS/AE3S; 27% Zeolite A; 12% sodium carbonate; 9% maleic/acrylic copolymer; the balance being moisture and minor ingredients, impurities etc.
- Anionic agglomerates 2 comprises 20% AS/AE3S; 20 LAS; 28% Zeolite A; 20% sodium carbonate; the
- Cationic agglomerates comprises 20% quaternary ammonium compound; 64%
- Nonionic agglomerates comprises 24% alkyl ethoxylate (AE7); 11 % Zeolite A;
- Bleach activator agglomerates comprises 81 % TAED; 17% acrylic/maleic copolymer and 2% water. Suds suppressor comprises 11.5% silicone oil; 4.5% hyfac; 13% TAE80 and 71% starch.
- Fluorescer comprises 87% Brightener 47 (81 % active) and 13% Brightener 49
- Tablets were then made in the following way. 42.3g of the mixture was introduced into a mould of square shape with dimensions of 42x42mm and compressed with a force of 1.5kN by means of an Instron Press, to give a tablet density of about 1050 g/l. Afterwards, the pressed tablets were coated with a mix (melted at 175°C) containing 96.5% of a dicarboxylic acid (adipic acid) and 3.5% of a disintegrant (purolite). The total coating weight of the tablet was 2.5g.
- step iii) of example 5 was dried in a Miele Novotronic T490 without the sheet prepared in step ii) of example 5.
- the fabric conditioning (level of softness) result in this experiment is as follows:
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Mechanical Engineering (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Detergent Compositions (AREA)
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Abstract
Description
Claims
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MXPA02010601A MXPA02010601A (en) | 2000-04-27 | 2001-04-25 | Packaging for unit dose of detergent and method of its use. |
CA002403582A CA2403582C (en) | 2000-04-27 | 2001-04-25 | Packaging for unit dose of detergent and method of its use |
AU2001257301A AU2001257301B2 (en) | 2000-04-27 | 2001-04-25 | Packaging for unit dose of detergent and method of its use |
DE60105581T DE60105581T2 (en) | 2000-04-27 | 2001-04-25 | PACKAGING FOR WASHING OR DETERGENT CASES AND ITS METHOD OF USE |
AU5730101A AU5730101A (en) | 2000-04-27 | 2001-04-25 | Packaging for unit dose of detergent and method of its use |
AT01930798T ATE276354T1 (en) | 2000-04-27 | 2001-04-25 | PACKAGING FOR SINGLE CANS OF DETERGENT OR CLEANING PRODUCT AND METHOD OF USE THEREOF |
BR0110365-2A BR0110365A (en) | 2000-04-27 | 2001-04-25 | Detergent unit dose packaging and use process |
EP01930798A EP1276847B1 (en) | 2000-04-27 | 2001-04-25 | Packaging for unit dose of detergent and method of its use |
JP2001578601A JP2003531282A (en) | 2000-04-27 | 2001-04-25 | Packaging for unit dosage of detergent and its use |
US10/278,239 US7022659B2 (en) | 2000-04-27 | 2002-10-23 | Packaged unit dose of detergent and method of treating fabrics |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00870086 | 2000-04-27 | ||
EP00870086.6 | 2000-04-27 | ||
EP00202542A EP1149897A1 (en) | 2000-04-27 | 2000-07-14 | Packaging for unit dose of detergent and method of its use |
EP00202542.7 | 2000-07-14 |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2001/007710 Continuation WO2001085898A1 (en) | 2000-04-27 | 2001-03-09 | Detergent product |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/278,239 Continuation US7022659B2 (en) | 2000-04-27 | 2002-10-23 | Packaged unit dose of detergent and method of treating fabrics |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001081530A1 true WO2001081530A1 (en) | 2001-11-01 |
Family
ID=26072510
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2001/013456 WO2001081530A1 (en) | 2000-04-27 | 2001-04-25 | Packaging for unit dose of detergent and method of its use |
Country Status (13)
Country | Link |
---|---|
EP (2) | EP1149897A1 (en) |
JP (1) | JP2003531282A (en) |
KR (1) | KR100496724B1 (en) |
CN (1) | CN1426453A (en) |
AR (1) | AR028045A1 (en) |
AT (1) | ATE276354T1 (en) |
AU (2) | AU2001257301B2 (en) |
BR (1) | BR0110365A (en) |
CA (1) | CA2403582C (en) |
DE (1) | DE60105581T2 (en) |
ES (1) | ES2227184T3 (en) |
MX (1) | MXPA02010601A (en) |
WO (1) | WO2001081530A1 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007111899A2 (en) * | 2006-03-22 | 2007-10-04 | The Procter & Gamble Company | Liquid treatment composition |
JP6352901B2 (en) * | 2012-04-24 | 2018-07-04 | スリーエム イノベイティブ プロパティズ カンパニー | Surfactant-containing fluorochemical composition, article, and method |
WO2013162704A1 (en) | 2012-04-24 | 2013-10-31 | 3M Innovative Properties Company | Fluorochemical compounds, compositions, articles, and methods |
CN110343580A (en) * | 2019-07-23 | 2019-10-18 | 广州立白企业集团有限公司 | A kind of unit dose detergent product of high-moisture |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001000781A1 (en) * | 1999-06-25 | 2001-01-04 | Henkel Kommanditgesellschaft Auf Aktien | Packaging for a portion of an active substance |
DE19934254A1 (en) * | 1999-07-21 | 2001-01-25 | Henkel Kgaa | Washing or detergent portion comprises a measured amount of a washing composition(s) and a polymer material enclosing it and also containing a washing composition(s) |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3435537A (en) | 1967-06-20 | 1969-04-01 | Joseph F Rumsey Jr | Apparatus for deodorizing or treating clothes in a clothes drier |
US3686025A (en) | 1968-12-30 | 1972-08-22 | Procter & Gamble | Textile softening agents impregnated into absorbent materials |
US3634947A (en) | 1970-10-20 | 1972-01-18 | Colgate Palmolive Co | Coating apparatus |
US3633538A (en) | 1970-10-20 | 1972-01-11 | Colgate Palmolive Co | Spherical device for conditioning fabrics in dryer |
US3701202A (en) | 1971-04-13 | 1972-10-31 | Russel Edward Compa | Distributor for liquid textile conditioners |
US3736668A (en) | 1971-05-19 | 1973-06-05 | Colgate Palmolive Co | Device for dryer applied textile conditioners |
US4000340A (en) | 1973-10-29 | 1976-12-28 | The Procter & Gamble Company | Clothes dryer additive containing crisping agents |
US4022938A (en) | 1974-04-16 | 1977-05-10 | The Procter & Gamble Company | Fabric treatment compositions |
US4055248A (en) | 1974-12-17 | 1977-10-25 | The Procter & Gamble Company | Fabric treating compositions and articles |
US3989631A (en) | 1974-12-17 | 1976-11-02 | The Procter & Gamble Company | Fabric treating compositions comprising clay mixtures |
US4073996A (en) | 1976-02-24 | 1978-02-14 | The Procter & Gamble Company | Fabric treating articles and processes |
US4808086A (en) | 1985-03-06 | 1989-02-28 | The Procter & Gamble Company | Articles and methods for treating fabrics |
US4764289A (en) | 1987-10-05 | 1988-08-16 | The Procter & Gamble Company | Articles and methods for treating fabrics in clothes dryer |
US6189417B1 (en) * | 1999-08-13 | 2001-02-20 | Nielsen & Bainbridge L.L.C. | Picture frame assembly machine |
-
2000
- 2000-07-14 EP EP00202542A patent/EP1149897A1/en not_active Withdrawn
-
2001
- 2001-04-25 JP JP2001578601A patent/JP2003531282A/en not_active Withdrawn
- 2001-04-25 AU AU2001257301A patent/AU2001257301B2/en not_active Expired - Fee Related
- 2001-04-25 AT AT01930798T patent/ATE276354T1/en not_active IP Right Cessation
- 2001-04-25 CA CA002403582A patent/CA2403582C/en not_active Expired - Fee Related
- 2001-04-25 MX MXPA02010601A patent/MXPA02010601A/en active IP Right Grant
- 2001-04-25 EP EP01930798A patent/EP1276847B1/en not_active Expired - Lifetime
- 2001-04-25 AU AU5730101A patent/AU5730101A/en active Pending
- 2001-04-25 WO PCT/US2001/013456 patent/WO2001081530A1/en active IP Right Grant
- 2001-04-25 BR BR0110365-2A patent/BR0110365A/en not_active IP Right Cessation
- 2001-04-25 ES ES01930798T patent/ES2227184T3/en not_active Expired - Lifetime
- 2001-04-25 KR KR10-2002-7014420A patent/KR100496724B1/en not_active IP Right Cessation
- 2001-04-25 CN CN01808560A patent/CN1426453A/en active Pending
- 2001-04-25 DE DE60105581T patent/DE60105581T2/en not_active Expired - Fee Related
- 2001-04-26 AR ARP010101956A patent/AR028045A1/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001000781A1 (en) * | 1999-06-25 | 2001-01-04 | Henkel Kommanditgesellschaft Auf Aktien | Packaging for a portion of an active substance |
DE19934254A1 (en) * | 1999-07-21 | 2001-01-25 | Henkel Kgaa | Washing or detergent portion comprises a measured amount of a washing composition(s) and a polymer material enclosing it and also containing a washing composition(s) |
Also Published As
Publication number | Publication date |
---|---|
DE60105581T2 (en) | 2005-09-29 |
EP1276847A1 (en) | 2003-01-22 |
CN1426453A (en) | 2003-06-25 |
CA2403582C (en) | 2007-06-19 |
AU5730101A (en) | 2001-11-07 |
EP1149897A1 (en) | 2001-10-31 |
JP2003531282A (en) | 2003-10-21 |
ES2227184T3 (en) | 2005-04-01 |
DE60105581D1 (en) | 2004-10-21 |
KR100496724B1 (en) | 2005-06-22 |
CA2403582A1 (en) | 2001-11-01 |
BR0110365A (en) | 2003-02-18 |
AR028045A1 (en) | 2003-04-23 |
EP1276847B1 (en) | 2004-09-15 |
MXPA02010601A (en) | 2003-03-10 |
AU2001257301B2 (en) | 2005-05-05 |
ATE276354T1 (en) | 2004-10-15 |
KR20020089532A (en) | 2002-11-29 |
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