WO2014089270A1 - Use of composition to reduce weeping and migration through a water soluble film - Google Patents

Use of composition to reduce weeping and migration through a water soluble film Download PDF

Info

Publication number
WO2014089270A1
WO2014089270A1 PCT/US2013/073259 US2013073259W WO2014089270A1 WO 2014089270 A1 WO2014089270 A1 WO 2014089270A1 US 2013073259 W US2013073259 W US 2013073259W WO 2014089270 A1 WO2014089270 A1 WO 2014089270A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
use according
composition
solvent
film
Prior art date
Application number
PCT/US2013/073259
Other languages
French (fr)
Inventor
Regine Labeque
Katrien Andrea Lieven VAN ELSEN
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to JP2015545832A priority Critical patent/JP6185075B2/en
Priority to BR112015012916A priority patent/BR112015012916A2/en
Priority to CN201380061599.3A priority patent/CN104812883A/en
Priority to RU2015126906A priority patent/RU2619119C2/en
Priority to MX2015006848A priority patent/MX2015006848A/en
Priority to CA2893757A priority patent/CA2893757C/en
Publication of WO2014089270A1 publication Critical patent/WO2014089270A1/en
Priority to ZA2015/03383A priority patent/ZA201503383B/en
Priority to US14/731,455 priority patent/US9404071B2/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/043Liquid or thixotropic (gel) compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/045Multi-compartment
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40Dyes ; Pigments
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43Solvents

Definitions

  • the present invention relates to the use of a composition comprising anionic surfactant and solvent, when encapsulated within a water-soluble film, for reducing migration and weeping of the composition through the film.
  • Water-soluble unitized dose products have become popular in recent years.
  • the compositions held within the water-soluble film must have a controlled amount of water so as not to preemptively dissolve the film.
  • unitized dose compositions comprise solvents to solubilise ingredients and act as a carrier.
  • solvents in the composition within the product or within the film plasticise the film, making it more elastic and supple.
  • the solvent can also negatively affect the film structure and integrity.
  • solvents can affect whether or not, or the speed of which components of the composition migrate or weep through the film. This is particularly a problem where the weeping is excessive and the pouch takes on a slimy, unpleasant feeling.
  • the object of the present invention has been to reduce the above problems, by reducing and controlling the level of weeping and migration of a composition or components of the composition through the film.
  • the present application relates to the use of a composition for controlling migration and weeping of a composition through a water soluble film.
  • weeping it is meant the travel of a composition, or components of the composition, encapsulated within a water-soluble film pouch, from within a pouch to outside the pouch.
  • migration it is meant weeping from one compartment of a multi-compartment pouch, to another compartment of the same pouch.
  • Plasticization is a term used to describe the elasticity, flexibility and brittleness of film. A film that is completely elastic, will recover its original shape once having been stretched. A film that is overplasticized tends to gain elasticity, eventually losing rigidity and becoming floppy.
  • plasticizing solvents can be incorporated into the film on production, indeed this is most often the case, for ease of processing. However in addition plasticizing solvent can also be present in the composition which the film encapsulates. It is the Applicants belief that incorporating the specific plasticizing solvents of the present invention provides a beneficial plasticization of the film, that encourages the reduction of migration and weeping.
  • the detergent composition comprises an anionic surfactant and a solvent system.
  • the solvent system comprises at least one primary solvent having Hansen solubility ( ⁇ ) of less than 29.
  • the composition of the present invention comprises an anionic surfactant.
  • the composition comprises from 1% to 80% by weight of an anionic surfactant. More preferably the composition comprises from 2 to 60%, more preferably from 7 to 50% and most preferably 10 to 40% anionic surfactant by weight of the composition.
  • Useful anionic surfactants can themselves be of several different types. For example, water-soluble salts of the higher fatty acids, i.e., "soaps", are useful anionic surfactants in the compositions herein. This includes alkali metal soaps such as the sodium, potassium, ammonium, and alkyl ammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms.
  • Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids.
  • Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
  • non-soap anionic surfactants which are suitable for use herein include the water-soluble salts, preferably the alkali metal, and ammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • alkyl is the alkyl portion of acyl groups.
  • this group of synthetic surfactants are a) the sodium, potassium and ammonium alkyl sulfates, especially those obtained by sulfating the higher alcohols (Cg-Cig carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; b) the sodium, potassium and ammonium alkyl polyethoxylate sulfates, particularly those in which the alkyl group contains from 10 to 22, preferably from 12 to 18 carbon atoms, and wherein the polyethoxylate chain contains from 1 to 15, preferably 1 to 6 ethoxylate moieties; and c) the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S.
  • linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as Cn-C ⁇ LAS, sodium, potassium and ammonium alkyl polyethoxylate sulfates having from 12 to 18 carbon atoms and mixtures thereof.
  • the composition of the present invention comprises a solvent system.
  • the solvent system comprises at least one primary solvent having Hansen solubility ( ⁇ ) of less than 29, more preferably less than 28.5 and preferably greater than 10, more preferably greater than 15.
  • the Hansen solubility parameter is a well known and calculated parameter based on a three component measuring system.
  • the Hansen solubility parameter is based on a dispersion force component (5a), a hydrogen bonding component (3 ⁇ 4) and a polar component ( ⁇ ⁇ ).
  • Dispersion forces are weak attractive forces between non-polar molecules. The magnitude of these forces depends on the polarizability of the molecule, and the dispersion hansen solubility parameter (5 d ) typically increases with increasing volume (and size) of the molecule, all other properties being roughly equal. Hansen solubility parameters are calculated at 25°C, with ChemSW's molecular modeling Pro v6.1.9 software package which uses an unpublished proprietary algorithm that is based on values published in the Handbook of solubility Parameters and other parameters by Allan F M Barton (CRC Press 1983) for solvents obtained experimentally by Hansen.
  • the primary solvent preferably has molecular weight of less than 1500, more preferably less than 1000, even more preferably less than 700.
  • the primary solvent preferably has a molecular weight of greater than 10, more preferably greater than 100.
  • the primary solvent preferably has a cLog P of greater than -1.0 and more preferably less than +10.
  • the primary solvent preferably has a Hydrogen bonding component (3 ⁇ 4) of less than 20.5, and preferably greater than 10.
  • the primary solvent is preferably selected from the group consisting of polyethylene glycol (PEG) polymer having molecular weight between 300 and 600, dipropylene glycol (DPG), nbutoxy propoxy propanol (nBPP) and mixtures thereof.
  • the primary solvent is selected from the group consisting of polyethylene glycol (PEG) polymer having molecular weight between 400 and 600, dipropylene glycol (DPG), nbutoxy propoxy propanol (nBPP) and mixtures thereof.
  • PEG polyethylene glycol
  • DPG dipropylene glycol
  • nBPP nbutoxy propoxy propanol
  • Table 1 shows the Hansen Solubility components of the preferred primary solvents and some comparative solvents falling outside of the scope of the invention.
  • the primary solvent is preferably present at a level of from 1 to 25%, preferably from 2.5 to 20%, more preferably from 4 to 19% by weight of the composition.
  • the solvent system also comprises a secondary solvent.
  • the secondary solvent is preferably selected from the group consisting of glycerol, water and mixtures thereof.
  • glycerol is preferably present at a level of less than 5%, more preferably less than 4%, more preferably less than 3%, most preferably less than 2% by weight of the composition.
  • the glycerol secondary solvent is present at a level of greater than 0.1%, more preferably greater than 0.5%, most preferably greater than 1% by weight of the composition.
  • the secondary solvent may also comprise water. When water is present it is preferably present at a level of less than 20%, more preferably less than 15%, most preferably less than 10% by weight of the composition.
  • the ratio of primary solvent to secondary solvent glycerol is from 7: 1 to 1:5, more preferably from 6.5: 1 to 1:3, most preferably 3: 1 to 1: 1.
  • compositions of the present invention preferably comprise a negatively charged hueing dye.
  • negatively charged hueing dye it is meant that the dye residue comprises a moiety capable of being negatively charged in the composition.
  • the composition will comprise from 0.00001wt% to 0.5wt% of hueing dye.
  • hueing dye provides a blue or violet shade to fabric.
  • Hueing dyes can be used either alone or in combination to create a specific shade of hueing and/or to shade different fabric types. This may be provided for example by mixing a red and green-blue dye to yield a blue or violet shade.
  • Hueing dyes may be selected from any known chemical class of dye chromophore including, but not limited to, acridine, anthraquinone (including polycyclic quinones), azine, azo (e.g., monoazo, disazo, trisazo, tetrakisazo, polyazo), including premetallized azo, benzodifurane and benzodifuranone, carotenoid, coumarin, cyanine, diazahemicyanine, diphenylmethane, formazan, hemicyanine, indigoids, methine, naphthalimides, naphthoquinone, nitro and nitroso, oxazine, phthalocyanine, pyrazoles, stilbene, styryl, triarylmethane, triphenylmethane, xanthenes, tripehnooxazine and mixtures thereof.
  • acridine e.g., monoazo,
  • Preferred negatively charged hueing dyes comprise those selected from the group having Formula I below.
  • D represents the residue of a dye comprising a chromophore group
  • A is a moiety selected from the group consisting of OS0 3 M, S0 3 M, C0 2 M, OC0 2 M, OP0 3 M 2 , OP0 3 HM and OP0 2 M . More preferably A is selected from the group consisting of OS0 3 M, S0 3 M, C0 2 M, and OC0 2 M. Even more preferably A is selected from the group consisting of S0 3 M and C0 2 M. M is any suitable charge balancing counterion. M is preferably selected from the group consisting of Hydrogen, an alkali or alkali earth metal ion. More preferably M is selected from the group consisting of hydrogen, sodium or potassium ion.
  • the dye or mixture of dyes of Formula I will be present in the composition in an amount from 0.00001 to 5 wt of the composition, more usually in an amount from 0.0001 or from 0.001 to lwt% or to 0.5 wt% or to 0.25 wt% of the composition.
  • the dye residue, D may comprise one or more of any suitable class of chromophore group.
  • Suitable chromophore groups include, but are not limited, to any suitable chromophore, preferably selected from the group listed above. More preferably the chromophore group is selected from the group consisting of benzodifurane, methine, triphenylmethane, azine, tripehnoxazine, naphthalimide, pyrazole, naphthoquinone, anthraquinone, mono-azo and bis-azo and mixtures thereof.
  • the dye residue, D is selected form the group consisting of Azine, anthraquinone and azo chromophores may be preferred in some embodiments.
  • the hueing dye is a blue or violet hueing dye, providing a blue or violet color to a white cloth or fabric with a hue angle of 240 to 345, more preferably 260 to 325, even more preferably 270 to 310.
  • a hueing dye suitable for use in the present invention has, in the wavelength range of about 400 nm to about 750 nm, in methanol solution, a maximum extinction coefficient greater than about 1000 liter/mol/cm. In one aspect, a hueing dye suitable for use in the present invention has, in the wavelength range of about 540 nm to about 630 nm, a maximum extinction coefficient from about 10,000 to about 100,000 liter/mol/cm. In one aspect, a hueing dye suitable for use in the present invention has, in the wavelength range of about 560 nm to about 610 nm, a maximum extinction coefficient from about 20,000 to about 70,000 liter/mol/cm.
  • Preferred hueing dyes are selected from the group consisting of thiophene azo carboxylate dyes having the generalized structure of Formula II:
  • R l d R 2 are independently selected from [(CH 2 CR'HO) x (CH 2 CR"HO) y Q], C i2 alkyl, C 6 -
  • each R 5 is selected from the group consisting of C C ⁇ linear or branched alkyl, C6-C 14 aryl and C 7 - C 16 arylalkyl; preferably R 5 is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, hexyl, 2-ethylhexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, phenyl, benzyl, 2-phenylethyl, naphthyl and mixtures thereof; and wherein Y is an organic radical represented by Formula III Formula III
  • M is H or a charge balancing cation
  • m is 0 to 5, preferably 0, 1, 2 or 3
  • n is 0 to 5, preferably 0, 1, 2 or 3
  • the sum of m + n is 1 to 10, preferably 1, 2 or 3
  • each R8 is independently selected from the group consisting of H and C3-18 or C4-C18 or even C4-7 and/or C9-18 alkenyl, and wherein at least one R8 group is not H.
  • Suitable negatively charged dyes may also be selected from the group consisting of carboxylate dyes having the structure of Formula IV:
  • D is as defined above and L is an organic linking group preferably having a molecular weight from 14 to 1000 Daltons, or 14 to 600, or 28 to 300, preferably consisting essentially only of C, H and optionally additionally O and/or N, and in the sequence of bonds starting from the carbonyl carbon of the C(0)OM group and ending at the dye moiety, any -(C a (0)-Ob)- groups are incorporated such that the oxygen atom O b is encountered prior to the carbonyl carbon C a .
  • L is a Ci_ 2 o alkylene chain having optionally therein ether (-0-) and/or ester and/or amide links, the chain being optionally substituted for example with -OH, -CN, -N0 2 , -SO 2 CH 3 ,-Cl, -Br; and M is any suitable counterion, typically hydrogen, sodium or potassium ion.
  • ether -0-
  • ester and/or amide links
  • M is any suitable counterion, typically hydrogen, sodium or potassium ion.
  • Suitable hueing dyes may also include small molecule dyes and polymeric dyes.
  • Suitable small molecule dyes may include small molecule dyes selected from the group consisting of dyes falling into the Colour Index (C.I.) classifications of Direct, Basic, Reactive or hydrolysed Reactive, Solvent or Disperse dyes for example that are classified as Blue, Violet, Red, Green or Black, and provide the desired shade either alone or in combination.
  • C.I. Colour Index
  • suitable small molecule dyes may include small molecule dyes selected from the group consisting of Colour Index (Society of Dyers and Colourists, Bradford, UK) numbers Direct Violet dyes such as 9, 35, 48, 51, 66, and 99, Direct Blue dyes such as 1, 71, 80 and 279, Acid Red dyes such as 17, 73, 52, 88 and 150, Acid Violet dyes such as 15, 17, 24, 43, 49 and 50, Acid Blue dyes such as 15, 17, 25, 29, 40, 45, 75, 80, 83, 90 and 113, Acid Black dyes such as 1, Basic Violet dyes such as 1, 3, 4, 10 and 35, Basic Blue dyes such as 3, 16, 22, 47, 66, 75 and 159, Disperse or Solvent dyes such as those described in US 2008/034511 Al or US 8,268,016 B2, or dyes as disclosed in US 7,208,459 B2, and mixtures thereof.
  • Colour Index Society of Dyers and Colourists, Bradford, UK
  • Direct Violet dyes such as 9, 35, 48, 51, 66,
  • suitable small molecule dyes may include small molecule dyes selected from the group consisting of C. I. numbers Acid Violet 17, Direct Blue 71, Direct Violet 51, Direct Blue 1, Acid Red 88, Acid Red 150, Acid Blue 29, Acid Blue 113 or mixtures thereof.
  • Suitable polymeric dyes may include polymeric dyes selected from the group consisting of polymers containing covalently bound (sometimes referred to as conjugated) chromogens, (dye- polymer conjugates), for example polymers with chromogens co-polymerized into the backbone of the polymer and mixtures thereof.
  • Polymeric dyes may include those described in WO2011/98355, US 2012/225803 Al, US 2012/090102 Al, US 7,686,892 B2, and WO2010/142503.
  • suitable polymeric dyes may include polymeric dyes selected from the group consisting of fabric-substantive colorants sold under the name of Liquitint® (Milliken, Spartanburg, South Carolina, USA), dye -polymer conjugates formed from at least one reactive dye and a polymer selected from the group consisting of polymers comprising a moiety selected from the group consisting of a hydroxyl moiety, a primary amine moiety, a secondary amine moiety, a thiol moiety and mixtures thereof.
  • suitable polymeric dyes may include polymeric dyes selected from the group consisting of Liquitint® Violet CT, carboxymethyl cellulose (CMC) covalently bound to a reactive blue, reactive violet or reactive red dye such as CMC conjugated with C.I. Reactive Blue 19, sold by Megazyme, Wicklow, Ireland under the product name AZO-CM-CELLULOSE, product code S-ACMC, alkoxylated triphenyl-methane polymeric colourants, alkoxylated thiophene polymeric colourants, and mixtures thereof.
  • CMC carboxymethyl cellulose
  • Preferred hueing dyes may include the whitening agents found in WO 08/87497 Al, WO2011/011799 and US 2012/129752 Al.
  • Preferred hueing dyes for use in the present invention may be the preferred dyes disclosed in these references, including those selected from Examples 1- 42 in Table 5 of WO2011/011799.
  • Other preferred dyes are disclosed in US 8,138,222.
  • Other preferred dyes are disclosed in US 7,909,890 B2.
  • the aforementioned fabric hueing agents can be used in combination (any mixture of fabric hueing agents can be used).
  • Unbrightened Multifiber Fabric Style 41 swatches (MFF41, 5cm x 10cm, average weight 1.46g) serged with unbrightened thread are purchased from Testfabrics, Inc. (West Pittston,
  • MFF41 swatches are stripped prior to use by washing two full cycles in AATCC heavy duty liquid laundry detergent (HDL) nil brightener at 49°C and washing 3 additional full cycles at 49°C without detergent. Four replicate swatches are placed into each flask.
  • HDL heavy duty liquid laundry detergent
  • a sufficient volume of AATCC standard nil brightener HDL detergent solution is prepared by dissolving the detergent in 0 gpg water at room temperature at a concentration of 1.55 g per liter.
  • a concentrated stock solution of dye is prepared in an appropriate solvent selected from dimethyl sulfoxide (DMSO), ethanol or 50:50 ethanokwater. Ethanol is preferred.
  • the dye stock is added to a beaker containing 400mL detergent solution (prepared in step Lb. above) in an amount sufficient to produce an aqueous solution absorbance at the of 0.4 AU (+ 0.01AU) in a cuvette of path length 1.0 cm.
  • Total organic solvent concentration in a wash solution from the concentrated stock solution is less than 0.5%.
  • a 125mL aliquot of the wash solution is placed into 3 separate disposable 250mL Erlenmeyer flasks (Thermo Fisher Scientific, Rochester, NY).
  • L*, a*, and b* values for the 3 most consumer relevant fabric types, cotton, nylon and polyester, are measured on the dry swatches using a LabScan XE reflectance spectrophotometer (HunterLabs, Reston, VA; D65 illumination, 10° observer, UV light excluded).
  • the L*, a*, and b* values of the 12 swatches (3 flasks each containing 4 swatches) are averaged and the hueing deposition (HD) of the dye is calculated for each fabric type using the following equation:
  • a dye is considered a shading dye (also known as a hueing dye) for the purposes of the present invention if the HD co tton, HD po iyester or HD ny i on is greater than or equal to 2.0 DE* units according to the formula above. If the value of HD for each fabric type is less than 2.0 DE* units, the dye is not a shading dye for the purposes of the present invention.
  • the film of the present invention is soluble or dispersible in water, and preferably has a water- solubility of at least 50%, preferably at least 75% or even at least 95%, as measured by the method set out here after using a glass-filter with a maximum pore size of 20 microns:
  • pouch material 50 grams ⁇ 0.1 gram of pouch material is added in a pre-weighed 400 ml beaker and 245ml ⁇ 1ml of distilled water is added. This is stirred vigorously on a magnetic stirrer set at 600 rpm, for 30 minutes. Then, the mixture is filtered through a folded qualitative sintered-glass filter with a pore size as defined above (max. 20 micron). The water is dried off from the collected filtrate by any conventional method, and the weight of the remaining material is determined (which is the dissolved or dispersed fraction). Then, the percentage solubility or dispersability can be calculated.
  • Preferred film materials are preferably polymeric materials.
  • the film material can, for example, be obtained by casting, blow-moulding, extrusion or blown extrusion of the polymeric material, as known in the art.
  • Preferred polymers, copolymers or derivatives thereof suitable for use as pouch material are selected from polyvinyl alcohols, polyvinyl pyrrolidone, polyalkylene oxides, acrylamide, acrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and salts, polyaminoacids or peptides, polyamides, polyacrylamide, copolymers of maleic/acrylic acids, polysaccharides including starch and gelatine, natural gums such as xanthum and carragum.
  • More preferred polymers are selected from polyacrylates and water-soluble acrylate copolymers, methylcellulose, carboxymethylcellulose sodium, dextrin, ethylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, maltodextrin, polymethacrylates, and most preferably selected from polyvinyl alcohols, polyvinyl alcohol copolymers and hydroxypropyl methyl cellulose (HPMC), and combinations thereof.
  • the level of polymer in the pouch material for example a PVA polymer, is at least 60%.
  • the polymer can have any weight average molecular weight, preferably from about 1000 to 1,000,000, more preferably from about 10,000 to 300,000 yet more preferably from about 20,000 to 150,000.
  • Mixtures of polymers can also be used as the pouch material. This can be beneficial to control the mechanical and/or dissolution properties of the compartments or pouch, depending on the application thereof and the required needs.
  • Suitable mixtures include for example mixtures wherein one polymer has a higher water-solubility than another polymer, and/or one polymer has a higher mechanical strength than another polymer.
  • mixtures of polymers having different weight average molecular weights for example a mixture of PVA or a copolymer thereof of a weight average molecular weight of about 10,000- 40,000, preferably around 20,000, and of PVA or copolymer thereof, with a weight average molecular weight of about 100,000 to 300,000, preferably around 150,000.
  • polymer blend compositions for example comprising hydrolytically degradable and water-soluble polymer blends such as polylactide and polyvinyl alcohol, obtained by mixing polylactide and polyvinyl alcohol, typically comprising about 1-35% by weight polylactide and about 65% to 99% by weight polyvinyl alcohol.
  • polymers which are from about 60% to about 98% hydrolysed, preferably about 80% to about 90% hydrolysed, to improve the dissolution characteristics of the material.
  • Preferred film materials are polymeric materials.
  • the film material can be obtained, for example, by casting, blow-moulding, extrusion or blown extrusion of the polymeric material, as known in the art.
  • Preferred polymers, copolymers or derivatives thereof suitable for use as pouch material are selected from polyvinyl alcohols, polyvinyl pyrrolidone, polyalkylene oxides, acrylamide, acrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and salts, polyaminoacids or peptides, polyamides, polyacrylamide, copolymers of maleic/acrylic acids, polysaccharides including starch and gelatine, natural gums such as xanthum and carragum.
  • More preferred polymers are selected from polyacrylates and water-soluble acrylate copolymers, methylcellulose, carboxymethylcellulose sodium, dextrin, ethylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, maltodextrin, polymethacrylates, and most preferably selected from polyvinyl alcohols, polyvinyl alcohol copolymers and hydroxypropyl methyl cellulose (HPMC), and combinations thereof.
  • the level of polymer in the pouch material for example a PVA polymer, is at least 60%.
  • the polymer can have any weight average molecular weight, preferably from about 1000 to 1,000,000, more preferably from about 10,000 to 300,000 yet more preferably from about 20,000 to 150,000.
  • Mixtures of polymers can also be used as the pouch material. This can be beneficial to control the mechanical and/or dissolution properties of the compartments or pouch, depending on the application thereof and the required needs.
  • Suitable mixtures include for example mixtures wherein one polymer has a higher water-solubility than another polymer, and/or one polymer has a higher mechanical strength than another polymer.
  • mixtures of polymers having different weight average molecular weights for example a mixture of PVA or a copolymer thereof of a weight average molecular weight of about 10,000- 40,000, preferably around 20,000, and of PVA or copolymer thereof, with a weight average molecular weight of about 100,000 to 300,000, preferably around 150,000.
  • polymer blend compositions for example comprising hydrolytically degradable and water-soluble polymer blends such as polylactide and polyvinyl alcohol, obtained by mixing polylactide and polyvinyl alcohol, typically comprising about 1-35% by weight polylactide and about 65% to 99% by weight polyvinyl alcohol.
  • polymers which are from about 60% to about 98% hydrolysed, preferably about 80% to about 90% hydrolysed, to improve the dissolution characteristics of the material.
  • Preferred films exhibit good dissolution in cold water, meaning unheated water straight from the tap. Preferably such films exhibit good dissolution at temperatures below 25°C, more preferably below 21°C, more preferably below 15°C. By good dissolution it is meant that the film exhibits water- solubility of at least 50%, preferably at least 75% or even at least 95%, as measured by the method set out here after using a glass-filter with a maximum pore size of 20 microns, described above.
  • Preferred films are those supplied by Monosol under the trade references M8630, M8900, M8779, M9467, M8310, films described in US 6 166 117 and US 6 787 512 and PVA films of corresponding solubility and deformability characteristics. Further preferred films are those describes in US2006/0213801, WO 2010/119022 and US6787512.
  • Preferred water soluble films are those resins comprising one or more PVA polymers, preferably said water soluble film resin comprises a blend of PVA polymers.
  • the PVA resin can include at least two PVA polymers, wherein as used herein the first PVA polymer has a viscosity less than the second PVA polymer.
  • a first PVA polymer can have a viscosity of at least 8 cP (cP means Centipoise), 10 cP, 12 cP, or 13 cP and at most 40 cP, 20 cP, 15 cP, or 13 cP, for example in a range of about 8 cP to about 40 cP, or 10 cP to about 20 cP, or about 10 cP to about 15 cP, or about 12 cP to about 14 cP, or 13 cP.
  • cP means Centipoise
  • a second PVA polymer can have a viscosity of at least about 10 cP, 20 cP, or 22 cP and at most about 40 cP, 30 cP, 25 cP, or 24 cP, for example in a range of about 10 cP to about 40 cP, or 20 to about 30 cP, or about 20 to about 25 cP, or about 22 to about 24, or about 23 cP.
  • the viscosity of a PVA polymer is determined by measuring a freshly made solution using a Brookfield LV type viscometer with UL adapter as described in British Standard EN ISO 15023-2:2006 Annex E Brookfield Test method.
  • the PVA resin can, in addition or in the alternative, include a first PVA polymer that has a Mw in a range of about 50,000 to about 300,000 Daltons, or about 60,000 to about 150,000 Daltons; and a second PVA polymer that has a Mw in a range of about 60,000 to about 300,000 Daltons, or about 80,000 to about 250,000 Daltons.
  • the PVA resin can still further include one or more additional PVA polymers that have a viscosity in a range of about 10 to about 40 cP and a degree of hydrolysis in a range of about 84% to about 92%.
  • the PVA resin includes a first PVA polymer having an average viscosity less than about 11 cP and a polydispersity index in a range of about 1.8 to about 2.3, then in one type of embodiment the PVA resin contains less than about 30 wt.% of the first PVA polymer.
  • the PVA resin includes a first PVA polymer having an average viscosity less than about 11 cP and a polydispersity index in a range of about 1.8 to about 2.3
  • the PVA resin contains less than about 30 wt.% of a PVA polymer having a Mw less than about 70,000 Daltons.
  • the PVA resin can comprise about 30 to about 85 wt.% of the first PVA polymer, or about 45 to about 55 wt.% of the first PVA polymer.
  • the PVA resin can contain about 50 wt.% of each PVA polymer, wherein the viscosity of the first PVA polymer is about 13 cP and the viscosity of the second PVA polymer is about 23 cP.
  • One type of embodiment is characterized by the PVA resin including about 40 to about 85 wt.% of a first PVA polymer that has a viscosity in a range of about 10 to about 15 cP and a degree of hydrolysis in a range of about 84% to about 92%.
  • Another type of embodiment is characterized by the PVA resin including about 45 to about 55 wt.% of the first PVA polymer that has a viscosity in a range of about 10 to about 15 cP and a degree of hydrolysis in a range of about 84% to about 92%.
  • the PVA resin can include about 15 to about 60 wt.% of the second PVA polymer that has a viscosity in a range of about 20 to about 25 cP and a degree of hydrolysis in a range of about 84% to about 92%.
  • One contemplated class of embodiments is characterized by the PVA resin including about 45 to about 55 wt.% of the second PVA polymer.
  • the PDI value of the PVA resin is greater than the PDI value of any individual, included PVA polymer.
  • the PDI value of the PVA resin is greater than 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.5, or 5.0.
  • the PVA resin that has a weighted, average degree of hydrolysis ( H .deg. ) between about 80 and about 92 %, or between about 83 and about 90 %, or about 85 and 89%.
  • a PVA resin that has a weighted log average viscosity between about 10 and about 25, or between about 12 and 22, or between about 13.5 and about 20.
  • a PVA resin that has a Resin Selection Index (RSI) in a range of 0.255 to 0.315, or 0.260 to 0.310, or 0.265 to 0.305, or 0.270 to 0.300, or 0.275 to 0.295, preferably 0.270 to 0.300.
  • the RSI is calculated by the formula (w[t] ⁇ .micro.[ ⁇ ] - A l)/.Sigma. ((W)iMi ) > wherein .micro. [(] is seventeen, /, is the average viscosity each of the respective PVA polymers, and Wi is the weight percentage of the respective PVA polymers.
  • Even more preferred films are water soluble copolymer films comprising a least one anionically modified monomer with formula:
  • G represents a vinyl alcohol monomer
  • G represents a monomer comprising an anionic group
  • index n is an integer of from 1 to 3.
  • G can be any suitable comonomer capable of carrying of carrying the anionic group, more preferably G is a carboxylic acid.
  • G is preferably selected from the group consisting of maleic acid, itaconic acid, coAMPS, acrylic acid, vinyl acetic acid, vinyl sulfonic acid, allyl sulfonic acid, ethylene sulfonic acid, 2 acrylamido 1 methyl propane sulfonic acid, 2 acrylamido 2 methyl propane sulfonic acid, 2 methyl acrylamido 2 methyl propane sulfonic acid and mixtures thereof.
  • the anionic group of G is preferably selected from the group consisting of OSO 3 M, SO 3 M, C0 2 M, OC0 2 M, OP0 3 M 2 , OP0 3 HM and OP0 2 M. More preferably anionic group of G is selected from the group consisting of OS0 3 M, S0 3 M, C0 2 M, and OC0 2 M. Most preferably the anionic group of G is selected from the group consisting of S0 3 M and C0 2 M.
  • compartments of the present invention may be employed in making the compartments of the present invention.
  • a benefit in selecting different films is that the resulting compartments may exhibit different solubility or release characteristics.
  • the film material herein can also comprise one or more additive ingredients.
  • plasticisers for example glycerol, ethylene glycol, diethyleneglycol, propylene glycol, sorbitol and mixtures thereof.
  • Other additives include functional detergent additives to be delivered to the wash water, for example organic polymeric dispersants, etc.
  • the pouches described herein may be single or multi-compartment pouch. Where the pouch is a multi-compartment pouch, the compartments preferably have a different aesthetic appearance. A difference in aesthetics can be achieved in any suitable way.
  • One compartment of the pouch may be made using translucent, transparent, semi-transparent, opaque or semi-opaque film, and the second compartment of the pouch may be made using a different film selected from translucent, transparent, semi-transparent, opaque or semi-opaque film such that the appearance of the compartments is different.
  • the compartments of the pouch may be the same size or volume. Alternatively the compartments of the pouch may have different sizes, with different internal volumes.
  • the compartments may also be different from one another in terms of texture or colour.
  • one compartment may be glossy whilst the other is matt.
  • This can be readily achieved as one side of a water-soluble film is often glossy, whilst the other has a matt finish.
  • the film used to make a compartment may be treated in a way so as to emboss, engrave or print the film.
  • Embossing may be achieved by adhering material to the film using any suitable means described in the art.
  • Engraving may be achieved by applying pressure into the film using a suitable technique available in the art.
  • Printing may be achieved using any suitable printer and process available in the art.
  • the film itself may be coloured, allowing the manufacturer to select different coloured films for each compartment.
  • the films may be transparent or translucent and the composition contained within may be coloured.
  • a first compartment has a colour selected from the group consisting of white, green, blue, orange, red, yellow, pink or purple and a second compartment has a different colour selected from the group consisting of white, yellow, orange, blue or green.
  • the compartments of a multi-compartment pouch can be separate, but are preferably conjoined in any suitable manner.
  • the second and optionally third or subsequent compartments are superimposed on the first compartment.
  • the third compartment may be superimposed on the second compartment, which is in turn superimposed on the first compartment in a sandwich configuration.
  • the second and third, and optionally subsequent, compartments may all be superimposed on the first compartment.
  • the first, second and optionally third and subsequent compartments may be attached to one another in a side by side relationship.
  • the present pouch comprises three compartments consisting of a large and two smaller compartments. The second and third smaller compartments are superposed on the first larger compartment.
  • compartments are chosen such that this arrangement is achievable.
  • the compartments may be packed in a string, each compartment being individually separable by a perforation line. Hence each compartment may be individually torn-off from the remainder of the string by the end-user, for example, so as to pre-treat or post treat a fabric with a composition from a compartment.
  • the geometry of the compartments may be the same or different.
  • the second and optionally third or subsequent compartment has a different geometry and shape to the first compartment.
  • the second and optionally third compartments are arranged in a design on the first compartment. Said design may be decorative, educative, illustrative for example to illustrate a concept or instruction, or used to indicate origin of the product.
  • the first compartment is the largest compartment having two large faces sealed around the perimeter. The second compartment is smaller covering less than 75%, more preferably less than 50% of the surface area of one face of the first compartment.
  • the above structure is the same but the second and third compartments cover less than 60%, more preferably less than 50%, even more preferably less than 45% of the surface area of one face of the first compartment.
  • the pouch of the present invention may be made using any suitable equipment and method.
  • Single compartment pouches are made using vertical, but preferably horizontal form filling techniques commonly known in the art.
  • the film is preferably dampened, more preferably heated to increase the malleability thereof.
  • the method also involves the use of a vacuum to draw the film into a suitable mould.
  • the vacuum drawing the film into the mould can be applied for 0.2 to 5 seconds, preferably 0.3 to 3 or even more preferably 0.5 to 1.5 seconds, once the film is on the horizontal portion of the surface.
  • This vacuum may preferably be such that it provides an under-pressure of between +10mbar to +1000mbar, more preferably from +100mbar to +600mbar.
  • the moulds in which the pouches are made, can have any shape, length, width and depth, depending on the required dimensions of the pouches.
  • the moulds can also vary in size and shape from one to another, if desirable. For example, it may be preferred that the volume of the final pouches is between 5 and 300ml, or even 10 and 150ml or even 20 and 100ml and that the mould sizes are adjusted accordingly.
  • Heat can be applied to the film, in the process commonly known as thermoforming, by any means.
  • the film may be heated directly by passing it under a heating element or through hot air, prior to feeding it onto the surface or once on the surface.
  • it may be heated indirectly, for example by heating the surface or applying a hot item onto the film.
  • the film is heated using an infra red light.
  • the film is preferably heated to a temperature of 50 to 120°C, or even 60 to 90°C.
  • the film can be wetted by any mean, for example directly by spraying a wetting agent (including water, solutions of the film material or plasticizers for the film material) onto the film, prior to feeding it onto the surface or once on the surface, or indirectly by wetting the surface or by applying a wet item onto the film.
  • a wetting agent including water, solutions of the film material or plasticizers for the film material
  • a film Once a film has been heated/wetted, it is drawn into an appropriate mould, preferably using a vacuum.
  • the filling of the moulded film can be done by any known method for filling (preferably moving) items. The most preferred method will depend on the product form and speed of filling required.
  • the moulded film is filled by in-line filling techniques.
  • the filled, open pouches are then closed, using a second film, by any suitable method. Preferably, this is also done while in horizontal position and in continuous, constant motion.
  • the closing is done by continuously feeding a second film, preferably water-soluble film, over and onto the open pouches and then preferably sealing the first and second film together, typically in the area between the moulds and thus between the pouches.
  • Preferred methods of sealing include heat sealing, solvent welding, and solvent or wet sealing. It is preferred that only the area which is to form the seal, is treated with heat or solvent.
  • the heat or solvent can be applied by any method, preferably on the closing material, preferably only on the areas which are to form the seal. If solvent or wet sealing or welding is used, it may be preferred that heat is also applied.
  • Preferred wet or solvent sealing/ welding methods include applying selectively solvent onto the area between the moulds, or on the closing material, by for example, spraying or printing this onto these areas, and then applying pressure onto these areas, to form the seal. Sealing rolls and belts as described above (optionally also providing heat) can be used, for example.
  • the formed pouches can then be cut by a cutting device.
  • Cutting can be done using any known method. It may be preferred that the cutting is also done in continuous manner, and preferably with constant speed and preferably while in horizontal position.
  • the cutting device can, for example, be a sharp item or a hot item, whereby in the latter case, the hot item 'burns' through the film/ sealing area.
  • the different compartments of a multi-compartment pouch may be made together in a side -by- side style and consecutive pouches are not cut. Alternatively, the compartments can be made separately. According to this process and preferred arrangement, the pouches are made according to the process comprising the steps of:
  • step (b) forming a recess within some or all of the closed compartment formed in step (a), to generate a second moulded compartment superposed above the first compartment;
  • step e cutting the films to produce a multi-compartment pouch.
  • Said recess formed in step b is preferably achieved by applying a vacuum to the compartment prepared in step a).
  • the second, and optionally third, compartment(s) can be made in a separate step and then combined with the first compartment as described in our co-pending application EP 08101442.5 which is incorporated herein by reference.
  • a particularly preferred process comprises the steps of:
  • the first and second forming machines are selected based on their suitability to perform the above process.
  • the first forming machine is preferably a horizontal forming machine.
  • the second forming machine is preferably a rotary drum forming machine, preferably located above the first forming machine.
  • the composition of the present invention is preferably a liquid.
  • 'liquid' it is meant to include liquid, paste, waxy or gel compositions.
  • the liquid composition may comprise a solid. Solids may include powder or agglomerates, such as micro-capsules, beads, noodles or one or more pearlised balls or mixtures thereof. Such a solid element may provide a technical benefit, through the wash or as a pre-treat, delayed or sequential release component. Alternatively it may provide an aesthetic effect.
  • the compositions of the present invention may comprise one or more of the ingredients discussed below.
  • composition of the present invention preferably comprises further surfactants.
  • the total surfactant level may be in the range of from about 1% to 80% by weight of the composition.
  • detersive surfactants utilized can be of the nonionic, zwitterionic, ampholytic or cationic type or can comprise compatible mixtures of these types. More preferably surfactants are selected from the group consisting of anionic, nonionic, cationic surfactants and mixtures thereof. Preferably the compositions are substantially free of betaine surfactants.
  • Detergent surfactants useful herein are described in U.S. Patent 3,664,961, Norris, issued May 23, 1972, U.S. Patent 3,919,678, Laughlin et al., issued December 30, 1975, U.S. Patent 4,222,905, Cockrell, issued September 16, 1980, and in U.S. Patent 4,239,659, Murphy, issued December 16, 1980. Anionic and nonionic surfactants are preferred.
  • Preferred nonionic surfactants are those of the formula R 1 (OC 2 H4) n OH, wherein R 1 is a CK T C 16 alkyl group or a C8-C 12 alkyl phenyl group, and n is from 3 to about 80.
  • Particularly preferred are condensation products of C 12 -C 15 alcohols with from about 5 to about 20 moles of ethylene oxide per mole of alcohol, e.g., C 12 -C 13 alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol.
  • compositions may comprise a fabric care benefit agent.
  • fabric care benefit agent refers to any material that can provide fabric care benefits such as fabric softening, color protection, pill/fuzz reduction, anti-abrasion, anti-wrinkle, and the like to garments and fabrics, particularly on cotton and cotton-rich garments and fabrics, when an adequate amount of the material is present on the garment/fabric.
  • fabric care benefit agents include cationic surfactants, silicones, polyolefin waxes, latexes, oily sugar derivatives, cationic polysaccharides, polyurethanes, fatty acids and mixtures thereof.
  • Fabric care benefit agents when present in the composition are suitably at levels of up to about 30% by weight of the composition, more typically from about 1% to about 20%, preferably from about 2% to about 10%.
  • Detersive enzymes are suitably at levels of up to about 30% by weight of the composition, more typically from about 1% to about 20%, preferably from about 2% to about 10%.
  • Detersive enzymes may be incorporated into the compositions of the present invention. Suitable detersive enzymes for use herein include protease, amylase, lipase, cellulase, carbohydrase including mannanase and endoglucanase, and mixtures thereof. Enzymes can be used at their art-taught levels, for example at levels recommended by suppliers such as Novo and Genencor. Typical levels in the compositions are from about 0.0001% to about 5%.
  • enzymes When enzymes are present, they can be used at very low levels, e.g., from about 0.001% or lower, in certain embodiments of the invention; or they can be used in heavier-duty laundry detergent formulations in accordance with the invention at higher levels, e.g., about 0.1% and higher. In accordance with a preference of some consumers for "non-biological" detergents, the present invention includes both enzyme-containing and enzyme-free embodiments.
  • Deposition aids may be incorporated into the composition of the present invention.
  • “deposition aid” refers to any cationic polymer or combination of cationic polymers that significantly enhance the deposition of a fabric care benefit agent onto the fabric during laundering.
  • the deposition aid is a cationic or amphoteric polymer.
  • the amphoteric polymers of the present invention will also have a net cationic charge, i.e.; the total cationic charges on these polymers will exceed the total anionic charge.
  • Nonlimiting examples of deposition enhancing agents are cationic polysaccharides, chitosan and its derivatives and cationic synthetic polymers.
  • Preferred cationic polysaccharides include cationic cellulose derivatives, cationic guar gum derivatives, chitosan and derivatives and cationic starches.
  • the composition comprises a rheology modifier.
  • the rheology modifier is selected from the group consisting of non-polymeric crystalline, hydroxy- functional materials, polymeric rheology modifiers which impart shear thinning characteristics to the aqueous liquid matrix of the composition.
  • Crystalline, hydroxy-functional materials are rheology modifiers which form thread-like structuring systems throughout the matrix of the composition upon in situ crystallization in the matrix.
  • Specific examples of preferred crystalline, hydroxyl-containing rheology modifiers include castor oil and its derivatives. Especially preferred are hydrogenated castor oil derivatives such as hydrogenated castor oil and hydrogenated castor wax.
  • polymeric rheology modifiers are preferably selected from polyacrylates, polymeric gums, other non-gum polysaccharides, and combinations of these polymeric materials.
  • Preferred polymeric gum materials include pectine, alginate, arabinogalactan (gum Arabic), carrageenan, gellan gum, xanthan gum, guar gum and mixtures thereof.
  • compositions of the present invention may optionally comprise a builder.
  • Suitable builders include polycarboxylate builders include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
  • Particularly preferred are citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt
  • ethylene diamine disuccinic acid and salts thereof ethylene diamine disuccinates, EDDS
  • ethylene diamine tetraacetic acid and salts thereof ethylene diamine tetraacetates, EDTA
  • diethylene triamine penta acetic acid and salts thereof diethylene triamine penta acetates, DTPA
  • aluminosilicates such as zeolite A, B or MAP
  • fatty acids or salts preferably sodium salts, thereof, preferably C12-C18 saturated and/or unsaturated fatty acids
  • alkali or alkali earth metal carbonates preferably sodium carbonate.
  • Bleaching agents suitable herein include chlorine and oxygen bleaches, especially inorganic perhydrate salts such as sodium perborate mono-and tetrahydrates and sodium percarbonate optionally coated to provide controlled rate of release (see, for example, GB-A- 1466799 on sulfate/carbonate coatings), preformed organic peroxyacids and mixtures thereof with organic peroxyacid bleach precursors and/or transition metal-containing bleach catalysts (especially manganese or cobalt).
  • Inorganic perhydrate salts are typically incorporated at levels in the range from about 1% to about 40% by weight, preferably from about 2% to about 30% by weight and more preferably from abut 5% to about 25% by weight of composition.
  • Peroxyacid bleach precursors preferred for use herein include precursors of perbenzoic acid and substituted perbenzoic acid; cationic peroxyacid precursors; peracetic acid precursors such as TAED, sodium acetoxybenzene sulfonate and pentaacetylglucose; pernonanoic acid precursors such as sodium 3,5,5-trimethylhexanoyloxybenzene sulfonate (iso-NOBS) and sodium nonanoyloxybenzene sulfonate (NOBS); amide substituted alkyl peroxyacid precursors (EP-A-0170386); and benzoxazin peroxyacid precursors (EP-A-0332294 and EP-A-0482807).
  • Bleach precursors are typically incorporated at levels in the range from about 0.5% to about 25%, preferably from about 1% to about 10% by weight of composition while the preformed organic peroxyacids themselves are typically incorporated at levels in the range from 0.5% to 25% by weight, more preferably from 1% to 10% by weight of composition.
  • Bleach catalysts preferred for use herein include the manganese triazacyclononane and related complexes (US-A-4246612, US-A-5227084); Co, Cu, Mn and Fe bispyridylamine and related complexes (US-A-5114611); and pentamine acetate cobalt(III) and related complexes(US-A-4810410).
  • cleaning adjunct materials include, but are not limited to; enzyme stabilizing systems; antioxidants, opacifier, pearlescent agent, hueing dye, scavenging agents including fixing agents for anionic dyes, complexing agents for anionic surfactants, and mixtures thereof; optical brighteners or fluorescers; soil release polymers; dispersants; suds suppressors; dyes; colorants; hydrotropes such as toluenesulfonates, cumenesulfonates and naphthalenesulfonates; color speckles; perfumes and perfume microcapsules, colored beads, spheres or extrudates; clay softening agents and mixtures thereof.
  • enzyme stabilizing systems antioxidants, opacifier, pearlescent agent, hueing dye, scavenging agents including fixing agents for anionic dyes, complexing agents for anionic surfactants, and mixtures thereof; optical brighteners or fluorescers; soil release polymers; dispersants; suds suppressors; dyes; colorants; hydrotropes
  • compositions herein can generally be prepared by mixing the ingredients together. If a pearlescent material is used it should be added in the late stages of mixing. If a rheology modifier is used, it is preferred to first form a pre-mix within which the rheology modifier is dispersed in a portion of the water and optionally other ingredients eventually used to comprise the compositions. This pre-mix is formed in such a way that it forms a structured liquid. To this structured pre-mix can then be added, while the pre-mix is under agitation, the surfactant(s) and essential laundry adjunct materials, along with water and whatever optional detergent composition adjuncts are to be used. Secondary Packaging
  • the multi-compartment pouches of the present invention are preferably further packaged in an outer package.
  • Said outer package may be a see-through or partially see-through container, for example a transparent or translucent bag, tub, carton or bottle.
  • the pack can be made of plastic or any other suitable material, provided the material is strong enough to protect the pouches during transport. This kind of pack is also very useful because the user does not need to open the pack to see how many pouches there are left.
  • the pack can have non- see-through outer packaging, perhaps with indicia or artwork representing the visually-distinctive contents of the pack.
  • the pouches of the present invention are suitable for laundry cleaning applications.
  • the pouches are suitable for hand or machine washing conditions.
  • the pouch may be delivered from the dispensing drawer or may be added directly into the washing machine drum.
  • Migration of liquid compounds through the film to the outside of the water soluble package can be quantified using a Corneometer CM825 equipped with CM-825 probe, manufactured by Courage- Khazaka Electronic, Koln, Germany.
  • the equipment is calibrated according to the supplier recommendation.
  • the equipment provides a corneometer value which is recorded.
  • the Corneometer can detect even slightest changes in weeping level since change in the dielectric constant (i.e. presence of fluid on the outside of the pouch) alters the Corneometer value.
  • the equipment is placed in a conditioned laboratory at 20°C +/- 3C and 50% +/- 10 relative humidity.
  • the pouches are brought to temperature of 20+/- 3C prior to the measurement.
  • the probe is cleaned with a dry and clean paper tissue; then blank measurements are made by slowly wiping the sensor on the clean paper tissue (VWR International bvba, Leuven, Belgium, Cat. No. 115- 0600), to ensure there is no contamination on the probe, until the instrument reads a Corneometer value of zero.
  • the probe is placed vertically on the pouch, as per the usage instructions. Ten replicates are measured for each pouch. The center and corners of the top and bottom face of the pouch are tested. Measurement are repeated on 5 different pouches. The data is thus the average of 50 measurements.
  • the probe is cleaned in between each measurement.
  • composition A The following detergent compositions (as set out below, composition A) were prepared comprising differing combinations and levels of solvents.
  • Mono compartment pouches are filled with liquid detergents of composition A, wherein the solvent system is selected as below from formulations 1 to 9.
  • the pouches are made using M8779 film, available from Monosol using standard thermoforming techniques. Specifically, 0.7g of a 76 ⁇ thick film M8779 are thermoformed to a single compartment pouch measuring 41mm by 43 mm. The pouch is filled with 23.7 mL (25.4 g) of composition A, above.
  • the following solvent system formulations 1 to 4 were prepared comprising differing combinations and levels of solvents.
  • the Corneometer value was measured after 4 weeks storage at 32°C and 80% relative humidity. Based on the value, the weeping profile is classified.
  • DPG dipropylene glycol
  • DEG diethylene glycol
  • Glycerol was supplied by Brenntag Sa, Louisiana, France.
  • Pdiol propanediol was supplied by Ineos Manufacturing, Koln, Germany.
  • the following solvent system formulations 2 to5 were prepared comprising differing combinations and levels of solvents.
  • the Comeometer value was measured after 4 weeks storage at 32°C and 80% relative humidity. Based on the value, the weeping profile is classified.
  • the following solvent system formulations 1, 2, 5 and 7 were prepared comprising differing combinations and levels of solvents.
  • Example 4 The following solvent system formulations 1 to8 were prepared comprising differing combinations and levels of solvents.
  • the Comeometer value was measured after 4 weeks storage at 32°C and 80% relative humidity. Based on the value, the weeping profile is classified.
  • the following solvent system formulations 5, 7, 8 and 9 were prepared comprising differing combinations and levels of solvents.
  • the Comeometer value was measured after 4 weeks storage at 32°C and 80% relative humidity. Based on the value, the weeping profile is classified.

Abstract

The present invention relates to the use of a composition comprising a) anionic surfactant; and b) solvent system comprising at least one primary solvent having Hansen solubility (δ) of less than 29 said composition being encapsulated in a water soluble film pouch, for reducing migration and weeping of said composition through said film.

Description

USE OF COMPOSITION TO REDUCE WEEPING AND MIGRATION THROUGH A WATER
SOLUBLE FILM
TECHNICAL FIELD
The present invention relates to the use of a composition comprising anionic surfactant and solvent, when encapsulated within a water-soluble film, for reducing migration and weeping of the composition through the film.
BACKGROUND OF THE INVENTION
Water-soluble unitized dose products have become popular in recent years. The compositions held within the water-soluble film must have a controlled amount of water so as not to preemptively dissolve the film. Instead of water, unitized dose compositions comprise solvents to solubilise ingredients and act as a carrier. In addition to these effects, solvents in the composition within the product or within the film, plasticise the film, making it more elastic and supple. However depending on the choice of solvent or amount thereof, the Applicants have found that the solvent can also negatively affect the film structure and integrity. The Applicants have found that solvents can affect whether or not, or the speed of which components of the composition migrate or weep through the film. This is particularly a problem where the weeping is excessive and the pouch takes on a slimy, unpleasant feeling. Moreover if weeping is too great, the external surface of the pouch becomes moist, and premature dissolution of points in the film results in adjacent pouches sticking to one another. Furthermore, if the pouch is a multi-compartment pouch comprising different, potentially incompatible, compositions in each compartment, then migration of the composition from one compartment to another can have other undesirable consequences. For example, a migrating component of the composition may deactivate andenzyme or perfume, or a dye may colour the other composition, or cause an unwanted reaction. Hence the object of the present invention has been to reduce the above problems, by reducing and controlling the level of weeping and migration of a composition or components of the composition through the film.
SUMMARY OF THE INVENTION
According to the present invention there is provided the use of a composition comprising
a) anionic surfactant; and b) solvent system comprising at least one primary solvent having Hansen solubility (δ) of less than 29, said composition being encapsulated in a water soluble film pouch, for reducing migration and weeping of said composition through said film. DETAILED DESCRIPTION OF THE INVENTION
The present application relates to the use of a composition for controlling migration and weeping of a composition through a water soluble film. By the term weeping it is meant the travel of a composition, or components of the composition, encapsulated within a water-soluble film pouch, from within a pouch to outside the pouch. By the term migration it is meant weeping from one compartment of a multi-compartment pouch, to another compartment of the same pouch.
Plasticization is a term used to describe the elasticity, flexibility and brittleness of film. A film that is completely elastic, will recover its original shape once having been stretched. A film that is overplasticized tends to gain elasticity, eventually losing rigidity and becoming floppy.
Eventually, if plasticization continues, the film can become so weak, that it fails, rips and/or developing holes. By contrast if a plasticizer is not used, is lost or too little is used then the film becomes increasingly brittle over time, which again results in failure. Plasticizing solvents can be incorporated into the film on production, indeed this is most often the case, for ease of processing. However in addition plasticizing solvent can also be present in the composition which the film encapsulates. It is the Applicants belief that incorporating the specific plasticizing solvents of the present invention provides a beneficial plasticization of the film, that encourages the reduction of migration and weeping.
Detergent Composition
The detergent composition comprises an anionic surfactant and a solvent system. The solvent system comprises at least one primary solvent having Hansen solubility (δ) of less than 29.
Anionic Surfactant
The composition of the present invention comprises an anionic surfactant. Preferably the composition comprises from 1% to 80% by weight of an anionic surfactant. More preferably the composition comprises from 2 to 60%, more preferably from 7 to 50% and most preferably 10 to 40% anionic surfactant by weight of the composition. Useful anionic surfactants can themselves be of several different types. For example, water-soluble salts of the higher fatty acids, i.e., "soaps", are useful anionic surfactants in the compositions herein. This includes alkali metal soaps such as the sodium, potassium, ammonium, and alkyl ammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms. Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
Additional non-soap anionic surfactants which are suitable for use herein include the water-soluble salts, preferably the alkali metal, and ammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl" is the alkyl portion of acyl groups.) Examples of this group of synthetic surfactants are a) the sodium, potassium and ammonium alkyl sulfates, especially those obtained by sulfating the higher alcohols (Cg-Cig carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; b) the sodium, potassium and ammonium alkyl polyethoxylate sulfates, particularly those in which the alkyl group contains from 10 to 22, preferably from 12 to 18 carbon atoms, and wherein the polyethoxylate chain contains from 1 to 15, preferably 1 to 6 ethoxylate moieties; and c) the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S. Patents 2,220,099 and 2,477,383. Especially preferred are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as Cn-C^ LAS, sodium, potassium and ammonium alkyl polyethoxylate sulfates having from 12 to 18 carbon atoms and mixtures thereof.
Solvent system
The composition of the present invention comprises a solvent system. The solvent system comprises at least one primary solvent having Hansen solubility (δ) of less than 29, more preferably less than 28.5 and preferably greater than 10, more preferably greater than 15. The Hansen solubility parameter is a well known and calculated parameter based on a three component measuring system. The Hansen solubility parameter is based on a dispersion force component (5a), a hydrogen bonding component (¾) and a polar component (δρ). The Hansen solubility parameter (δ) is derived from the fact that the total cohesive energy, which is the energy required to break all the cohesive bonds, is the combination of the dispersion forces (d), the molecular dipole forces (p) and the hydrogen bonding forces (h) according to the following equation: δ 2 = 5<j 2 + δρ 2 + ¾ 2 δ is achieved by finding the square root of δ 2
Dispersion forces are weak attractive forces between non-polar molecules. The magnitude of these forces depends on the polarizability of the molecule, and the dispersion hansen solubility parameter (5d) typically increases with increasing volume (and size) of the molecule, all other properties being roughly equal. Hansen solubility parameters are calculated at 25°C, with ChemSW's molecular modeling Pro v6.1.9 software package which uses an unpublished proprietary algorithm that is based on values published in the Handbook of solubility Parameters and other parameters by Allan F M Barton (CRC Press 1983) for solvents obtained experimentally by Hansen.
The primary solvent preferably has molecular weight of less than 1500, more preferably less than 1000, even more preferably less than 700. The primary solvent preferably has a molecular weight of greater than 10, more preferably greater than 100. The primary solvent preferably has a cLog P of greater than -1.0 and more preferably less than +10. The primary solvent preferably has a Hydrogen bonding component (¾) of less than 20.5, and preferably greater than 10. The primary solvent is preferably selected from the group consisting of polyethylene glycol (PEG) polymer having molecular weight between 300 and 600, dipropylene glycol (DPG), nbutoxy propoxy propanol (nBPP) and mixtures thereof. More preferably the primary solvent is selected from the group consisting of polyethylene glycol (PEG) polymer having molecular weight between 400 and 600, dipropylene glycol (DPG), nbutoxy propoxy propanol (nBPP) and mixtures thereof. Table 1 shows the Hansen Solubility components of the preferred primary solvents and some comparative solvents falling outside of the scope of the invention. Solvent δ Dispersion δ Polarity δ H-bonding δ cLog P
PEG 200 16.54 11.22 20.91 28.9 -1.47
PEG 300 16.23 10.09 20.17 27.8 -1.22
PEG 400 15.81 8.21 19.12 26.1 -0.7
PEG 600 18.98 11.22 20.91 28.9 -0.74
DPG 16.67 10.86 20.35 28.5 -0.6
Propane diol 16.41 10.82 23.07 30.3 -1.1
Glycerol 17.29 12.22 27.34 34.6 -1.94
Sorbitol 19.24 11.5 23.4 32.4 -2.54
nBPP 15.99 5.42 8.91 19.1 +1.99
Table 1 : Hansen solubility component parameters
The primary solvent is preferably present at a level of from 1 to 25%, preferably from 2.5 to 20%, more preferably from 4 to 19% by weight of the composition.
In a preferred embodiment, the solvent system also comprises a secondary solvent. The secondary solvent is preferably selected from the group consisting of glycerol, water and mixtures thereof. When the secondary solvent comprises glycerol, glycerol is preferably present at a level of less than 5%, more preferably less than 4%, more preferably less than 3%, most preferably less than 2% by weight of the composition. Preferably the glycerol secondary solvent is present at a level of greater than 0.1%, more preferably greater than 0.5%, most preferably greater than 1% by weight of the composition. The secondary solvent may also comprise water. When water is present it is preferably present at a level of less than 20%, more preferably less than 15%, most preferably less than 10% by weight of the composition.
In a further preferred embodiment the ratio of primary solvent to secondary solvent glycerol is from 7: 1 to 1:5, more preferably from 6.5: 1 to 1:3, most preferably 3: 1 to 1: 1.
Negatively Charged Hueing Dye
The compositions of the present invention preferably comprise a negatively charged hueing dye. By the term negatively charged hueing dye it is meant that the dye residue comprises a moiety capable of being negatively charged in the composition. Preferably the composition will comprise from 0.00001wt% to 0.5wt% of hueing dye. Typically the hueing dye provides a blue or violet shade to fabric. Hueing dyes can be used either alone or in combination to create a specific shade of hueing and/or to shade different fabric types. This may be provided for example by mixing a red and green-blue dye to yield a blue or violet shade. Hueing dyes may be selected from any known chemical class of dye chromophore including, but not limited to, acridine, anthraquinone (including polycyclic quinones), azine, azo (e.g., monoazo, disazo, trisazo, tetrakisazo, polyazo), including premetallized azo, benzodifurane and benzodifuranone, carotenoid, coumarin, cyanine, diazahemicyanine, diphenylmethane, formazan, hemicyanine, indigoids, methine, naphthalimides, naphthoquinone, nitro and nitroso, oxazine, phthalocyanine, pyrazoles, stilbene, styryl, triarylmethane, triphenylmethane, xanthenes, tripehnooxazine and mixtures thereof.
Preferred negatively charged hueing dyes comprise those selected from the group having Formula I below.
[D]-[A]„
Formula I
wherein D represents the residue of a dye comprising a chromophore group, and A is a moiety selected from the group consisting of OS03M, S03M, C02M, OC02M, OP03M2, OP03HM and OP02M . More preferably A is selected from the group consisting of OS03M, S03M, C02M, and OC02M. Even more preferably A is selected from the group consisting of S03M and C02M. M is any suitable charge balancing counterion. M is preferably selected from the group consisting of Hydrogen, an alkali or alkali earth metal ion. More preferably M is selected from the group consisting of hydrogen, sodium or potassium ion. The index n is preferably an integer from 1 to 6, more preferably from 1 to 4, even more preferably n = 1 or 2.
Typically the dye or mixture of dyes of Formula I will be present in the composition in an amount from 0.00001 to 5 wt of the composition, more usually in an amount from 0.0001 or from 0.001 to lwt% or to 0.5 wt% or to 0.25 wt% of the composition.
The dye residue, D, may comprise one or more of any suitable class of chromophore group. Suitable chromophore groups include, but are not limited, to any suitable chromophore, preferably selected from the group listed above. More preferably the chromophore group is selected from the group consisting of benzodifurane, methine, triphenylmethane, azine, tripehnoxazine, naphthalimide, pyrazole, naphthoquinone, anthraquinone, mono-azo and bis-azo and mixtures thereof. More preferably the dye residue, D, is selected form the group consisting of Azine, anthraquinone and azo chromophores may be preferred in some embodiments. Preferably the hueing dye is a blue or violet hueing dye, providing a blue or violet color to a white cloth or fabric with a hue angle of 240 to 345, more preferably 260 to 325, even more preferably 270 to 310.
In one aspect, a hueing dye suitable for use in the present invention has, in the wavelength range of about 400 nm to about 750 nm, in methanol solution, a maximum extinction coefficient greater than about 1000 liter/mol/cm. In one aspect, a hueing dye suitable for use in the present invention has, in the wavelength range of about 540 nm to about 630 nm, a maximum extinction coefficient from about 10,000 to about 100,000 liter/mol/cm. In one aspect, a hueing dye suitable for use in the present invention has, in the wavelength range of about 560 nm to about 610 nm, a maximum extinction coefficient from about 20,000 to about 70,000 liter/mol/cm.
Preferred hueing dyes are selected from the group consisting of thiophene azo carboxylate dyes having the generalized structure of Formula II:
Figure imgf000008_0001
Formula II
wherein Rl d R2 are independently selected from [(CH2CR'HO)x(CH2CR"HO)yQ], C i2 alkyl, C6-
1 2 io aryl, C7-C22 aryl alkyl, with the requirement that at least one of R or R is
[(CH2CR'HO)x(CH2CR"HO)yQ] , wherein R' is selected from the group consisting of H, C M alkyl, CH20(CH2CH20)zQ, phenyl and -CH2OR5; wherein R" is selected from the group consisting of H, C 1-4 alkyl, CH20(CH2CH20)zQ, phenyl and CH2OR5; wherein 1 or 2 < x + y < 50, preferably x + y < 25, more preferably x + y < 10 ; wherein y > 1 ; wherein z = 0 or 1 to 20 preferably 0 to 10 or 5; and wherein Q is selected from the group consisting of H and Y wherein Y is as defined below; with the proviso that the dye comprises at least one Q group that is Y;
each R5 is selected from the group consisting of C C^ linear or branched alkyl, C6-C14 aryl and C7- C16 arylalkyl; preferably R5 is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, hexyl, 2-ethylhexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, phenyl, benzyl, 2-phenylethyl, naphthyl and mixtures thereof; and wherein Y is an organic radical represented by Formula III
Figure imgf000008_0002
Formula III
wherein independently for each Y group, M is H or a charge balancing cation; m is 0 to 5, preferably 0, 1, 2 or 3; n is 0 to 5, preferably 0, 1, 2 or 3; the sum of m + n is 1 to 10, preferably 1, 2 or 3; each R8 is independently selected from the group consisting of H and C3-18 or C4-C18 or even C4-7 and/or C9-18 alkenyl, and wherein at least one R8 group is not H. Such dyes are discussed in the Applicants co-pending currently unpublished patent application serial number US61/598014 (Attorney docket CM3724)
Suitable negatively charged dyes may also be selected from the group consisting of carboxylate dyes having the structure of Formula IV:
D L C02M
Formula IV
wherein D is as defined above and L is an organic linking group preferably having a molecular weight from 14 to 1000 Daltons, or 14 to 600, or 28 to 300, preferably consisting essentially only of C, H and optionally additionally O and/or N, and in the sequence of bonds starting from the carbonyl carbon of the C(0)OM group and ending at the dye moiety, any -(Ca(0)-Ob)- groups are incorporated such that the oxygen atom Ob is encountered prior to the carbonyl carbon Ca . Preferably L is a Ci_2o alkylene chain having optionally therein ether (-0-) and/or ester and/or amide links, the chain being optionally substituted for example with -OH, -CN, -N02, -SO2CH3 ,-Cl, -Br; and M is any suitable counterion, typically hydrogen, sodium or potassium ion. Such dyes are discussed in the applicants co-pending patent application, serial number US61/612539 (Attorney docket CM3732).
Other dyes suitable for use in the present invention include those described in the applicants co-pending patent application, serial number US 13/478148 (attorney docket number 12149) and WO 2012/054058 Al.
Suitable hueing dyes may also include small molecule dyes and polymeric dyes. Suitable small molecule dyes may include small molecule dyes selected from the group consisting of dyes falling into the Colour Index (C.I.) classifications of Direct, Basic, Reactive or hydrolysed Reactive, Solvent or Disperse dyes for example that are classified as Blue, Violet, Red, Green or Black, and provide the desired shade either alone or in combination. In another aspect, suitable small molecule dyes may include small molecule dyes selected from the group consisting of Colour Index (Society of Dyers and Colourists, Bradford, UK) numbers Direct Violet dyes such as 9, 35, 48, 51, 66, and 99, Direct Blue dyes such as 1, 71, 80 and 279, Acid Red dyes such as 17, 73, 52, 88 and 150, Acid Violet dyes such as 15, 17, 24, 43, 49 and 50, Acid Blue dyes such as 15, 17, 25, 29, 40, 45, 75, 80, 83, 90 and 113, Acid Black dyes such as 1, Basic Violet dyes such as 1, 3, 4, 10 and 35, Basic Blue dyes such as 3, 16, 22, 47, 66, 75 and 159, Disperse or Solvent dyes such as those described in US 2008/034511 Al or US 8,268,016 B2, or dyes as disclosed in US 7,208,459 B2, and mixtures thereof. In another aspect, suitable small molecule dyes may include small molecule dyes selected from the group consisting of C. I. numbers Acid Violet 17, Direct Blue 71, Direct Violet 51, Direct Blue 1, Acid Red 88, Acid Red 150, Acid Blue 29, Acid Blue 113 or mixtures thereof.
Suitable polymeric dyes may include polymeric dyes selected from the group consisting of polymers containing covalently bound (sometimes referred to as conjugated) chromogens, (dye- polymer conjugates), for example polymers with chromogens co-polymerized into the backbone of the polymer and mixtures thereof. Polymeric dyes may include those described in WO2011/98355, US 2012/225803 Al, US 2012/090102 Al, US 7,686,892 B2, and WO2010/142503.
In another aspect, suitable polymeric dyes may include polymeric dyes selected from the group consisting of fabric-substantive colorants sold under the name of Liquitint® (Milliken, Spartanburg, South Carolina, USA), dye -polymer conjugates formed from at least one reactive dye and a polymer selected from the group consisting of polymers comprising a moiety selected from the group consisting of a hydroxyl moiety, a primary amine moiety, a secondary amine moiety, a thiol moiety and mixtures thereof. In still another aspect, suitable polymeric dyes may include polymeric dyes selected from the group consisting of Liquitint® Violet CT, carboxymethyl cellulose (CMC) covalently bound to a reactive blue, reactive violet or reactive red dye such as CMC conjugated with C.I. Reactive Blue 19, sold by Megazyme, Wicklow, Ireland under the product name AZO-CM-CELLULOSE, product code S-ACMC, alkoxylated triphenyl-methane polymeric colourants, alkoxylated thiophene polymeric colourants, and mixtures thereof.
Preferred hueing dyes may include the whitening agents found in WO 08/87497 Al, WO2011/011799 and US 2012/129752 Al. Preferred hueing dyes for use in the present invention may be the preferred dyes disclosed in these references, including those selected from Examples 1- 42 in Table 5 of WO2011/011799. Other preferred dyes are disclosed in US 8,138,222. Other preferred dyes are disclosed in US 7,909,890 B2.
The aforementioned fabric hueing agents can be used in combination (any mixture of fabric hueing agents can be used). Test Methods
I. Method for Determining Deposition for a Dye
a. ) Unbrightened Multifiber Fabric Style 41 swatches (MFF41, 5cm x 10cm, average weight 1.46g) serged with unbrightened thread are purchased from Testfabrics, Inc. (West Pittston,
PA). MFF41 swatches are stripped prior to use by washing two full cycles in AATCC heavy duty liquid laundry detergent (HDL) nil brightener at 49°C and washing 3 additional full cycles at 49°C without detergent. Four replicate swatches are placed into each flask.
b. ) A sufficient volume of AATCC standard nil brightener HDL detergent solution is prepared by dissolving the detergent in 0 gpg water at room temperature at a concentration of 1.55 g per liter.
c. ) A concentrated stock solution of dye is prepared in an appropriate solvent selected from dimethyl sulfoxide (DMSO), ethanol or 50:50 ethanokwater. Ethanol is preferred. The dye stock is added to a beaker containing 400mL detergent solution (prepared in step Lb. above) in an amount sufficient to produce an aqueous solution absorbance at the
Figure imgf000011_0001
of 0.4 AU (+ 0.01AU) in a cuvette of path length 1.0 cm. Total organic solvent concentration in a wash solution from the concentrated stock solution is less than 0.5%. A 125mL aliquot of the wash solution is placed into 3 separate disposable 250mL Erlenmeyer flasks (Thermo Fisher Scientific, Rochester, NY).
d. ) Four MFF41 swatches are placed into each flask, flasks are capped and manually shaken to wet the swatches. Flasks are placed onto a Model 75 wrist action shaker from Burrell
Scientific, Inc. (Pittsburg, PA) and agitated on the highest setting of 10 (390 oscillations per minute with an arc of 14.6°). After 12 minutes, the wash solution is removed by vacuum aspiration, 125mL of Ogpg water is added for a rinse, and the flasks agitated for 4 additional minutes. Rinse solution is removed by vacuum aspiration and swatches are spun in a Mini Countertop Spin Dryer (The Laundry Alternative Inc., Nashua, NH) for 5 minutes, after which they are allowed to air dry in the dark.
e. ) L*, a*, and b* values for the 3 most consumer relevant fabric types, cotton, nylon and polyester, are measured on the dry swatches using a LabScan XE reflectance spectrophotometer (HunterLabs, Reston, VA; D65 illumination, 10° observer, UV light excluded). The L*, a*, and b* values of the 12 swatches (3 flasks each containing 4 swatches) are averaged and the hueing deposition (HD) of the dye is calculated for each fabric type using the following equation:
HD = DE* = ((L*c - L*s)2 + (a*c - a*s)2 + (b*c - b*s)2)1/2 wherein the subscripts c and s respectively refer to the control, i.e., the fabric washed in detergent with no dye, and the fabric washed in detergent containing dye according to the method described above.
II. Method to Determine if a Dye is a Shading Dye
A dye is considered a shading dye (also known as a hueing dye) for the purposes of the present invention if the HDcotton, HDpoiyester or HDnyion is greater than or equal to 2.0 DE* units according to the formula above. If the value of HD for each fabric type is less than 2.0 DE* units, the dye is not a shading dye for the purposes of the present invention. Water-Soluble Film
The film of the present invention is soluble or dispersible in water, and preferably has a water- solubility of at least 50%, preferably at least 75% or even at least 95%, as measured by the method set out here after using a glass-filter with a maximum pore size of 20 microns:
50 grams ± 0.1 gram of pouch material is added in a pre-weighed 400 ml beaker and 245ml ± 1ml of distilled water is added. This is stirred vigorously on a magnetic stirrer set at 600 rpm, for 30 minutes. Then, the mixture is filtered through a folded qualitative sintered-glass filter with a pore size as defined above (max. 20 micron). The water is dried off from the collected filtrate by any conventional method, and the weight of the remaining material is determined (which is the dissolved or dispersed fraction). Then, the percentage solubility or dispersability can be calculated.
Preferred film materials are preferably polymeric materials. The film material can, for example, be obtained by casting, blow-moulding, extrusion or blown extrusion of the polymeric material, as known in the art.
Preferred polymers, copolymers or derivatives thereof suitable for use as pouch material are selected from polyvinyl alcohols, polyvinyl pyrrolidone, polyalkylene oxides, acrylamide, acrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and salts, polyaminoacids or peptides, polyamides, polyacrylamide, copolymers of maleic/acrylic acids, polysaccharides including starch and gelatine, natural gums such as xanthum and carragum. More preferred polymers are selected from polyacrylates and water-soluble acrylate copolymers, methylcellulose, carboxymethylcellulose sodium, dextrin, ethylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, maltodextrin, polymethacrylates, and most preferably selected from polyvinyl alcohols, polyvinyl alcohol copolymers and hydroxypropyl methyl cellulose (HPMC), and combinations thereof. Preferably, the level of polymer in the pouch material, for example a PVA polymer, is at least 60%. The polymer can have any weight average molecular weight, preferably from about 1000 to 1,000,000, more preferably from about 10,000 to 300,000 yet more preferably from about 20,000 to 150,000.
Mixtures of polymers can also be used as the pouch material. This can be beneficial to control the mechanical and/or dissolution properties of the compartments or pouch, depending on the application thereof and the required needs. Suitable mixtures include for example mixtures wherein one polymer has a higher water-solubility than another polymer, and/or one polymer has a higher mechanical strength than another polymer. Also suitable are mixtures of polymers having different weight average molecular weights, for example a mixture of PVA or a copolymer thereof of a weight average molecular weight of about 10,000- 40,000, preferably around 20,000, and of PVA or copolymer thereof, with a weight average molecular weight of about 100,000 to 300,000, preferably around 150,000. Also suitable herein are polymer blend compositions, for example comprising hydrolytically degradable and water-soluble polymer blends such as polylactide and polyvinyl alcohol, obtained by mixing polylactide and polyvinyl alcohol, typically comprising about 1-35% by weight polylactide and about 65% to 99% by weight polyvinyl alcohol. Preferred for use herein are polymers which are from about 60% to about 98% hydrolysed, preferably about 80% to about 90% hydrolysed, to improve the dissolution characteristics of the material.
Preferred film materials are polymeric materials. The film material can be obtained, for example, by casting, blow-moulding, extrusion or blown extrusion of the polymeric material, as known in the art. Preferred polymers, copolymers or derivatives thereof suitable for use as pouch material are selected from polyvinyl alcohols, polyvinyl pyrrolidone, polyalkylene oxides, acrylamide, acrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and salts, polyaminoacids or peptides, polyamides, polyacrylamide, copolymers of maleic/acrylic acids, polysaccharides including starch and gelatine, natural gums such as xanthum and carragum. More preferred polymers are selected from polyacrylates and water-soluble acrylate copolymers, methylcellulose, carboxymethylcellulose sodium, dextrin, ethylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, maltodextrin, polymethacrylates, and most preferably selected from polyvinyl alcohols, polyvinyl alcohol copolymers and hydroxypropyl methyl cellulose (HPMC), and combinations thereof. Preferably, the level of polymer in the pouch material, for example a PVA polymer, is at least 60%. The polymer can have any weight average molecular weight, preferably from about 1000 to 1,000,000, more preferably from about 10,000 to 300,000 yet more preferably from about 20,000 to 150,000. Mixtures of polymers can also be used as the pouch material. This can be beneficial to control the mechanical and/or dissolution properties of the compartments or pouch, depending on the application thereof and the required needs. Suitable mixtures include for example mixtures wherein one polymer has a higher water-solubility than another polymer, and/or one polymer has a higher mechanical strength than another polymer. Also suitable are mixtures of polymers having different weight average molecular weights, for example a mixture of PVA or a copolymer thereof of a weight average molecular weight of about 10,000- 40,000, preferably around 20,000, and of PVA or copolymer thereof, with a weight average molecular weight of about 100,000 to 300,000, preferably around 150,000. Also suitable herein are polymer blend compositions, for example comprising hydrolytically degradable and water-soluble polymer blends such as polylactide and polyvinyl alcohol, obtained by mixing polylactide and polyvinyl alcohol, typically comprising about 1-35% by weight polylactide and about 65% to 99% by weight polyvinyl alcohol. Preferred for use herein are polymers which are from about 60% to about 98% hydrolysed, preferably about 80% to about 90% hydrolysed, to improve the dissolution characteristics of the material.
Preferred films exhibit good dissolution in cold water, meaning unheated water straight from the tap. Preferably such films exhibit good dissolution at temperatures below 25°C, more preferably below 21°C, more preferably below 15°C. By good dissolution it is meant that the film exhibits water- solubility of at least 50%, preferably at least 75% or even at least 95%, as measured by the method set out here after using a glass-filter with a maximum pore size of 20 microns, described above. Preferred films are those supplied by Monosol under the trade references M8630, M8900, M8779, M9467, M8310, films described in US 6 166 117 and US 6 787 512 and PVA films of corresponding solubility and deformability characteristics. Further preferred films are those describes in US2006/0213801, WO 2010/119022 and US6787512.
Preferred water soluble films are those resins comprising one or more PVA polymers, preferably said water soluble film resin comprises a blend of PVA polymers. For example, the PVA resin can include at least two PVA polymers, wherein as used herein the first PVA polymer has a viscosity less than the second PVA polymer. A first PVA polymer can have a viscosity of at least 8 cP (cP means Centipoise), 10 cP, 12 cP, or 13 cP and at most 40 cP, 20 cP, 15 cP, or 13 cP, for example in a range of about 8 cP to about 40 cP, or 10 cP to about 20 cP, or about 10 cP to about 15 cP, or about 12 cP to about 14 cP, or 13 cP. Furthermore, a second PVA polymer can have a viscosity of at least about 10 cP, 20 cP, or 22 cP and at most about 40 cP, 30 cP, 25 cP, or 24 cP, for example in a range of about 10 cP to about 40 cP, or 20 to about 30 cP, or about 20 to about 25 cP, or about 22 to about 24, or about 23 cP. The viscosity of a PVA polymer is determined by measuring a freshly made solution using a Brookfield LV type viscometer with UL adapter as described in British Standard EN ISO 15023-2:2006 Annex E Brookfield Test method. It is international practice to state the viscosity of 4% aqueous polyvinyl alcohol solutions at 20 .deg.C. All viscosities specified herein in cP should be understood to refer to the viscosity of 4% aqueous polyvinyl alcohol solution at 20 .deg.C, unless specified otherwise. Similarly, when a resin is described as having (or not having) a particular viscosity, unless specified otherwise, it is intended that the specified viscosity is the average viscosity for the resin, which inherently has a corresponding molecular weight distribution. The individual PVA polymers can have any suitable degree of hydrolysis, as long as the degree of hydrolysis of the PVA resin is within the ranges described herein. Optionally, the PVA resin can, in addition or in the alternative, include a first PVA polymer that has a Mw in a range of about 50,000 to about 300,000 Daltons, or about 60,000 to about 150,000 Daltons; and a second PVA polymer that has a Mw in a range of about 60,000 to about 300,000 Daltons, or about 80,000 to about 250,000 Daltons.
The PVA resin can still further include one or more additional PVA polymers that have a viscosity in a range of about 10 to about 40 cP and a degree of hydrolysis in a range of about 84% to about 92%.
When the PVA resin includes a first PVA polymer having an average viscosity less than about 11 cP and a polydispersity index in a range of about 1.8 to about 2.3, then in one type of embodiment the PVA resin contains less than about 30 wt.% of the first PVA polymer. Similarly, when the PVA resin includes a first PVA polymer having an average viscosity less than about 11 cP and a polydispersity index in a range of about 1.8 to about 2.3, then in another, non-exclusive type of embodiment the PVA resin contains less than about 30 wt.% of a PVA polymer having a Mw less than about 70,000 Daltons.
Of the total PVA resin content in the film described herein, the PVA resin can comprise about 30 to about 85 wt.% of the first PVA polymer, or about 45 to about 55 wt.% of the first PVA polymer. For example, the PVA resin can contain about 50 wt.% of each PVA polymer, wherein the viscosity of the first PVA polymer is about 13 cP and the viscosity of the second PVA polymer is about 23 cP. One type of embodiment is characterized by the PVA resin including about 40 to about 85 wt.% of a first PVA polymer that has a viscosity in a range of about 10 to about 15 cP and a degree of hydrolysis in a range of about 84% to about 92%. Another type of embodiment is characterized by the PVA resin including about 45 to about 55 wt.% of the first PVA polymer that has a viscosity in a range of about 10 to about 15 cP and a degree of hydrolysis in a range of about 84% to about 92%. The PVA resin can include about 15 to about 60 wt.% of the second PVA polymer that has a viscosity in a range of about 20 to about 25 cP and a degree of hydrolysis in a range of about 84% to about 92%. One contemplated class of embodiments is characterized by the PVA resin including about 45 to about 55 wt.% of the second PVA polymer.
When the PVA resin includes a plurality of PVA polymers the PDI value of the PVA resin is greater than the PDI value of any individual, included PVA polymer. Optionally, the PDI value of the PVA resin is greater than 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.5, or 5.0.
Preferably the PVA resin that has a weighted, average degree of hydrolysis ( H .deg. ) between about 80 and about 92 %, or between about 83 and about 90 %, or about 85 and 89%. For example, H .deg. for a PVA resin that comprises two or more PVA polymers is calculated by the formula H.deg. = (Wi - H, ) where 1/2 is the weight percentage of the respective PVA polymer and and H, is the respective degrees of hydrolysis. Still further it is desirable to choose a PVA resin that has a weighted log average viscosity between about 10 and about 25, or between about 12 and 22, or between about 13.5 and about 20. The .micro, for a PVA resin that comprises two or more PVA polymers is calculated - YW - In / by the formula .micro. = e (1 1) where .micro. [ ] is the viscosity for the respective PVA polymers.
Yet further, it is desirable to choose a PVA resin that has a Resin Selection Index (RSI) in a range of 0.255 to 0.315, or 0.260 to 0.310, or 0.265 to 0.305, or 0.270 to 0.300, or 0.275 to 0.295, preferably 0.270 to 0.300. The RSI is calculated by the formula (w[t] \.micro.[{] - A l)/.Sigma. ((W)iMi ) > wherein .micro. [(] is seventeen, /, is the average viscosity each of the respective PVA polymers, and Wi is the weight percentage of the respective PVA polymers.
Even more preferred films are water soluble copolymer films comprising a least one anionically modified monomer with formula:
m- [G]n
wherein Y represents a vinyl alcohol monomer, G represents a monomer comprising an anionic group and index n is an integer of from 1 to 3. G can be any suitable comonomer capable of carrying of carrying the anionic group, more preferably G is a carboxylic acid. G is preferably selected from the group consisting of maleic acid, itaconic acid, coAMPS, acrylic acid, vinyl acetic acid, vinyl sulfonic acid, allyl sulfonic acid, ethylene sulfonic acid, 2 acrylamido 1 methyl propane sulfonic acid, 2 acrylamido 2 methyl propane sulfonic acid, 2 methyl acrylamido 2 methyl propane sulfonic acid and mixtures thereof.
The anionic group of G is preferably selected from the group consisting of OSO3M, SO3M, C02M, OC02M, OP03M2, OP03HM and OP02M. More preferably anionic group of G is selected from the group consisting of OS03M, S03M, C02M, and OC02M. Most preferably the anionic group of G is selected from the group consisting of S03M and C02M.
Naturally, different film material and/or films of different thickness may be employed in making the compartments of the present invention. A benefit in selecting different films is that the resulting compartments may exhibit different solubility or release characteristics.
The film material herein can also comprise one or more additive ingredients. For example, it can be beneficial to add plasticisers, for example glycerol, ethylene glycol, diethyleneglycol, propylene glycol, sorbitol and mixtures thereof. Other additives include functional detergent additives to be delivered to the wash water, for example organic polymeric dispersants, etc.
Unitised Dose Pouch
The pouches described herein may be single or multi-compartment pouch. Where the pouch is a multi-compartment pouch, the compartments preferably have a different aesthetic appearance. A difference in aesthetics can be achieved in any suitable way. One compartment of the pouch may be made using translucent, transparent, semi-transparent, opaque or semi-opaque film, and the second compartment of the pouch may be made using a different film selected from translucent, transparent, semi-transparent, opaque or semi-opaque film such that the appearance of the compartments is different. The compartments of the pouch may be the same size or volume. Alternatively the compartments of the pouch may have different sizes, with different internal volumes. The compartments may also be different from one another in terms of texture or colour. Hence one compartment may be glossy whilst the other is matt. This can be readily achieved as one side of a water-soluble film is often glossy, whilst the other has a matt finish. Alternatively the film used to make a compartment may be treated in a way so as to emboss, engrave or print the film. Embossing may be achieved by adhering material to the film using any suitable means described in the art. Engraving may be achieved by applying pressure into the film using a suitable technique available in the art. Printing may be achieved using any suitable printer and process available in the art. Alternatively, the film itself may be coloured, allowing the manufacturer to select different coloured films for each compartment. Alternatively the films may be transparent or translucent and the composition contained within may be coloured. Thus in a preferred embodiment of the present invention a first compartment has a colour selected from the group consisting of white, green, blue, orange, red, yellow, pink or purple and a second compartment has a different colour selected from the group consisting of white, yellow, orange, blue or green.
The compartments of a multi-compartment pouch can be separate, but are preferably conjoined in any suitable manner. Most preferably the second and optionally third or subsequent compartments are superimposed on the first compartment. In one embodiment, the third compartment may be superimposed on the second compartment, which is in turn superimposed on the first compartment in a sandwich configuration. Alternatively the second and third, and optionally subsequent, compartments may all be superimposed on the first compartment. However it is also equally envisaged that the first, second and optionally third and subsequent compartments may be attached to one another in a side by side relationship. In a preferred embodiment the present pouch comprises three compartments consisting of a large and two smaller compartments. The second and third smaller compartments are superposed on the first larger compartment. The size and geometry of the compartments are chosen such that this arrangement is achievable. The compartments may be packed in a string, each compartment being individually separable by a perforation line. Hence each compartment may be individually torn-off from the remainder of the string by the end-user, for example, so as to pre-treat or post treat a fabric with a composition from a compartment.
The geometry of the compartments may be the same or different. In a preferred embodiment the second and optionally third or subsequent compartment has a different geometry and shape to the first compartment. In this embodiment the second and optionally third compartments are arranged in a design on the first compartment. Said design may be decorative, educative, illustrative for example to illustrate a concept or instruction, or used to indicate origin of the product. In a preferred embodiment the first compartment is the largest compartment having two large faces sealed around the perimeter. The second compartment is smaller covering less than 75%, more preferably less than 50% of the surface area of one face of the first compartment. In the embodiment wherein there is a third compartment, the above structure is the same but the second and third compartments cover less than 60%, more preferably less than 50%, even more preferably less than 45% of the surface area of one face of the first compartment. Process for Making the Pouch Unitized Dose Product
The pouch of the present invention may be made using any suitable equipment and method. Single compartment pouches are made using vertical, but preferably horizontal form filling techniques commonly known in the art. The film is preferably dampened, more preferably heated to increase the malleability thereof. Even more preferably, the method also involves the use of a vacuum to draw the film into a suitable mould. The vacuum drawing the film into the mould can be applied for 0.2 to 5 seconds, preferably 0.3 to 3 or even more preferably 0.5 to 1.5 seconds, once the film is on the horizontal portion of the surface. This vacuum may preferably be such that it provides an under-pressure of between +10mbar to +1000mbar, more preferably from +100mbar to +600mbar.
The moulds, in which the pouches are made, can have any shape, length, width and depth, depending on the required dimensions of the pouches. The moulds can also vary in size and shape from one to another, if desirable. For example, it may be preferred that the volume of the final pouches is between 5 and 300ml, or even 10 and 150ml or even 20 and 100ml and that the mould sizes are adjusted accordingly.
Heat can be applied to the film, in the process commonly known as thermoforming, by any means. For example the film may be heated directly by passing it under a heating element or through hot air, prior to feeding it onto the surface or once on the surface. Alternatively it may be heated indirectly, for example by heating the surface or applying a hot item onto the film. Most preferably the film is heated using an infra red light. The film is preferably heated to a temperature of 50 to 120°C, or even 60 to 90°C. Alternatively, the film can be wetted by any mean, for example directly by spraying a wetting agent (including water, solutions of the film material or plasticizers for the film material) onto the film, prior to feeding it onto the surface or once on the surface, or indirectly by wetting the surface or by applying a wet item onto the film.
Once a film has been heated/wetted, it is drawn into an appropriate mould, preferably using a vacuum. The filling of the moulded film can be done by any known method for filling (preferably moving) items. The most preferred method will depend on the product form and speed of filling required. Preferably the moulded film is filled by in-line filling techniques. The filled, open pouches are then closed, using a second film, by any suitable method. Preferably, this is also done while in horizontal position and in continuous, constant motion. Preferably the closing is done by continuously feeding a second film, preferably water-soluble film, over and onto the open pouches and then preferably sealing the first and second film together, typically in the area between the moulds and thus between the pouches.
Preferred methods of sealing include heat sealing, solvent welding, and solvent or wet sealing. It is preferred that only the area which is to form the seal, is treated with heat or solvent. The heat or solvent can be applied by any method, preferably on the closing material, preferably only on the areas which are to form the seal. If solvent or wet sealing or welding is used, it may be preferred that heat is also applied. Preferred wet or solvent sealing/ welding methods include applying selectively solvent onto the area between the moulds, or on the closing material, by for example, spraying or printing this onto these areas, and then applying pressure onto these areas, to form the seal. Sealing rolls and belts as described above (optionally also providing heat) can be used, for example.
The formed pouches can then be cut by a cutting device. Cutting can be done using any known method. It may be preferred that the cutting is also done in continuous manner, and preferably with constant speed and preferably while in horizontal position. The cutting device can, for example, be a sharp item or a hot item, whereby in the latter case, the hot item 'burns' through the film/ sealing area.
The different compartments of a multi-compartment pouch may be made together in a side -by- side style and consecutive pouches are not cut. Alternatively, the compartments can be made separately. According to this process and preferred arrangement, the pouches are made according to the process comprising the steps of:
a) forming an first compartment (as described above);
b) forming a recess within some or all of the closed compartment formed in step (a), to generate a second moulded compartment superposed above the first compartment;
c) filling and closing the second compartments by means of a third film;
d) sealing said first, second and third films; and
e) cutting the films to produce a multi-compartment pouch. Said recess formed in step b is preferably achieved by applying a vacuum to the compartment prepared in step a).
Alternatively the second, and optionally third, compartment(s) can be made in a separate step and then combined with the first compartment as described in our co-pending application EP 08101442.5 which is incorporated herein by reference. A particularly preferred process comprises the steps of:
a) forming a first compartment, optionally using heat and/or vacuum, using a first film on a first forming machine;
b) filling said first compartment with a first composition;
c) on a second forming machine, deforming a second film, optionally using heat and vacuum, to make a second and optionally third moulded compartment;
d) filling the second and optionally third compartments;
e) sealing the second and optionally third compartment using a third film;
f) placing the sealed second and optionally third compartments onto the first compartment; g) sealing the first, second and optionally third compartments; and
h) cutting the films to produce a multi-compartment pouch
The first and second forming machines are selected based on their suitability to perform the above process. The first forming machine is preferably a horizontal forming machine. The second forming machine is preferably a rotary drum forming machine, preferably located above the first forming machine.
It will be understood moreover that by the use of appropriate feed stations, it is possible to manufacture multi-compartment pouches incorporating a number of different or distinctive compositions and/or different or distinctive liquid, gel or paste compositions.
Optional Detergent Composition Components
The composition of the present invention is preferably a liquid. By the term 'liquid' it is meant to include liquid, paste, waxy or gel compositions. The liquid composition may comprise a solid. Solids may include powder or agglomerates, such as micro-capsules, beads, noodles or one or more pearlised balls or mixtures thereof. Such a solid element may provide a technical benefit, through the wash or as a pre-treat, delayed or sequential release component. Alternatively it may provide an aesthetic effect. The compositions of the present invention may comprise one or more of the ingredients discussed below.
Surfactants or Detersive Surfactants
The composition of the present invention preferably comprises further surfactants. The total surfactant level may be in the range of from about 1% to 80% by weight of the composition.
Further detersive surfactants utilized can be of the nonionic, zwitterionic, ampholytic or cationic type or can comprise compatible mixtures of these types. More preferably surfactants are selected from the group consisting of anionic, nonionic, cationic surfactants and mixtures thereof. Preferably the compositions are substantially free of betaine surfactants. Detergent surfactants useful herein are described in U.S. Patent 3,664,961, Norris, issued May 23, 1972, U.S. Patent 3,919,678, Laughlin et al., issued December 30, 1975, U.S. Patent 4,222,905, Cockrell, issued September 16, 1980, and in U.S. Patent 4,239,659, Murphy, issued December 16, 1980. Anionic and nonionic surfactants are preferred.
Preferred nonionic surfactants are those of the formula R1(OC2H4)nOH, wherein R1 is a CKTC16 alkyl group or a C8-C12 alkyl phenyl group, and n is from 3 to about 80. Particularly preferred are condensation products of C12-C15 alcohols with from about 5 to about 20 moles of ethylene oxide per mole of alcohol, e.g., C12-C13 alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol.
Fabric Care Benefit Agents
The compositions may comprise a fabric care benefit agent. As used herein, "fabric care benefit agent" refers to any material that can provide fabric care benefits such as fabric softening, color protection, pill/fuzz reduction, anti-abrasion, anti-wrinkle, and the like to garments and fabrics, particularly on cotton and cotton-rich garments and fabrics, when an adequate amount of the material is present on the garment/fabric. Non-limiting examples of fabric care benefit agents include cationic surfactants, silicones, polyolefin waxes, latexes, oily sugar derivatives, cationic polysaccharides, polyurethanes, fatty acids and mixtures thereof. Fabric care benefit agents when present in the composition, are suitably at levels of up to about 30% by weight of the composition, more typically from about 1% to about 20%, preferably from about 2% to about 10%. Detersive enzymes
Detersive enzymes may be incorporated into the compositions of the present invention. Suitable detersive enzymes for use herein include protease, amylase, lipase, cellulase, carbohydrase including mannanase and endoglucanase, and mixtures thereof. Enzymes can be used at their art-taught levels, for example at levels recommended by suppliers such as Novo and Genencor. Typical levels in the compositions are from about 0.0001% to about 5%. When enzymes are present, they can be used at very low levels, e.g., from about 0.001% or lower, in certain embodiments of the invention; or they can be used in heavier-duty laundry detergent formulations in accordance with the invention at higher levels, e.g., about 0.1% and higher. In accordance with a preference of some consumers for "non-biological" detergents, the present invention includes both enzyme-containing and enzyme-free embodiments.
Deposition Aid
Deposition aids may be incorporated into the composition of the present invention. As used herein, "deposition aid" refers to any cationic polymer or combination of cationic polymers that significantly enhance the deposition of a fabric care benefit agent onto the fabric during laundering.
Preferably, the deposition aid is a cationic or amphoteric polymer. The amphoteric polymers of the present invention will also have a net cationic charge, i.e.; the total cationic charges on these polymers will exceed the total anionic charge. Nonlimiting examples of deposition enhancing agents are cationic polysaccharides, chitosan and its derivatives and cationic synthetic polymers. Preferred cationic polysaccharides include cationic cellulose derivatives, cationic guar gum derivatives, chitosan and derivatives and cationic starches. Rheology Modifier
In a preferred embodiment of the present invention, the composition comprises a rheology modifier. The rheology modifier is selected from the group consisting of non-polymeric crystalline, hydroxy- functional materials, polymeric rheology modifiers which impart shear thinning characteristics to the aqueous liquid matrix of the composition. Crystalline, hydroxy-functional materials are rheology modifiers which form thread-like structuring systems throughout the matrix of the composition upon in situ crystallization in the matrix. Specific examples of preferred crystalline, hydroxyl-containing rheology modifiers include castor oil and its derivatives. Especially preferred are hydrogenated castor oil derivatives such as hydrogenated castor oil and hydrogenated castor wax. Commercially available, castor oil-based, crystalline, hydroxyl-containing rheology modifiers include THIXCIN® from Rheox, Inc. (now Elementis). Polymeric rheology modifiers are preferably selected from polyacrylates, polymeric gums, other non-gum polysaccharides, and combinations of these polymeric materials. Preferred polymeric gum materials include pectine, alginate, arabinogalactan (gum Arabic), carrageenan, gellan gum, xanthan gum, guar gum and mixtures thereof.
Builder
The compositions of the present invention may optionally comprise a builder. Suitable builders include polycarboxylate builders include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903. Particularly preferred are citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt
Other preferred builders include ethylene diamine disuccinic acid and salts thereof (ethylene diamine disuccinates, EDDS), ethylene diamine tetraacetic acid and salts thereof (ethylene diamine tetraacetates, EDTA), and diethylene triamine penta acetic acid and salts thereof (diethylene triamine penta acetates, DTPA), aluminosilicates such as zeolite A, B or MAP; fatty acids or salts, preferably sodium salts, thereof, preferably C12-C18 saturated and/or unsaturated fatty acids; and alkali or alkali earth metal carbonates preferably sodium carbonate.
Bleaching System
Bleaching agents suitable herein include chlorine and oxygen bleaches, especially inorganic perhydrate salts such as sodium perborate mono-and tetrahydrates and sodium percarbonate optionally coated to provide controlled rate of release (see, for example, GB-A- 1466799 on sulfate/carbonate coatings), preformed organic peroxyacids and mixtures thereof with organic peroxyacid bleach precursors and/or transition metal-containing bleach catalysts (especially manganese or cobalt). Inorganic perhydrate salts are typically incorporated at levels in the range from about 1% to about 40% by weight, preferably from about 2% to about 30% by weight and more preferably from abut 5% to about 25% by weight of composition. Peroxyacid bleach precursors preferred for use herein include precursors of perbenzoic acid and substituted perbenzoic acid; cationic peroxyacid precursors; peracetic acid precursors such as TAED, sodium acetoxybenzene sulfonate and pentaacetylglucose; pernonanoic acid precursors such as sodium 3,5,5-trimethylhexanoyloxybenzene sulfonate (iso-NOBS) and sodium nonanoyloxybenzene sulfonate (NOBS); amide substituted alkyl peroxyacid precursors (EP-A-0170386); and benzoxazin peroxyacid precursors (EP-A-0332294 and EP-A-0482807). Bleach precursors are typically incorporated at levels in the range from about 0.5% to about 25%, preferably from about 1% to about 10% by weight of composition while the preformed organic peroxyacids themselves are typically incorporated at levels in the range from 0.5% to 25% by weight, more preferably from 1% to 10% by weight of composition. Bleach catalysts preferred for use herein include the manganese triazacyclononane and related complexes (US-A-4246612, US-A-5227084); Co, Cu, Mn and Fe bispyridylamine and related complexes (US-A-5114611); and pentamine acetate cobalt(III) and related complexes(US-A-4810410).
Other adjuncts
Examples of other suitable cleaning adjunct materials include, but are not limited to; enzyme stabilizing systems; antioxidants, opacifier, pearlescent agent, hueing dye, scavenging agents including fixing agents for anionic dyes, complexing agents for anionic surfactants, and mixtures thereof; optical brighteners or fluorescers; soil release polymers; dispersants; suds suppressors; dyes; colorants; hydrotropes such as toluenesulfonates, cumenesulfonates and naphthalenesulfonates; color speckles; perfumes and perfume microcapsules, colored beads, spheres or extrudates; clay softening agents and mixtures thereof. Composition Preparation
The compositions herein can generally be prepared by mixing the ingredients together. If a pearlescent material is used it should be added in the late stages of mixing. If a rheology modifier is used, it is preferred to first form a pre-mix within which the rheology modifier is dispersed in a portion of the water and optionally other ingredients eventually used to comprise the compositions. This pre-mix is formed in such a way that it forms a structured liquid. To this structured pre-mix can then be added, while the pre-mix is under agitation, the surfactant(s) and essential laundry adjunct materials, along with water and whatever optional detergent composition adjuncts are to be used. Secondary Packaging
The multi-compartment pouches of the present invention are preferably further packaged in an outer package. Said outer package may be a see-through or partially see-through container, for example a transparent or translucent bag, tub, carton or bottle. The pack can be made of plastic or any other suitable material, provided the material is strong enough to protect the pouches during transport. This kind of pack is also very useful because the user does not need to open the pack to see how many pouches there are left. Alternatively, the pack can have non- see-through outer packaging, perhaps with indicia or artwork representing the visually-distinctive contents of the pack.
Process of washing
The pouches of the present invention are suitable for laundry cleaning applications. The pouches are suitable for hand or machine washing conditions. When machine washing, the pouch may be delivered from the dispensing drawer or may be added directly into the washing machine drum.
Method for Measuring Weeping
Migration of liquid compounds through the film to the outside of the water soluble package can be quantified using a Corneometer CM825 equipped with CM-825 probe, manufactured by Courage- Khazaka Electronic, Koln, Germany. The equipment is calibrated according to the supplier recommendation. The equipment provides a corneometer value which is recorded. The Corneometer can detect even slightest changes in weeping level since change in the dielectric constant (i.e. presence of fluid on the outside of the pouch) alters the Corneometer value.
The equipment is placed in a conditioned laboratory at 20°C +/- 3C and 50% +/- 10 relative humidity. The pouches are brought to temperature of 20+/- 3C prior to the measurement. The probe is cleaned with a dry and clean paper tissue; then blank measurements are made by slowly wiping the sensor on the clean paper tissue (VWR International bvba, Leuven, Belgium, Cat. No. 115- 0600), to ensure there is no contamination on the probe, until the instrument reads a Corneometer value of zero. The probe is placed vertically on the pouch, as per the usage instructions. Ten replicates are measured for each pouch. The center and corners of the top and bottom face of the pouch are tested. Measurement are repeated on 5 different pouches. The data is thus the average of 50 measurements. The probe is cleaned in between each measurement.
The following table provides an interpretation of the corneometer value for weeping. Weeping classification Corneometer value
Extremely light <50
Very light 50-59
Light 60-64
Light/Medium 65-59
Medium 70-74
Medium/Heavy 75-79
Heavy 80-84
Very heavy 85-89
Extremely heavy >90
The following are examples of the present invention. The following detergent compositions (as set out below, composition A) were prepared comprising differing combinations and levels of solvents.
Ingredients A
Linear C9-Ci5 Alkylbenzene sulfonic acid 18.3
C12-14 alkyl 9-ethoxylate 14.7
Citric Acid 0.7
Fatty acid 6.0
CI 2- 14 alkyl ethoxy 3 sulfate 8.7
Chelant 0.6
Polymer 5.9
Enzymes - Structurant 0.15
Solvent system 37.8
neutralize to pH to
Mono-ethanolamine or NaOH (or mixture thereof)
about 7.4
Additives, Minor To 100%
All levels are in weight percent of the composition.
Mono compartment pouches are filled with liquid detergents of composition A, wherein the solvent system is selected as below from formulations 1 to 9. The pouches are made using M8779 film, available from Monosol using standard thermoforming techniques. Specifically, 0.7g of a 76 μιη thick film M8779 are thermoformed to a single compartment pouch measuring 41mm by 43 mm. The pouch is filled with 23.7 mL (25.4 g) of composition A, above. Example 1
The following solvent system formulations 1 to 4 were prepared comprising differing combinations and levels of solvents. The Corneometer value was measured after 4 weeks storage at 32°C and 80% relative humidity. Based on the value, the weeping profile is classified.
Figure imgf000028_0001
DPG (dipropylene glycol) was supplied by Ineos Manufacturing, Koln, Germany. The solvent has an HSP of 28.5 and a clog P of -0.6.
DEG (diethylene glycol) was supplied by Sabic Petrochemicals, Sittard, The Netherlands.
Glycerol was supplied by Brenntag Sa, Orleans, France. Pdiol (propanediol) was supplied by Ineos Manufacturing, Koln, Germany.
Example 2
The following solvent system formulations 2 to5 were prepared comprising differing combinations and levels of solvents. The Comeometer value was measured after 4 weeks storage at 32°C and 80% relative humidity. Based on the value, the weeping profile is classified.
Figure imgf000029_0001
Example 3
The following solvent system formulations 1, 2, 5 and 7 were prepared comprising differing combinations and levels of solvents. The Comeometer value after 4 weeks storage at 32°C and 80% relative humidity. Based on the value, the weeping profile is classified.
Figure imgf000029_0002
Example 4 The following solvent system formulations 1 to8 were prepared comprising differing combinations and levels of solvents. The Comeometer value was measured after 4 weeks storage at 32°C and 80% relative humidity. Based on the value, the weeping profile is classified.
Figure imgf000030_0001
Example 5
The following solvent system formulations 5, 7, 8 and 9 were prepared comprising differing combinations and levels of solvents. The Comeometer value was measured after 4 weeks storage at 32°C and 80% relative humidity. Based on the value, the weeping profile is classified.
DPG Water Glycerol Pdiol DEG Comeometer Weeping level level level level level value classification
Formulation 9 19.9% 8.8% 9.0% 0.0% 0.0% 72 Medium
Formulation 5 19.9% 6.1% 9.0% 0.0% 2.7% 66 Light/Medium
Formulation 7 19.9% 6.1% 4.7% 7.0% 0.0% 64 Light Formulation 8 19.9% 10.9% 0.0% 7.0% 0.0% 59 Very Light
The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."

Claims

CLAIMS What is claimed is:
1. The use of a composition comprising
a) anionic surfactant; and
b) solvent system comprising at least one primary solvent having Hansen solubility (δ) of less than 29, said composition being encapsulated in a water soluble film, for reducing migration and weeping of said composition through said film.
2. A use according to the preceding claim wherein the primary solvent has molecular weight of less than 1500, more preferably less than 1000, even more preferably less than 700.
3. A use according to any preceding claim wherein the primary solvent has a cLog P of greater than -1.0.
4. A use according to any preceding claim wherein the primary solvent has a Hydrogen bonding component of less than 20.5.
5. A use according to any preceding claim wherein the water soluble film is selected from those having Formula V:
m- [G]„
Formula V
wherein Y represents a vinyl alcohol monomer and G represents a monomer comprising an anionic group selected from the group consisting of OSO3M, SO3M, C02M, OC02M, OP03M2, OP03HM and OP02M and the index is n is from 1 to X.
6. A use according to claim 5 wherein G is selected from the group consisting of carboxylic acids, more preferably G is selected from the group consisting of maleic acid, itaconic acid, co AMPS, acrylic acid, vinyl acetic acid, vinyl sulfonic acid, allyl sulfonic acid, ethylene sulfonic acid, 2 acrylamido 1 methyl propane sulfonic acid, 2 acrylamido 2 methyl propane sulfonic acid, 2 methyl acrylamido 2 methyl propane sulfonic acid and mixtures thereof.
7. A use according to any preceding claim wherein the anionic surfactant is present at a level of from 2% to 60%, preferably from 7% to 50%, most preferably from 10% to 40%.
8. A use according to any preceding claim wherein the primary solvent is selected from the group consisting of polyethylene glycol (PEG) polymer having molecular weight between 400 and 600, dipropylene glycol (DPG), nbutoxy propoxy propanol (nBPP) and mixtures thereof.
9. A use according to any preceding claim wherein the primary solvent is present at a level of from 1 to 25%, preferably from 2.5 to 20%, more preferably from 4 to 19%.
10. A use according to any preceding claim wherein the solvent system additionally comprises a secondary solvent selected from the group consisting of glycerol, water and mixtures thereof.
11. A use according to claim 11 wherein the secondary solvent is glycerol and is present at a level of less than 5%, more preferably less than 4%, most preferably less than 3% by weight of the composition.
12. A use according to claim 11 wherein the secondary solvent is water and is present at a level of less than 20%, more preferably less than 15%, most preferably less than 10% by weight of the composition.
13. A use according to claims 10 to 12 wherein the ratio of primary solvent to glycerol is from 7: 1 to 1:5, more preferably from 6.5: 1 to 1:3, most preferably 3: 1 to 1: 1.
14. A use according to any preceding claim wherein the composition comprises a hueing dye.
15. A use according to claim 14 wherein the hueing dye is selected from the group having Formula I below:
[D]-[A]„
Formula I wherein D represents the residue of a dye comprising a chromophore and A is a moiety selected from the group consisting of OS03M, S03M, C02M, OC02M, OP03M2, OP03HM and OP02M, M is selected from the group consisting of Hydrogen, an alkali or alkali earth metal ion and the index n is an integer from 1 to 6.
16. The use according to claim 15 wherein in formula I, A is selected from the group consisting of OS03M, S03M, C02M, and OC02M.
17. The use according to either of claims 15 or 16 wherein M is selected from the group consisting of hydrogen, sodium or potassium ion.
18. The use according to either of claims 15 to 17 wherein the index n is from 1 to 4, preferably n is 1 or 2.
19. The use according to any of claims 15 to 18 wherein the chromophore group of dye residue, D, provides the negatively charged hueing dye with a maximum extinction coefficient in methanol solution greater than about 1000 liter/mol/cm in the wavelength range of about 400 nm to about 750 nm, preferably from about 10,000 to 100,000 liter/mol/cm in the wavelength range of about 540 nm to about 630 nm, even more preferably from about 20,000 to 70,000 liter/mol/cm in the wavelength range of about 560 nm to about 610 nm.
20. The use according to any of claims 15 to 19 wherein chromophore group of dye residue, D, is selected from the group consisting of benzodifurane, methine, triphenylmethane, azine, tripehnoxazine, naphthalimide, pyrazole, naphthoquinone, anthraquinone, mono-azo and bis- azo and mixtures thereof, more preferably the dye residue, D, is selected form the group consisting of Azine, anthraquinone, azo chromophores and mixtures thereof.
PCT/US2013/073259 2012-12-06 2013-12-05 Use of composition to reduce weeping and migration through a water soluble film WO2014089270A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
JP2015545832A JP6185075B2 (en) 2012-12-06 2013-12-05 Use of compositions to reduce migration and leakage through water-soluble films
BR112015012916A BR112015012916A2 (en) 2012-12-06 2013-12-05 use of composition to reduce exudation and migration through a water-soluble film
CN201380061599.3A CN104812883A (en) 2012-12-06 2013-12-05 Use of composition to reduce weeping and migration through water soluble film
RU2015126906A RU2619119C2 (en) 2012-12-06 2013-12-05 Use of composition to reduce weeping and migration through water soluble film
MX2015006848A MX2015006848A (en) 2012-12-06 2013-12-05 Use of composition to reduce weeping and migration through a water soluble film.
CA2893757A CA2893757C (en) 2012-12-06 2013-12-05 Use of composition to reduce weeping and migration through a water soluble film
ZA2015/03383A ZA201503383B (en) 2012-12-06 2015-05-14 Use of composition to reduce weeping and migration through a water soluble film
US14/731,455 US9404071B2 (en) 2012-12-06 2015-06-05 Use of composition to reduce weeping and migration through a water soluble film

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP12195792.2 2012-12-06
EP12195792.2A EP2740785A1 (en) 2012-12-06 2012-12-06 Use of composition to reduce weeping and migration through a water soluble film

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US14/731,455 Continuation US9404071B2 (en) 2012-12-06 2015-06-05 Use of composition to reduce weeping and migration through a water soluble film

Publications (1)

Publication Number Publication Date
WO2014089270A1 true WO2014089270A1 (en) 2014-06-12

Family

ID=47290765

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2013/073259 WO2014089270A1 (en) 2012-12-06 2013-12-05 Use of composition to reduce weeping and migration through a water soluble film

Country Status (9)

Country Link
EP (1) EP2740785A1 (en)
JP (1) JP6185075B2 (en)
CN (1) CN104812883A (en)
BR (1) BR112015012916A2 (en)
CA (1) CA2893757C (en)
MX (1) MX2015006848A (en)
RU (1) RU2619119C2 (en)
WO (1) WO2014089270A1 (en)
ZA (1) ZA201503383B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017043512A1 (en) * 2015-09-11 2017-03-16 日本合成化学工業株式会社 Water-soluble film and chemical package
EP3286292B1 (en) 2015-04-23 2019-03-20 The Procter and Gamble Company Detergent compositions comprising and a shading dye incorporated into a water-soluble film
JP2019508538A (en) * 2016-02-05 2019-03-28 ザ プロクター アンド ギャンブル カンパニー Liquid laundry detergent composition
RU2712693C2 (en) * 2014-10-13 2020-01-30 МОНОСОЛ, ЭлЭлСи Water-soluble film from polyvinyl alcohol mixture, related methods and related products

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2645335C1 (en) * 2014-03-07 2018-02-21 Дзе Проктер Энд Гэмбл Компани Compositions containing bitter agent
US10240114B2 (en) * 2014-10-13 2019-03-26 The Procter & Gamble Company Articles comprising water-soluble polyvinyl alcohol blend film and related methods
TWI677525B (en) * 2014-10-13 2019-11-21 美商摩諾索公司 Water-soluble polyvinyl alcohol blend film, related methods, and related articles
TWI689547B (en) 2014-10-13 2020-04-01 美商摩諾索公司 Water-soluble polyvinyl alcohol film with plasticizer blend, related methods, and related articles
US10155868B2 (en) * 2015-10-13 2018-12-18 Milliken & Company Whitening agents for cellulosic substrates
US11085012B2 (en) * 2017-10-30 2021-08-10 Henkel IP & Holding GmbH Detergent single dose packs and methods of producing the same
AU2019262763A1 (en) 2018-05-02 2020-11-26 Monosol, Llc Water-soluble polyvinyl alcohol blend film, related methods, and related articles
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
EP3828255B1 (en) * 2019-11-29 2023-11-22 Henkel AG & Co. KGaA Multiple chamber detergent product with high contrast between chambers

Citations (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2220099A (en) 1934-01-10 1940-11-05 Gen Aniline & Flim Corp Sulphonic acids
US2477383A (en) 1946-12-26 1949-07-26 California Research Corp Sulfonated detergent and its method of preparation
US3664961A (en) 1970-03-31 1972-05-23 Procter & Gamble Enzyme detergent composition containing coagglomerated perborate bleaching agent
US3835163A (en) 1973-08-02 1974-09-10 Monsanto Co Tetrahydrofuran polycarboxylic acids
US3919678A (en) 1974-04-01 1975-11-11 Telic Corp Magnetic field generation apparatus
GB1466799A (en) 1973-04-20 1977-03-09 Interox Particulate peroxygen compounds
US4102903A (en) 1977-01-05 1978-07-25 Monsanto Company Tetrahydropyran and 1,4-dioxane polycarboxylate compounds, methods for making such compounds and compositions and methods employing same
US4120874A (en) 1977-01-05 1978-10-17 Monsanto Company Diesters of 6-cyano-2,2-tetrahydropyrandicarboxylates
US4158635A (en) 1977-12-05 1979-06-19 Monsanto Company Detergent formulations containing tetrahydropyran or 1,4-dioxane polycarboxylates and method for using same
US4222905A (en) 1978-06-26 1980-09-16 The Procter & Gamble Company Laundry detergent compositions having enhanced particulate soil removal performance
US4239659A (en) 1978-12-15 1980-12-16 The Procter & Gamble Company Detergent compositions containing nonionic and cationic surfactants, the cationic surfactant having a long alkyl chain of from about 20 to about 30 carbon atoms
US4246612A (en) 1979-02-28 1981-01-20 Barr & Stroud Limited Optical raster scanning system
EP0170386A2 (en) 1984-06-21 1986-02-05 The Procter & Gamble Company Bleaching compounds and compositions comprising fatty peroxy acids, salts thereof, and precursors therefor
US4810410A (en) 1986-12-13 1989-03-07 Interox Chemicals Limited Bleach activation
EP0332294A2 (en) 1988-02-11 1989-09-13 BP Chemicals Limited Bleach activators in detergent compositions
EP0482807A1 (en) 1990-10-23 1992-04-29 WARWICK INTERNATIONAL GROUP LIMITED (Co. n 2864019) Releasably encapsulated active substrates
US5114611A (en) 1989-04-13 1992-05-19 Lever Brothers Company, Divison Of Conopco, Inc. Bleach activation
US5227084A (en) 1991-04-17 1993-07-13 Lever Brothers Company, Division Of Conopco, Inc. Concentrated detergent powder compositions
US6166117A (en) 1997-06-11 2000-12-26 Kuraray Co., Ltd. Water-soluble film
US6787512B1 (en) 2003-03-19 2004-09-07 Monosol, Llc Water-soluble copolymer film packet
US20050244444A1 (en) * 2001-01-31 2005-11-03 The Procter & Gamble Company Rapidly dissolvable polymer films and articles made therefrom
US20060213801A1 (en) 2003-10-07 2006-09-28 Ipek Karaoren Film packaged product portion and method for producing the same
US7208459B2 (en) 2004-06-29 2007-04-24 The Procter & Gamble Company Laundry detergent compositions with efficient hueing dye
US20080034511A1 (en) 2004-09-23 2008-02-14 Batchelor Stephen N Laundry Treatment Compositions
WO2008087497A1 (en) 2007-01-19 2008-07-24 The Procter & Gamble Company Laundry care composition comprising a whitening agent for cellulosic substrates
US7686892B2 (en) 2004-11-19 2010-03-30 The Procter & Gamble Company Whiteness perception compositions
WO2010119022A1 (en) 2009-04-16 2010-10-21 Unilever Plc Polymer particles
WO2010142503A1 (en) 2009-06-12 2010-12-16 Unilever Plc Cationic dye polymers
WO2011011799A2 (en) 2010-11-12 2011-01-27 The Procter & Gamble Company Thiophene azo dyes and laundry care compositions containing the same
US7909890B2 (en) 2007-11-26 2011-03-22 The Procter & Gamble Company Shading compositions
WO2011098355A1 (en) 2010-02-09 2011-08-18 Unilever Plc Dye polymers
US20110303576A1 (en) * 2010-06-15 2011-12-15 Carlo Ricci Multi-Compartment Pouch
US8138222B2 (en) 2007-01-19 2012-03-20 Milliken & Company Whitening agents for cellulosic substrates
US20120090102A1 (en) 2009-06-15 2012-04-19 Stephen Norman Batchelor Anionic dye polymers
WO2012054058A1 (en) 2010-10-22 2012-04-26 The Procter & Gamble Company Bis-azo colorants for use as bluing agents
US20120129752A1 (en) 2010-10-22 2012-05-24 Stenger Patrick Christopher Low built detergent composition comprising bluing agent
EP2476744A1 (en) * 2011-01-12 2012-07-18 The Procter & Gamble Company Method for controlling the plasticization of a water soluble film
US20120225803A1 (en) 2009-10-23 2012-09-06 Stephen Norman Batchelor Dye polymers
US8268016B2 (en) 2004-09-23 2012-09-18 The Sun Products Corporation Laundry treatment compositions

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19621673A1 (en) 1996-05-30 1997-12-04 Bayerische Motoren Werke Ag Front structure of a motor vehicle
AR049537A1 (en) * 2004-06-29 2006-08-09 Procter & Gamble DETERGENT COMPOSITIONS FOR LAUNDRY WITH DYING COLOR
US20060275567A1 (en) * 2005-06-07 2006-12-07 Richard Vicari Borate resistant films
ATE539141T1 (en) * 2008-06-13 2012-01-15 Procter & Gamble MULTI-CHAMBER BAGS
CA2843135C (en) * 2011-01-13 2018-03-13 Lift2Sell, LLC Scissor lift pallet lifter

Patent Citations (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2220099A (en) 1934-01-10 1940-11-05 Gen Aniline & Flim Corp Sulphonic acids
US2477383A (en) 1946-12-26 1949-07-26 California Research Corp Sulfonated detergent and its method of preparation
US3664961A (en) 1970-03-31 1972-05-23 Procter & Gamble Enzyme detergent composition containing coagglomerated perborate bleaching agent
GB1466799A (en) 1973-04-20 1977-03-09 Interox Particulate peroxygen compounds
US3835163A (en) 1973-08-02 1974-09-10 Monsanto Co Tetrahydrofuran polycarboxylic acids
US3923679A (en) 1973-08-02 1975-12-02 Monsanto Co Salts of tetrahydrofuran polycarboxylic acids as detergent builders and complexing agents
US3919678A (en) 1974-04-01 1975-11-11 Telic Corp Magnetic field generation apparatus
US4102903A (en) 1977-01-05 1978-07-25 Monsanto Company Tetrahydropyran and 1,4-dioxane polycarboxylate compounds, methods for making such compounds and compositions and methods employing same
US4120874A (en) 1977-01-05 1978-10-17 Monsanto Company Diesters of 6-cyano-2,2-tetrahydropyrandicarboxylates
US4158635A (en) 1977-12-05 1979-06-19 Monsanto Company Detergent formulations containing tetrahydropyran or 1,4-dioxane polycarboxylates and method for using same
US4222905A (en) 1978-06-26 1980-09-16 The Procter & Gamble Company Laundry detergent compositions having enhanced particulate soil removal performance
US4239659A (en) 1978-12-15 1980-12-16 The Procter & Gamble Company Detergent compositions containing nonionic and cationic surfactants, the cationic surfactant having a long alkyl chain of from about 20 to about 30 carbon atoms
US4246612A (en) 1979-02-28 1981-01-20 Barr & Stroud Limited Optical raster scanning system
EP0170386A2 (en) 1984-06-21 1986-02-05 The Procter & Gamble Company Bleaching compounds and compositions comprising fatty peroxy acids, salts thereof, and precursors therefor
US4810410A (en) 1986-12-13 1989-03-07 Interox Chemicals Limited Bleach activation
EP0332294A2 (en) 1988-02-11 1989-09-13 BP Chemicals Limited Bleach activators in detergent compositions
US5114611A (en) 1989-04-13 1992-05-19 Lever Brothers Company, Divison Of Conopco, Inc. Bleach activation
EP0482807A1 (en) 1990-10-23 1992-04-29 WARWICK INTERNATIONAL GROUP LIMITED (Co. n 2864019) Releasably encapsulated active substrates
US5227084A (en) 1991-04-17 1993-07-13 Lever Brothers Company, Division Of Conopco, Inc. Concentrated detergent powder compositions
US6166117A (en) 1997-06-11 2000-12-26 Kuraray Co., Ltd. Water-soluble film
US20050244444A1 (en) * 2001-01-31 2005-11-03 The Procter & Gamble Company Rapidly dissolvable polymer films and articles made therefrom
US6787512B1 (en) 2003-03-19 2004-09-07 Monosol, Llc Water-soluble copolymer film packet
US20060213801A1 (en) 2003-10-07 2006-09-28 Ipek Karaoren Film packaged product portion and method for producing the same
US7208459B2 (en) 2004-06-29 2007-04-24 The Procter & Gamble Company Laundry detergent compositions with efficient hueing dye
US20080034511A1 (en) 2004-09-23 2008-02-14 Batchelor Stephen N Laundry Treatment Compositions
US8268016B2 (en) 2004-09-23 2012-09-18 The Sun Products Corporation Laundry treatment compositions
US7686892B2 (en) 2004-11-19 2010-03-30 The Procter & Gamble Company Whiteness perception compositions
WO2008087497A1 (en) 2007-01-19 2008-07-24 The Procter & Gamble Company Laundry care composition comprising a whitening agent for cellulosic substrates
US8138222B2 (en) 2007-01-19 2012-03-20 Milliken & Company Whitening agents for cellulosic substrates
US7909890B2 (en) 2007-11-26 2011-03-22 The Procter & Gamble Company Shading compositions
WO2010119022A1 (en) 2009-04-16 2010-10-21 Unilever Plc Polymer particles
WO2010142503A1 (en) 2009-06-12 2010-12-16 Unilever Plc Cationic dye polymers
US20120090102A1 (en) 2009-06-15 2012-04-19 Stephen Norman Batchelor Anionic dye polymers
US20120225803A1 (en) 2009-10-23 2012-09-06 Stephen Norman Batchelor Dye polymers
WO2011098355A1 (en) 2010-02-09 2011-08-18 Unilever Plc Dye polymers
US20110303576A1 (en) * 2010-06-15 2011-12-15 Carlo Ricci Multi-Compartment Pouch
WO2012054058A1 (en) 2010-10-22 2012-04-26 The Procter & Gamble Company Bis-azo colorants for use as bluing agents
US20120129752A1 (en) 2010-10-22 2012-05-24 Stenger Patrick Christopher Low built detergent composition comprising bluing agent
WO2011011799A2 (en) 2010-11-12 2011-01-27 The Procter & Gamble Company Thiophene azo dyes and laundry care compositions containing the same
EP2476744A1 (en) * 2011-01-12 2012-07-18 The Procter & Gamble Company Method for controlling the plasticization of a water soluble film

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ALLAN F; M BARTON: "Handbook of solubility Parameters and other parameters", 1983, CRC PRESS

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2712693C2 (en) * 2014-10-13 2020-01-30 МОНОСОЛ, ЭлЭлСи Water-soluble film from polyvinyl alcohol mixture, related methods and related products
EP3286292B1 (en) 2015-04-23 2019-03-20 The Procter and Gamble Company Detergent compositions comprising and a shading dye incorporated into a water-soluble film
WO2017043512A1 (en) * 2015-09-11 2017-03-16 日本合成化学工業株式会社 Water-soluble film and chemical package
JPWO2017043512A1 (en) * 2015-09-11 2018-06-28 日本合成化学工業株式会社 Water-soluble film and drug package
JP2019508538A (en) * 2016-02-05 2019-03-28 ザ プロクター アンド ギャンブル カンパニー Liquid laundry detergent composition

Also Published As

Publication number Publication date
RU2015126906A (en) 2017-01-13
JP6185075B2 (en) 2017-08-23
BR112015012916A2 (en) 2017-07-11
EP2740785A1 (en) 2014-06-11
JP2016504440A (en) 2016-02-12
RU2619119C2 (en) 2017-05-12
ZA201503383B (en) 2017-09-27
CA2893757C (en) 2018-07-10
MX2015006848A (en) 2015-09-16
CA2893757A1 (en) 2014-06-12
CN104812883A (en) 2015-07-29

Similar Documents

Publication Publication Date Title
US9404071B2 (en) Use of composition to reduce weeping and migration through a water soluble film
CA2893757C (en) Use of composition to reduce weeping and migration through a water soluble film
WO2014089386A1 (en) Soluble pouch comprising hueing dye
EP2258820B1 (en) Water-soluble pouch
CA2725687C (en) Multi-compartment pouch for laundry care comprising a whitening agent
CA2823212C (en) Method for controlling the plasticization of a water soluble film

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13808424

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: MX/A/2015/006848

Country of ref document: MX

ENP Entry into the national phase

Ref document number: 2893757

Country of ref document: CA

Ref document number: 2015545832

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112015012916

Country of ref document: BR

ENP Entry into the national phase

Ref document number: 2015126906

Country of ref document: RU

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 13808424

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 112015012916

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20150602