WO2013163491A1 - Ensemble applicateur pour l'application d'une composition - Google Patents

Ensemble applicateur pour l'application d'une composition Download PDF

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Publication number
WO2013163491A1
WO2013163491A1 PCT/US2013/038311 US2013038311W WO2013163491A1 WO 2013163491 A1 WO2013163491 A1 WO 2013163491A1 US 2013038311 W US2013038311 W US 2013038311W WO 2013163491 A1 WO2013163491 A1 WO 2013163491A1
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WO
WIPO (PCT)
Prior art keywords
composition
tine
container
applicator assembly
scalp
Prior art date
Application number
PCT/US2013/038311
Other languages
English (en)
Inventor
William Dale Murdock
Mikah Coffindaffer
James Douglas Still
Joseph Allen BERLEPSCH
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 CA2870208A priority Critical patent/CA2870208A1/fr
Priority to EP13720207.3A priority patent/EP2840928A1/fr
Priority to CN201380022237.3A priority patent/CN104254262A/zh
Priority to JP2015509158A priority patent/JP2015515495A/ja
Priority to MX2014011551A priority patent/MX2014011551A/es
Publication of WO2013163491A1 publication Critical patent/WO2013163491A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A45—HAND OR TRAVELLING ARTICLES
    • A45D—HAIRDRESSING OR SHAVING EQUIPMENT; EQUIPMENT FOR COSMETICS OR COSMETIC TREATMENTS, e.g. FOR MANICURING OR PEDICURING
    • A45D34/00—Containers or accessories specially adapted for handling liquid toiletry or cosmetic substances, e.g. perfumes
    • A—HUMAN NECESSITIES
    • A45—HAND OR TRAVELLING ARTICLES
    • A45D—HAIRDRESSING OR SHAVING EQUIPMENT; EQUIPMENT FOR COSMETICS OR COSMETIC TREATMENTS, e.g. FOR MANICURING OR PEDICURING
    • A45D44/00—Other cosmetic or toiletry articles, e.g. for hairdressers' rooms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B11/00—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use
    • B05B11/0005—Components or details
    • B05B11/0089—Dispensing tubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D83/00—Containers or packages with special means for dispensing contents
    • B65D83/14—Containers or packages with special means for dispensing contents for delivery of liquid or semi-liquid contents by internal gaseous pressure, i.e. aerosol containers comprising propellant for a product delivered by a propellant
    • B65D83/28—Nozzles, nozzle fittings or accessories specially adapted therefor
    • B65D83/285—Nozzles, nozzle fittings or accessories specially adapted therefor for applying the contents, e.g. brushes, rollers, pads, spoons, razors, scrapers

Definitions

  • the present invention relates to an applicator assembly and a method for applying a composition. More particularly, the invention relates to an applicator assembly having a container, an extended tip actuator with a hollow tine, and an engine for applying a composition, and methods thereof.
  • compositions for the purposes of conditioning, cleansing, dying, and/or applying one or more benefit agents.
  • the designs of currently marketed devices can lead to consumer confusion as to how to use the device, resulting in decreased efficacy and inefficient delivery of the composition.
  • a method for delivering a composition to the scalp comprising: (a) providing a composition in an applicator assembly, the applicator assembly comprising: (i) a container for holding the composition; (ii) an extended tip actuator in fluid communication with the container, the extended tip actuator comprising: (1) a base portion configured to fluidly connect the extended tip actuator to the container; and (2) a body portion configured to fluidly connect the base portion to a hollow tine, wherein the tine comprises a face located distally from the body portion, wherein the tine comprises an aperture in fluid communication with the container, and wherein the tine has a protrusion length of from about 0.5 mm to about 100 mm; and (iii) an engine for delivering the composition from the container through the extended tip actuator; and (b) dispensing the composition from the applicator assembly directly onto the scalp.
  • an applicator assembly for delivering a composition to the scalp comprising: (a) a container for holding the composition; (b) an extended tip actuator in fluid communication with the container, the extended tip actuator comprising: (i) a base portion configured to fluidly connect the extended tip actuator to the container; and (ii) a body portion configured to fluidly connect the base portion to a hollow tine, wherein the tine comprises a face located distally from the body portion, wherein the tine comprises an aperture in fluid communication with the container, and wherein the tine has a protrusion length of from about 0.5 mm to about 100 mm; and (c) an engine for delivering the composition from the container through the extended tip actuator to the scalp.
  • Fig. 1 is a perspective front view of one embodiment of the applicator assembly
  • Fig. 2 is a front view of the applicator assembly of Fig. 1;
  • Fig. 3 is a top view of the applicator assembly of Fig. 1;
  • Fig. 4 is a right side view of the applicator assembly of Fig. 1.
  • compositions and methods/processes of the present invention can comprise, consist of, and consist essentially of the elements and limitations of the invention described herein, as well as any of the additional or optional ingredients, components, steps, or limitations described herein.
  • scaling includes the roots of the hair.
  • test methods disclosed in the Test Methods Section of the present application should be used to determine the respective values of the parameters of Applicants' inventions.
  • component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.
  • the applicator assembly 100 may comprise a container 150.
  • the container 150 may be of any type that is suitable for holding a composition.
  • the container 150 may be substantially rigid.
  • the container 150 is substantially rigid if it does not collapse under external atmospheric pressure when it is subject to an interior partial vacuum.
  • the container 150 may comprise a non-rigid material.
  • the non-rigid material may be designed for being squeezed.
  • the container 150 may be made out of any suitable material selected from the group consisting of plastic, metal, alloy, laminate, and combinations thereof.
  • the container 150 may be any shape that fits the holding structure and may comprise at least one interior compartment for containing at least one fluid.
  • the container 150 may be a refillable container such as a pour- in or screw-on container, or the container 150 may be for one-time use.
  • the container 150 may also be removable from the applicator assembly 100. Alternatively, the container 150 may be integrated with applicator assembly 100.
  • the applicator assembly 100 may comprise an extended tip actuator 200.
  • the extended tip actuator 200 may be in fluid communication with the container 150.
  • the extended tip actuator 200 may comprise a base portion 210, a body portion 220, and a hollow tine 225.
  • the extended tip actuator 200 may be made out of any suitable material selected from the group consisting of plastic, metal, alloy, and combinations thereof.
  • the extended tip actuator 200 may be removable from the applicator assembly 100. Alternatively, the extended tip actuator 200 may be integrated with the applicator assembly 100.
  • the extended tip actuator 200 may comprise a base portion 210.
  • the base portion 210 may be configured to fluidly connect the extended tip actuator 200 to the container 150.
  • the base portion 210 may be removable from the extended tip actuator 200.
  • the base portion 210 may be integrated with the extended tip actuator 200.
  • the extended tip actuator 200 may comprise a body portion 220.
  • the body portion 220 may be configured to fluidly connect the base portion 210 to a hollow tine 225.
  • the body portion 220 may be removable from the extended tip actuator 200.
  • the body portion 210 may be integrated with the extended tip actuator 200.
  • the extended tip actuator 200 may comprise a hollow tine 225.
  • the hollow tine 225 may comprise a face located distally from the body portion 220.
  • the tine may also comprise an aperture in fluid communication with the container 150.
  • the tine may be removable from the extended tip actuator 200.
  • the tine may be integrated with the extended tip actuator 200.
  • the extended tip actuator 200 may only have one hollow tine 225.
  • the hollow tine 225 may have a protrusion length 420.
  • the protrusion length 420 is the distance that hollow tine 225 protrudes from the outer contours of the container 150.
  • the hollow tine 225 may have a protrusion length 420 of from about 0.5 mm to about 100 mm, alternatively from about 5 mm to about 80 mm, alternatively from about 10 mm to about 60 mm, alternatively from about 15 mm to about 55 mm, alternatively from about 20 mm to about 50 mm, and alternatively from about 25 mm to about 45 mm.
  • the hollow tine 225 may have a protrusion length 420 of from about 0.5 mm to about 30 mm, and alternatively from about 10 mm to about 25 mm.
  • the applicator assembly 100 may further comprise a longitudinal axis 300 therethrough.
  • the hollow tine 225 is angled from about 20 ° to about 100 ° from the longitudinal axis 300, alternatively from about 25 ° to about 70 ° from the longitudinal axis 300, alternatively from about 30 ° to about 60 ° from the longitudinal axis 300, alternatively from about 35 ° to about 55 ° from the longitudinal axis 300, and alternatively at about 45 ° from the longitudinal axis 300.
  • the hollow tine 225 is angled from about 70 ° to about 110 ° from the longitudinal axis 300, alternatively from about 80 ° to about 100 ° from the longitudinal axis 300, alternatively from about 85 ° to about 95 ° from the longitudinal axis 300, and alternatively at about 90 ° from the longitudinal axis 300.
  • the angle measurement may be calculated counterclockwise from the upper portion of the longitudinal axis 300 shown in Fig. 4.
  • the hollow tine 225 may comprise a face 226 located distally from the body portion 220 of the extended tip actuator 200.
  • the applicator assembly 100 may further comprise a longitudinal axis 300 therethrough.
  • the face 226 is angled from about 10 ° to about 30 ° from the longitudinal axis 300, alternatively from about 15 ° to about 25 ° from the longitudinal axis 300, alternatively from about 20 ° to about 25 ° from the longitudinal axis 300, and alternatively at about 23 ° from the longitudinal axis 300.
  • the face 226 is angled from about 35 ° to about 55 ° from the longitudinal axis 300, alternatively from about 40 ° to about 50 ° from the longitudinal axis 300, alternatively from about 43 ° to about 48 ° from the longitudinal axis 300, and alternatively at about 45 ° from the longitudinal axis 300.
  • the face 226 angle measurement may be calculated counterclockwise from the upper portion of the longitudinal axis 300 shown in Fig. 4. b. Aperture
  • the hollow tine 225 may comprise an aperture 227 in fluid communication with the container 150.
  • the aperture 227 may be of any shape, including but not limited to, circular or square.
  • each aperture 227 may have a diameter of from about 0.1 mm to about 5 mm. In another embodiment, each aperture 227 may have a diameter of from about 0.2 mm to about 2 mm. In yet another embodiment, each aperture 227 may have a diameter of from about 0.5 mm to about 1.5 mm.
  • the applicator assembly 100 may also comprise an engine for delivering a composition from the container 150 through the extended tip actuator 200.
  • the engine may be of any type suitable for dispensing a composition from the container 150, including but not limited to a mechanical pump, aerosol, or squeezing. In one embodiment, the engine may be powered by any means capable of delivering electricity.
  • the engine may dispense from about 0.05 mL to about 4 mL of a composition per complete stroke. In another embodiment, the engine may dispense from about 0.1 mL to about 1 mL of the composition per complete stroke. In yet another embodiment, the engine may dispense from about 0.3 mL to about 0.5 mL per complete stroke.
  • the engine may deliver an unmetered dose.
  • the consumer may control the dosage delivered by the applicator assembly 100 by deciding, for example, how long to hold down a button.
  • the applicator assembly 100 may further comprise a composition.
  • the composition may be a rinse-off product or a leave-on product, and can be formulated in a wide variety of product forms, including but not limited to liquids, foams, creams, gels, emulsions, powders, and mousses.
  • the composition may have a neat viscosity of from about 2,000 cps to about 45,000 cps, alternatively from about 9,000 cps to about 25,000 cps, alternatively from about 9,000 cps to about 12,000 cps, alternatively from about 20,000 cps to about 25,000 cps, alternatively from about 3,000 to about 10,000 cps, and alternatively from about 5,000 to about 8,000 cps.
  • the neat viscosity of the composition is determined by measuring the viscosity of the composition at a shear rate of 2 Vsec. Scientifically, neat viscosity is the ratio of shear stress to shear rate. Neat viscosity of the composition can be measured with a rheometer. A TA Instrument AR2000 may be used to measure the shear stress curve of the composition.
  • the composition may be of any type suitable for application to human skin, including the scalp. In another embodiment, the composition may be of any type suitable for application to pet skin, including the roots of pet hair. In yet another embodiment, the composition may be of any type suitable for application to fabric and/or carpet.
  • the composition may comprise one or more components known for use in hair care or personal care products, provided that the additional components do not otherwise unduly impair product stability, aesthetics, or performance.
  • additional components do not otherwise unduly impair product stability, aesthetics, or performance.
  • Such optional ingredients are most typically those described in reference books such as the CTFA Cosmetic Ingredient Handbook, Second Edition, The Cosmetic, Toiletries, and Fragrance Association, Inc. 1988, 1992.
  • Non-limiting examples of components for use in the composition include conditioning agents (e.g., silicones, hydrocarbon oils, fatty esters), natural cationic deposition polymers, synthetic cationic deposition polymers, anti-dandruff agents, particles, particulate tapioca starch, suspending agents, paraffinic hydrocarbons, propellants, viscosity modifiers, dyes, non-volatile solvents or diluents (water-soluble and water-insoluble), pearlescent aids, foam boosters, surfactants or nonionic cosurfactants, pediculocides, pH adjusting agents, perfumes, preservatives, proteins, skin active agents, sunscreens, UV absorbers, and vitamins.
  • conditioning agents e.g., silicones, hydrocarbon oils, fatty esters
  • natural cationic deposition polymers e.g., hydrocarbon oils, fatty esters
  • synthetic cationic deposition polymers e.g., anti-dandruff agents, particles, particulate tapioca star
  • the composition may comprise one or more conditioning agents.
  • Conditioning agents include materials that are used to give a particular conditioning benefit to hair and/or scalp.
  • the conditioning agents that may be useful in the composition typically comprise a water-insoluble, water-dispersible, non-volatile, liquid that forms emulsified, liquid particles.
  • Suitable conditioning agents for use in the composition are those conditioning agents characterized generally as silicones (e.g., silicone oils, cationic silicones, silicone gums, high refractive silicones, and silicone resins), organic conditioning oils (e.g., hydrocarbon oils, polyolefins, and fatty esters) or combinations thereof, or those conditioning agents which otherwise form liquid, dispersed particles in the aqueous surfactant matrix.
  • One or more conditioning agents may be present from about 0.01 wt to about 10 wt , alternatively from about 0.1 wt to about 8 wt , and alternatively from about 0.2 wt to about 4 wt , by weight of the composition.
  • the conditioning agent of the composition may be an insoluble silicone conditioning agent.
  • the silicone conditioning agent particles may comprise volatile silicone, non-volatile silicone, or combinations thereof. If volatile silicones are present, it will typically be incidental to their use as a solvent or carrier for commercially available forms of non-volatile silicone materials ingredients, such as silicone gums and resins.
  • the silicone conditioning agent particles may comprise a silicone fluid conditioning agent and may also comprise other ingredients, such as a silicone resin to improve silicone fluid deposition efficiency or enhance glossiness of the hair.
  • the concentration of the silicone conditioning agent may range from about 0.01% to about 10%, by weight of the composition, alternatively from about 0.1% to about 8%, alternatively from about 0.1% to about 5%, and alternatively from about 0.2% to about 3%.
  • suitable silicone conditioning agents, and optional suspending agents for the silicone are described in U.S. Reissue Pat. No. 34,584, U.S. Pat. No. 5,104,646, and U.S. Pat. No. 5,106,609, which are incorporated herein by reference.
  • the silicone conditioning agents for use in the composition may have a viscosity, as measured at 25 A° C, from about 20 to about 2,000,000 centistokes ("csk”), alternatively from about 1,000 to about 1,800,000 csk, alternatively from about 50,000 to about 1,500,000 csk, and alternatively from about 100,000 to about 1,500,000 csk.
  • csk centistokes
  • the dispersed silicone conditioning agent particles typically have a volume average particle diameter ranging from about 0.01 micrometer to about 50 micrometer.
  • the volume average particle diameters typically range from about 0.01 micrometer to about 4 micrometer, alternatively from about 0.01 micrometer to about 2 micrometer, and alternatively from about 0.01 micrometer to about 0.5 micrometer.
  • the volume average particle diameters typically range from about 5 micrometer to about 125 micrometer, alternatively from about 10 micrometer to about 90 micrometer, alternatively from about 15 micrometer to about 70 micrometer, and alternatively from about 20 micrometer to about 50 micrometer.
  • Silicone fluids include silicone oils, which are flowable silicone materials having a viscosity, as measured at 25° C, less than 1,000,000 csk, alternatively from about 5 csk to about 1,000,000 csk, and alternatively from about 100 csk to about 600,000 csk.
  • Suitable silicone oils for use in the hair care composition include polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, polyether siloxane copolymers, and mixtures thereof.
  • Other insoluble, non-volatile silicone fluids having hair conditioning properties may also be used.
  • Silicone oils include polyalkyl or polyaryl siloxanes which conform to the following Formula (I):
  • R is aliphatic, in some embodiments alkyl, alkenyl, or aryl, R can be substituted or unsubstituted, and x is an integer from 1 to about 8,000.
  • Suitable R groups for use in the compositions include, but are not limited to: alkoxy, aryloxy, alkaryl, arylalkyl, arylalkenyl, alkamino, and ether- substituted, hydroxyl-substituted, and halogen-substituted aliphatic and aryl groups.
  • Suitable R groups also include cationic amines and quaternary ammonium groups.
  • Possible alkyl and alkenyl substituents include Ci to C5 alkyls and alkenyls, alternativelyfrom Ci to C 4 , and alternatively from Ci to C 2 .
  • the aliphatic portions of other alkyl-, alkenyl-, or alkynyl-containing groups can be straight or branched chains, and may be from Ci to C5, alternatively from Ci to C 4 , alternatively from Ci to C3, and alternatively from Ci to C 2 .
  • the R substituents can also contain amino functionalities (e.g. alkamino groups), which can be primary, secondary or tertiary amines or quaternary ammonium. These include mono-, di-and tri-alkylamino and alkoxyamino groups, wherein the aliphatic portion chain protrusion length may be as described herein,
  • Cationic silicone fluids suitable for use in the composition include, but are not limited to, those which conform to the general formula (II):
  • R 1 is a G 3 -a-Si-(-OSiG 2 ) n -(-OSiG b (R 1 ) 2 _ b)m -0-SiG 3 -a (R ] ) a
  • G is hydrogen, phenyl, hydroxy, or CrC 8 alkyl, in some embodiments, methyl; a is 0 or an integer having a value from 1 to 3; b is 0 or 1; n is a number from 0 to 1,999, alternatively from 49 to 499; m is an integer from 1 to 2,000, alternatively from 1 to 10; the sum of n and m is a number from 1 to 2,000, alternatively from 50 to 500; R 1 is a monovalent radical conforming to the general formula CqH 2q L, wherein q is an integer having a value from 2 to 8 and L is selected from the following groups:
  • R is hydrogen, phenyl, benzyl, or a saturated hydrocarbon radical, in some embodiments an alkyl radical from about Q to about C 2 o, and A " is a halide ion.
  • the cationic silicone corresponding to formula (II) is the polymer known as "trimethylsilylamodimethicone", which is shown below in formula (III):
  • silicone cationic polymers which may be used in the composition are represented by the general formula (IV):
  • R 3 is a monovalent hydrocarbon radical from Ci to C 18 , in some embodiments an alkyl or alkenyl radical, such as methyl;
  • R 4 is a hydrocarbon radical, in some embodiments a Ci to C 18 alkylene radical or a C 10 to C 18 alkyleneoxy radical, alternatively a Ci to Cs alkyleneoxy radical;
  • Q " is a halide ion, in some embodiments chloride;
  • r is an average statistical value from 2 to 20, in some embodiments from 2 to 8;
  • s is an average statistical value from 20 to 200, in some embodiments from 20 to 50.
  • UCARE SILICONE ALE 56® available from Union Carbide
  • silicone fluids suitable for use in the composition may be insoluble silicone gums.
  • These gums are polyorganosiloxane materials having a viscosity, as measured at 25° C, of greater than or equal to 1,000,000 csk. Silicone gums are described in U.S. Pat. No. 4,152,416; Noll and Walter, Chemistry and Technology of Silicones, New York: Academic Press (1968); and in General Electric Silicone Rubber Product Data Sheets SE 30, SE 33, SE 54 and SE 76, all of which are incorporated herein by reference.
  • silicone gums for use in the hair care include polydimethylsiloxane, (polydimethylsiloxane)(methylvinylsiloxane)copolymer, poly(dimethylsiloxane)(diphenyl siloxane)(methylvinylsiloxane)copolymer and mixtures thereof.
  • non- volatile, insoluble silicone fluid conditioning agents that are suitable for use in the hair care composition are those known as "high refractive index silicones," having a refractive index of at least about 1.46, altemativelyy at least about 1.48, alternatively at least about 1.52, and alternatively at least about 1.55.
  • the refractive index of the polysiloxane fluid will generally be less than about 1.70, typically less than about 1.60.
  • polysiloxane "fluid” includes oils as well as gums.
  • the high refractive index polysiloxane fluid includes those represented by general Formula (I) above, as well as cyclic polysiloxanes such as those represented by Formula (V) below:
  • R is as defined above, and n is a number from about 3 to about 7, alternatively from about 3 to about 5.
  • the high refractive index polysiloxane fluids contain an amount of aryl-containing R substituents sufficient to increase the refractive index to the desired level, which is described herein. Additionally, R and n may be selected so that the material is non- volatile.
  • Aryl-containing substituents include those which contain alicyclic and heterocyclic five and six member aryl rings and those which contain fused five or six member rings. The aryl rings themselves can be substituted or unsubstituted.
  • the high refractive index polysiloxane fluids will have a degree of aryl- containing substituents of at least about 15%, alternatively at least about 20%, alternatively at least about 25%, alternatively at least about 35%, and alternatively at least about 50%.
  • the degree of aryl substitution will be less than about 90%, more generally less than about 85%, alternativelyfrom about 55% to about 80%.
  • the high refractive index polysiloxane fluids have a combination of phenyl or phenyl derivative substituents, with alkyl substituents, in some embodiments CrC 4 alkyl, hydroxy, or CrC 4 alkylamino (especially— R 4 NHR 5 NH2 wherein each R 4 and R 5 independently is a C1-C3 alkyl, alkenyl, and/or alkoxy).
  • high refractive index silicones When used in the composition, they may be used in composition with a spreading agent, such as a silicone resin or a surfactant, to reduce the surface tension by a sufficient amount to enhance spreading and thereby enhance the glossiness (subsequent to drying) of hair treated with the compositions.
  • a spreading agent such as a silicone resin or a surfactant
  • Silicone fluids suitable for use in the composition are disclosed in U.S. Pat. No. 2,826,551, U.S. Pat. No. 3,964,500, U.S. Pat. No. 4,364,837, British Pat. No. 849,433, and Silicon Compounds, Petrarch Systems, Inc. (1984), all of which are incorporated herein by reference.
  • Silicone resins may be included in composition. These resins are highly cross-linked polymeric siloxane systems. The cross-linking is introduced through the incorporation of trifunctional and tetrafunctional silanes with monofunctional or difunctional, or both, silanes during manufacture of the silicone resin.
  • Silicone materials and silicone resins in particular, can conveniently be identified according to a shorthand nomenclature system known to those of ordinary skill in the art as "MDTQ" nomenclature. Under this system, the silicone is described according to presence of various siloxane monomer units which make up the silicone. Briefly, the symbol M denotes the monofunctional unit (CT ⁇ SiOos; D denotes the difunctional unit (CH 3 )2SiO; T denotes the trifunctional unit (CT ⁇ SiOi . s; and Q denotes the quadra-or tetra-functional unit Si0 2 . Primes of the unit symbols (e.g.
  • Silicone resins for use in the composition may include, but are not limited to MQ, MT, MTQ, MDT and MDTQ resins. Methyl is a possible silicone substituent.
  • silicone resins are MQ resins, wherein the M:Q ratio is from about 0.5:1.0 to about 1.5:1.0 and the average molecular weight of the silicone resin is from about 1000 to about 10,000.
  • the weight ratio of the non- volatile silicone fluid, having refractive index below 1.46, to the silicone resin component, when used, may be from about 4:1 to about 400:1, alternatively from about 9:1 to about 200:1, and alternatively from about 19:1 to about 100: 1, particularly when the silicone fluid component is a polydimethylsiloxane fluid or a mixture of polydimethylsiloxane fluid and polydimethylsiloxane gum as described herein.
  • the silicone resin forms a part of the same phase in the compositions hereof as the silicone fluid, i.e. the conditioning active, the sum of the fluid and resin should be included in determining the level of silicone conditioning agent in the composition.
  • the conditioning agent of the composition may also comprise at least one organic conditioning oil, either alone or in combination with other conditioning agents, such as the silicones described above.
  • Suitable organic conditioning oils for use as conditioning agents in the composition may include, but are not limited to, hydrocarbon oils having at least about 10 carbon atoms, such as cyclic hydrocarbons, straight chain aliphatic hydrocarbons (saturated or unsaturated), and branched chain aliphatic hydrocarbons (saturated or unsaturated), including polymers and mixtures thereof.
  • Hydrocarbon oils may be from about C12 to about C19.
  • Branched chain hydrocarbon oils, including hydrocarbon polymers typically will contain more than 19 carbon atoms.
  • Organic conditioning oils for use in the composition may also include liquid polyolefins, alternatively liquid poly- a-olef ins, alternatively hydrogenated liquid poly- a-olef ins.
  • Polyolefins for use herein are prepared by polymerization of C 4 to about Ci 4 olefenic monomers, in some embodiments from about C 6 to about C12.
  • Suitable organic conditioning oils for use as the conditioning agent in the composition may include fatty esters having at least 10 carbon atoms. These fatty esters include esters with hydrocarbyl chains derived from fatty acids or alcohols. The hydrocarbyl radicals of the fatty esters hereof may include or have covalently bonded thereto other compatible functionalities, such as amides and alkoxy moieties (e.g., ethoxy or ether linkages, etc.).
  • Fluorinated compounds suitable for delivering conditioning to hair or skin as organic conditioning oils include perfluoropoly ethers, perfluorinated olefins, fluorine based specialty polymers that may be in a fluid or elastomer form similar to the silicone fluids previously described, and perfluorinated dimethicones.
  • suitable organic conditioning oils for use in the composition may include, but are not limited to, fatty alcohols having at least about 10 carbon atoms, alternativelyfrom about 10 to about 22 carbon atoms, and alternatively from about 12 to about 16 carbon atoms.
  • Suitable organic conditioning oils for use in the composition may include, but are not limited to, alkyl glucosides and alkyl glucoside derivatives.
  • suitable alkyl glucosides and alkyl glucoside derivatives include Glucam E-10, Glucam E-20, Glucam P-10, and Glucquat 125 commercially available from Amerchol.
  • Suitable quaternary ammonium compounds for use as conditioning agents in the composition may include, but are not limited to, hydrophilic quaternary ammonium compounds with a long chain substituent having a carbonyl moiety, like an amide moiety, or a phosphate ester moiety or a similar hydrophilic moiety.
  • hydrophilic quaternary ammonium compounds include, but are not limited to, compounds designated in the CTFA Cosmetic Dictionary as ricinoleamidopropyl trimonium chloride, ricinoleamido trimonium ethylsulfate, hydroxy stearamidopropyl trimoniummethylsulfate and hydroxy stearamidopropyl trimonium chloride, or combinations thereof.
  • conditioning agents include polyethylene glycols and polypropylene glycols having a molecular weight of up to about 2,000,000 such as those with CTFA names PEG-200, PEG-400, PEG-600, PEG-1000, PEG-2M, PEG-7M, PEG-14M, PEG-45M and mixtures thereof.
  • the cationic deposition polymer may be included in the composition at a level from about 0.01 wt to about 2 wt , in one embodiment from about 1.5 wt to about 1.9 wt , in another embodiment from about 1.8 wt to about 2.0 wt , in view of providing the benefits of the composition.
  • the cationic deposition polymer may be a water soluble polymer with a charge density from about 0.5 milliequivalents per gram to about 12 milliequivalents per gram.
  • the cationic deposition polymer used in the composition may have a molecular weight of about 100,000 Daltons to about 5,000,000 Daltons.
  • the cationic deposition polymer may be a low charge density cationic polymer.
  • the cationic deposition polymer is a synthetic cationic deposition polymer.
  • a variety of synthetic cationic deposition polymers can be used including mono- and di-alkyl chain cationic surfactants.
  • mono-alkyl chain cationic surfactants are chosen including, for example, mono-alkyl quaternary ammonium salts and mono-alkyl amines.
  • di-alkyl chain cationic surfactants include, for example, dialkyl (14-18) dimethyl ammonium chloride, ditallow alkyl dimethyl ammonium chloride, dihydrogenated tallow alkyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, dicetyl dimethyl ammonium chloride, and mixtures thereof.
  • the cationic deposition polymer is a naturally derived cationic polymer.
  • naturally derived cationic polymer refers to cationic deposition polymers which are obtained from natural sources.
  • the natural sources may be polysaccharide polymers. Therefore, the naturally derived cationic polymer may be selected from the group comprising starches, guar, cellulose, Cassia, locust bean, Konjac, Tara, galactomannan, tapioca, and synthetic polymers.
  • cationic deposition polymers are selected from Mirapol® 100S (Rhodia), Jaguar® C17, polyDADMAC, Tapioca starch (Akzo), TriquatTM, and mixtures thereof.
  • Anionic Emulsifiers are selected from Mirapol® 100S (Rhodia), Jaguar® C17, polyDADMAC, Tapioca starch (Akzo), TriquatTM, and mixtures thereof.
  • anionic emulsifiers can be used in the composition as described below.
  • the anionic emulsifiers include, by way of illustrating and not limitation, water-soluble salts of alkyl sulfates, alkyl ether sulfates, alkyl isothionates, alkyl carboxylates, alkyl sulfosuccinates, alkyl succinamates, alkyl sulfate salts such as sodium dodecyl sulfate, alkyl sarcosinates, alkyl derivatives of protein hydrolyzates, acyl aspartates, alkyl or alkyl ether or alkylaryl ether phosphate esters, sodium dodecyl sulphate, phospholipids or lecithin, or soaps, sodium, potassium or ammonium stearate, oleate or palmitate, alkylarylsulfonic acid salts such as sodium dodecylbenzenesulfonate, sodium
  • anionic emulsifiers that have acrylate functionality may also be used in the composition.
  • Anionic emulsifiers useful herein include, but aren't limited to: poly (me th) acrylic acid; copolymers of (meth)acrylic acids and its (meth)acrylates with Cl-22 alkyl, C1-C8 alkyl, butyl; copolymers of (meth)acrylic acids and (meth)acrylamide; Carboxyvinylpolymer; acrylate copolymers such as Acrylate/ClO-30 alkyl acrylate crosspolymer, Acrylic acid/vinyl ester copolymer/Acrylates/Vinyl Isodecanoate crosspolymer, Acrylates/Palmeth-25 Acrylate copolymer, Acrylate/Steareth-20 Itaconate copolymer, and Acrylate/Celeth-20 Itaconate copolymer; Polystyrene sulphonate, copoly
  • Neutralizing agents may be included to neutralize the anionic emulsifiers herein.
  • neutralizing agents include sodium hydroxide, potassium hydroxide, ammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine, diisopropanolamine, aminomethylpropanol, tromethamine, tetrahydroxypropyl ethylenediamine, and mixtures thereof.
  • anionic emulsifiers include, for example, Carbomer supplied from Noveon under the tradename Carbopol 981 and Carbopol 980; Acrylates/ClO-30 Alkyl Acrylate Crosspolymer having tradenames Pemulen TR-1, Pemulen TR-2, Carbopol 1342, Carbopol 1382, and Carbopol ETD 2020, all available from Noveon; sodium carboxymethylcellulose supplied from Hercules as CMC series; and Acrylate copolymer having a tradename Capigel supplied from Seppic.
  • anionic emulsifiers are carboxymethylcelluloses.
  • the composition further comprises one or more additional benefit agents.
  • the benefit agents comprise a material selected from the group consisting of anti- dandruff agents, vitamins, lipid soluble vitamins, chelants, perfumes, brighteners, enzymes, sensates, attractants, anti-bacterial agents, dyes, pigments, bleaches, hops, caffeine, resorcinol, cleaning agents, and mixtures thereof,
  • the composition may include a vitamin B3 compound.
  • the vitamin B3 compound is niacinamide.
  • Vitamin B3 compounds may be useful for regulating skin conditions, as described in U.S. Patent No. 5,939,082.
  • the composition may comprise from about 0.1% to about 25% of a vitamin B3 compound, in another embodiment from about 0.5% to about 15% of a vitamin B3 compound, and in yet another embodiment from about 3.5% to about 7.5% of a vitamin B 3 compound.
  • vitamin B3 com ound means a one or more compounds having the formula:
  • R is - CONH2 (i.e., niacinamide), - COOH (i.e., nicotinic acid) or - CH20H (i.e., nicotinyl alcohol); derivatives thereof; mixtures thereof; and salts of any of the foregoing.
  • CONH2 i.e., niacinamide
  • COOH i.e., nicotinic acid
  • CH20H i.e., nicotinyl alcohol
  • Exemplary derivatives of the foregoing vitamin B3 compounds include nicotinic acid esters, including non-vasodilating esters of nicotinic acid (e.g, tocopherol nicotinate, myristyl nicotinate), nicotinyl amino acids, nicotinyl alcohol esters of carboxylic acids, nicotinic acid N- oxide and niacinamide N-oxide.
  • nicotinic acid esters including non-vasodilating esters of nicotinic acid (e.g, tocopherol nicotinate, myristyl nicotinate), nicotinyl amino acids, nicotinyl alcohol esters of carboxylic acids, nicotinic acid N- oxide and niacinamide N-oxide.
  • Additional exemplary derivatives of vitamin B3 compounds are set forth in U.S. Patent App. No. 11/897084, which is incorporated
  • the composition may comprise an alcohol. Alcohol may be used for faster drying and skin penetration of the composition.
  • the composition comprises from about 10 % to about 90 % alcohol, alternatively from about 15 % to about 75 % alcohol, or alternatively from about 25 % to about 50 % alcohol. Any suitable alcohol, such as ethanol, can be used.
  • Any suitable alcohol such as ethanol, can be used.
  • the composition may comprise an anti-dandruff agent, which may be an anti-dandruff active particulate.
  • anti-dandruff particulate should be physically and chemically compatible with the components of the composition, and should not otherwise unduly impair product stability, aesthetics or performance.
  • the anti-dandruff agent may be selected from the group consisting of: pyridinethione salts; azoles, such as ketoconazole, econazole, and elubiol; selenium sulphide; particulate sulfur; keratolytic agents such as salicylic acid; and mixtures thereof.
  • Pyridinethione salts may be suitable anti-dandruff active particulates.
  • the anti-dandruff active may be a l-hydroxy-2-pyridinethione salt and is in particulate form.
  • the concentration of pyridinethione anti-dandruff particulate ranges from about 0.01 wt to about 5 wt , or from about 0.1 wt to about 3 wt , or from about 0.1 wt to about 2 wt .
  • the pyridinethione salts are those formed from heavy metals such as zinc, tin, cadmium, magnesium, aluminium and zirconium, generally zinc, typically the zinc salt of l-hydroxy-2-pyridinethione (known as "zinc pyridinethione" or "ZPT"), commonly l-hydroxy-2-pyridinethione salts in platelet particle form.
  • the l-hydroxy-2- pyridinethione salts in platelet particle form have an average particle size of up to about 20 microns, or up to about 5 microns, or up to about 2.5 microns. Salts formed from other cations, such as sodium, may also be suitable.
  • the composition may further comprise one or more anti-fungal and/or anti- microbial actives.
  • the anti-microbial active is selected from the group consisting of: coal tar, sulfur, charcoal, whitfield's ointment, castellani's paint, aluminum chloride, gentian violet, octopirox (piroctone olamine), ciclopirox olamine, undecylenic acid and its metal salts, potassium permanganate, selenium sulphide, sodium thiosulfate, propylene glycol, oil of bitter orange, urea preparations, griseofulvin, 8 -hydroxy quinoline ciloquinol, thiobendazole, thiocarbamates, haloprogin, polyenes, hydroxypyridone, morpholine, benzylamine, allylamines (such as
  • the azole anti-microbials is an imidazole selected from the group consisting of: benzimidazole, benzothiazole, bifonazole, butaconazole nitrate, climbazole, clotrimazole, croconazole, eberconazole, econazole, elubiol, fenticonazole, fluconazole, flutimazole, isoconazole, ketoconazole, lanoconazole, metronidazole, miconazole, neticonazole, omoconazole, oxiconazole nitrate, sertaconazole, sulconazole nitrate, tioconazole, thiazole, and mixtures thereof, or the azole anti-microbials is a triazole selected from the group consisting of: terconazole, itraconazole, and mixtures thereof.
  • the azole anti- microbial active When present in the composition, the azole anti- microbial active may be included in an amount of from about 0.01 wt to about 5 wt , or from about 0.1 wt to about 3 wt , or from about 0.3 wt to about 2 wt .
  • the azole anti-microbial active is ketoconazole.
  • the sole anti-microbial active is ketoconazole.
  • Embodiments of the composition may also comprise a combination of anti-microbial actives.
  • the combination of anti-microbial actives is selected from the group of combinations consisting of: octopirox and zinc pyrithione, pine tar and sulfur, salicylic acid and zinc pyrithione, salicylic acid and elubiol, zinc pyrithione and elubiol, zinc pyrithione and climbasole, octopirox and climbasole, salicylic acid and octopirox, and mixtures thereof.
  • the composition comprises an effective amount of a zinc-containing layered material.
  • the composition comprises from about 0.001 wt to about 10 wt , or from about 0.01 wt to about 7 wt , or from about 0.1 wt to about 5 wt of a zinc-containing layered material, by total weight of the composition.
  • Zinc -containing layered materials may be those with crystal growth primarily occurring in two dimensions. It is conventional to describe layered structures as not only those in which all the atoms are incorporated in well-defined layers, but also those in which there are ions or molecules between the layers, called gallery ions (A.F. Wells "Structural Inorganic Chemistry” Clarendon Press, 1975).
  • Zinc-containing layered materials may have zinc incorporated in the layers and/or be components of the gallery ions.
  • the following classes of ZLMs represent relatively common examples of the general category and are not intended to be limiting as to the broader scope of materials which fit this definition.
  • the ZLM is selected from the group consisting of: hydrozincite (zinc carbonate hydroxide), aurichalcite (zinc copper carbonate hydroxide), rosasite (copper zinc carbonate hydroxide), and mixtures thereof.
  • Related minerals that are zinc-containing may also be included in the composition.
  • Natural ZLMs can also occur wherein anionic layer species such as clay-type minerals (e.g., phyllosilicates) contain ion-exchanged zinc gallery ions. All of these natural materials can also be obtained synthetically or formed in situ in a composition or during a production process.
  • the ZLM is a layered double hydroxide conforming to the formula [M 2+ 1 . x M 3+ x (OH) 2 ] x+ A m ⁇ x/m -nH 2 0 wherein some or all of the divalent ions (M 2+ ) are zinc ions (Crepaldi, EL, Pava, PC, Tronto, J, Valim, JB /. Colloid Interfac. Set 2002, 248, 429- 42).
  • ZLMs can be prepared called hydroxy double salts (Morioka, H., Tagaya, H., Karasu, M, Kadokawa, J, Chiba, K Inorg. Chem. 1999, 38, 4211-6).
  • the ZLM is a hydroxy double salt conforming to the formula [M 2+ i_ x M 2+ i +x (OH)3 ( i_ y) ] + where the two metal ions (M 2+ ) may be the same or different. If they are the same and represented by zinc, the formula simplifies to [Zni +x (OH) 2 ] 2x+ 2x A ⁇ 2 0.
  • the ZLM is zinc hydroxychloride and/or zinc hydroxynitrate. These are related to hydrozincite as well wherein a divalent anion replace the monovalent anion. These materials can also be formed in situ in a composition or in or during a production process.
  • the ratio of zinc-containing layered material to pyrithione or a polyvalent metal salt of pyrithione is from about 5: 100 to about 10: 1, or from about 2: 10 to about 5: 1, or from about 1:2 to about 3: 1.
  • the on-scalp deposition of the anti-dandruff active is at least about 1 microgram/cm 2 .
  • the on-scalp deposition of the anti-dandruff active is important in view of ensuring that the anti- dandruff active reaches the scalp where it is able to perform its function.
  • the deposition of the anti-dandruff active on the scalp is at least about 1.5 microgram/cm 2 , or at least about 2.5 microgram/cm 2 , or at least about 3 microgram/cm 2 , or at least about 4 microgram/cm 2 , or at least about 6 microgram/cm 2 , or at least about 7 microgram/cm 2 , or at least about 8 microgram/cm 2 , or at least about 8 microgram/cm 2 , or at least about 10 microgram/cm 2 .
  • the on- scalp deposition of the anti-dandruff active is measured by having the hair of individuals washed with a composition comprising an anti-dandruff active, for example a composition pursuant to the present invention, by trained a cosmetician according to a conventional washing protocol. The hair is then parted on an area of the scalp to allow an open-ended glass cylinder to be held on the surface while an aliquot of an extraction composition is added and agitated prior to recovery and analytical determination of anti-dandruff active content by conventional methodology, such as HPLC.
  • Embodiments of the composition may also comprise fatty alcohol gel networks, which have been used for years in cosmetic creams and hair conditioners. These gel networks are formed by combining fatty alcohols and surfactants in the ratio of about 1:1 to about 40:1 (alternatively from about 2:1 to about 20:1, and alternatively from about 3: 1 to about 10:1).
  • the formation of a gel network involves heating a dispersion of the fatty alcohol in water with the surfactant to a temperature above the melting point of the fatty alcohol. During the mixing process, the fatty alcohol melts, allowing the surfactant to partition into the fatty alcohol droplets. The surfactant brings water along with it into the fatty alcohol. This changes the isotropic fatty alcohol drops into liquid crystalline phase drops. When the mixture is cooled below the chain melt temperature, the liquid crystal phase is converted into a solid crystalline gel network.
  • the gel network contributes a stabilizing benefit to cosmetic creams and hair conditioners. In addition, they deliver conditioned feel benefits for hair conditioners.
  • the fatty alcohol is included in the fatty alcohol gel network at a level by weight of from about 0.05 wt to about 14 wt .
  • the fatty alcohol may be present in an amount ranging from about 1 wt to about 10 wt , and alternatively from about 6 wt to about 8 wt .
  • the fatty alcohols useful herein are those having from about 10 to about 40 carbon atoms, from about 12 to about 22 carbon atoms, from about 16 to about 22 carbon atoms, or about 16 to about 18 carbon atoms. These fatty alcohols can be straight or branched chain alcohols and can be saturated or unsaturated. Nonlimiting examples of fatty alcohols include, cetyl alcohol, stearyl alcohol, behenyl alcohol, and mixtures thereof. Mixtures of cetyl and stearyl alcohol in a ratio of from about 20:80 to about 80:20, are suitable.
  • the fatty alcohols useful herein are those having from about 10 to about 40 carbon atoms, from about 12 to about 22 carbon atoms, from about 16 to about 22 carbon atoms, or about 16 to about 18 carbon atoms. These fatty alcohols can be straight or branched chain alcohols and can be saturated or unsaturated. Nonlimiting examples of fatty alcohols include, cetyl alcohol, stearyl alcohol, behenyl alcohol, and mixtures thereof. Mixtures of cetyl and stearyl alcohol in a ratio of from about 20:80 to about 80:20, are suitable.
  • the applicator assembly 100 described above may also be used in a method for dispensing a composition.
  • the method for dispensing a composition may comprise providing the applicator assembly 100 described above, disposing a composition in the applicator assembly 100, and activating the applicator assembly 100.
  • the activating of the applicator assembly 100 may include actuating a mechanical pump, an aerosol container, or a squeeze container.
  • the method may be used for dispensing the composition from the applicator assembly directly onto the scalp.
  • the method may also be used for improving the efficacy of a composition after being delivered to the scalp.
  • the spray applicator is a common in-store applicator used for applying compositions to the scalp.
  • the single tine applicator is an embodiment of the present invention used for applying compositions to the scalp.
  • the consumers were asked to rate the scalp applicators on a scale of 1 to 10, 10 being most useful for scalp application, and 1 being most useful for hair application.
  • the mean values were then calculated and listed in Table 1. Using the Student T method at a 95% confidence level, there was a statistically significant difference in the consumers' preference for the single tine applicator for being most useful for scalp application. Table 1: Usefulness for Scalp Application
  • the spray applicator is a common in-store applicator used for applying compositions to the scalp.
  • the single tine applicator is an embodiment of the present invention used for applying compositions to the scalp.
  • the consumers were asked to rate the scalp applicators on a scale of 1 to 10, 10 being easiest to apply to the composition to the scalp, and 1 being hardest to apply the composition to the scalp.
  • the mean values were then calculated and listed in Table 2. Using the Student T method at a 95% confidence level, there was a statistically significant difference in the consumers' preference for the single tine applicator for being easiest to apply a composition to the scalp.
  • the spray applicator is a common in-store applicator used for applying compositions to the scalp.
  • 100 consumers were asked to use and rate the single tine applicator on ability to deliver product benefits.
  • the single tine applicator is an embodiment of the present invention used for applying compositions to the scalp.
  • the consumers were asked to rate the scalp applicators on a scale of 1 to 100, 100 being the most able to deliver product benefits, and 1 being least able to deliver product benefits.
  • the mean values were then calculated and listed in Table 3. Using an 85% confidence level, there was a statistically significant difference in the consumers' ratings for the single tine applicator for being most able to deliver product benefits.
  • Table 3 Delivers Product Benefits
  • the spray applicator is a common in-store applicator used for applying compositions to the scalp.
  • the single tine applicator is an embodiment of the present invention used for applying compositions to the scalp.
  • Product spread on each consumer's scalp was then quantified by using florescent formula and image analysis. The mean values are listed in Table 4. The results show that the single tine applicator delivered substantially more product to the scalp than the spray applicator - an increase in coverage of 62.9 % versus the spray applicator.
  • Table 4 Area Intensity Coverage
  • Panelists use a delivery system on their own scalp with wet hair to apply a product with a fluorescent agent (curcumin).
  • Panelists have their hair sectioned by a stylist - sectioning must be consistent over all panelists.
  • Image J The computer program Image J is used to perform analysis on all of the images, measuring the area (reported in pixels) and intensity of the fluorescent agent in that area. The value for area intensity coverage is calculated by area*intensity.

Abstract

L'invention concerne un procédé permettant d'appliquer une composition sur le cuir chevelu, comprenant (a) la mise à disposition d'une composition dans un ensemble applicateur, l'ensemble applicateur comprenant (i) un contenant destiné à contenir la composition; (ii) un actionneur à pointe allongée en communication fluidique avec le contenant, l'actionneur à pointe allongée comprenant (1) une partie base conçue pour relier de façon fluidique l'actionneur à pointe allongée au contenant; et (2) une partie corps conçue pour relier de façon fluidique la partie base à une dent creuse; et (iii) un moteur pour distribuer la composition depuis le contenant à travers l'actionneur à pointe allongée; et (b) la distribution de la composition depuis l'ensemble applicateur directement sur le cuir chevelu. La dent présente une face située de manière distale par rapport à la partie corps. La dent comprend une ouverture en communication fluidique avec le contenant. La dent a une longueur de saillie d'environ 0,5 mm à environ 100 mm.
PCT/US2013/038311 2012-04-27 2013-04-26 Ensemble applicateur pour l'application d'une composition WO2013163491A1 (fr)

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CA2870208A CA2870208A1 (fr) 2012-04-27 2013-04-26 Ensemble applicateur pour l'application d'une composition
EP13720207.3A EP2840928A1 (fr) 2012-04-27 2013-04-26 Ensemble applicateur pour l'application d'une composition
CN201380022237.3A CN104254262A (zh) 2012-04-27 2013-04-26 用于施用组合物的施用装置组件
JP2015509158A JP2015515495A (ja) 2012-04-27 2013-04-26 組成物を適用するアプリケーターアセンブリー
MX2014011551A MX2014011551A (es) 2012-04-27 2013-04-26 Unidad aplicadora para aplicar una composicion.

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US61/639,446 2012-04-27

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EP (1) EP2840928A1 (fr)
JP (2) JP2015515495A (fr)
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CA2870208A1 (fr) 2013-10-31
CN104254262A (zh) 2014-12-31
US20130284195A1 (en) 2013-10-31
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