WO2013122861A2 - Conditioning composition additive for providing immediate and long lasting benefits to keratin substrates - Google Patents

Conditioning composition additive for providing immediate and long lasting benefits to keratin substrates Download PDF

Info

Publication number
WO2013122861A2
WO2013122861A2 PCT/US2013/025531 US2013025531W WO2013122861A2 WO 2013122861 A2 WO2013122861 A2 WO 2013122861A2 US 2013025531 W US2013025531 W US 2013025531W WO 2013122861 A2 WO2013122861 A2 WO 2013122861A2
Authority
WO
WIPO (PCT)
Prior art keywords
conditioning composition
composition additive
hair
modified
additive
Prior art date
Application number
PCT/US2013/025531
Other languages
English (en)
French (fr)
Other versions
WO2013122861A3 (en
Inventor
Paquita Erazo-Majewicz
Gijsbert Kroon
Nabil Naouli
Tuttu Maria Nuutinen
Nathalie Sieverling
Original Assignee
Hercules Incorporated
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 Hercules Incorporated filed Critical Hercules Incorporated
Priority to ES13705697.4T priority Critical patent/ES2672494T3/es
Priority to KR1020147025169A priority patent/KR102041898B1/ko
Priority to BR112014019623-0A priority patent/BR112014019623B1/pt
Priority to JP2014556775A priority patent/JP6189868B2/ja
Priority to IN6546DEN2014 priority patent/IN2014DN06546A/en
Priority to MX2014009704A priority patent/MX345955B/es
Priority to EP13705697.4A priority patent/EP2814575B1/en
Priority to RU2014137019A priority patent/RU2623909C2/ru
Priority to CN201380019742.2A priority patent/CN104487139B/zh
Publication of WO2013122861A2 publication Critical patent/WO2013122861A2/en
Publication of WO2013122861A3 publication Critical patent/WO2013122861A3/en

Links

Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73Polysaccharides
    • A61K8/731Cellulose; Quaternized cellulose derivatives
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00Medicinal preparations containing organic active ingredients
    • A61K31/74Synthetic polymeric materials
    • A61K31/785Polymers containing nitrogen
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8158Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/12Preparations containing hair conditioners
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/54Polymers characterized by specific structures/properties
    • A61K2800/542Polymers characterized by specific structures/properties characterized by the charge
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52Amides or imides
    • C08F220/54Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56Acrylamide; Methacrylamide

Definitions

  • the conditioning composition additive for use on keratin substrates in order to provide immediate and long lasting benefits to the keratin substrate such as conditioning systems for hair and skin.
  • the conditioning composition additive comprises a hydrophobically modified poiyCacrylamido-N-propyltrimethylammontum chloride) and water.
  • the conditioning composition additives of the presently disclosed and claimed inventive concept(s) can provide excellent detangling properties, increased
  • the presently disclosed and claimed inventive concepts also relates to a conditioning composition containing the conditioning composition additive and a method of applying the
  • Undamaged virgin hair is smooth and shiny; its cuticles on the surface of the hair lie down smoothly making the combing easy.
  • the hair surface is also hydrophobic in nature preventing excessive water absorption during washing.
  • the hair is either mechanically or chemically damaged throug bleaching, perming or coloring, the hair surface becomes rough and frizzy, and difficult to detang!e and comb.
  • the resulting hair fibers swell during washing making the hair even more difficult to comb.
  • wet conditioning of damaged hair is accomplished by neutralizing the anionic charge of the hair by positively charged surfactants and polymers and creating a hydrophobic layer from surfactant and polymers. This hydrophobic layer results a reduction of the swelling of the hair fibers by making the hair more hydrophobic and reducing f iction of the hair fibers.
  • An overaii result of wet conditioning is improved detangiing, manageability and soft feel of the hair.
  • cleansing systems like shampoo's, 2/1 shampoo's, body washes or shower gels, the combing performance, detangiing properties, hydrophobicity of the hair and lubricity are not maintained sufficiently.
  • Silicones are traditionall used in hair care applications to provide conditioning properties such as ease of combing and detangiing, color retention, smoothness and hydrophobicity. Silicones function by forming a film on the hair surface and depending on the nature of the silicone they are either self-deposited or they require additional cationic ingredients for deposition.
  • Figure 1 is a photograph of a water droplet on the surface of a bleached Caucasian hair tress treated with a conditioning composition additive of the presently disclosed and claimed inventive coneept(s) demonstrating the hydrophobicity imparted to the hair tress by the conditioning composition additive.
  • Figure 2 is a photograph of a water droplet on the surface of a bleached Caucasian hair tress treated with a conditioning composition additive of the presently disclosed and claimed inventive conoept(s) after 5 washes with non-conditioning shampoo demonstrating the hydrophobicity imparted to the hair tress by the
  • FIG. 3 is a photograph of a water dropiet on the surface of a bleached Caucasian hair tress treated with a commercially available conditioner
  • Figure 4 is a photograph of a water droplet on the surface of a bleached Caucasian hair tress treated with a conditioning composition additive in Example 2f as a 1 wt% active in conjunction with cetearyi alcohol at 2,45 wt% and with a cafionic surfactant at 0.65 wt% with the balance being water.
  • the tress is being washed 5 times with a si!icone-free shampoo.
  • Figure 5 is an AFSV1 image of the surface of a bleached Caucasian hair tress treated with a conditioning composition additive in Example 2f and treated 5 times with following washing cycle: 0.1 grams per gram hair clarifying shampoo containing SLES/CAPB 12/2% and 0.2 grams per gram hair conditioner in Example 2f.
  • Figure 6 is a SE image of the surface of a bleached Caucasian hair tress treated with a conditioning composition additive in Example 2f as a 1 wt% active in conjunction with cetearyi alcohol at 2.45 wt% and with a caiionic surfactant at 0,65 wt% with the balance being water. After applying the conditioner the tress has been washed 5 times with 0.1 grams per gram hair clarifying shampoo SLES/CAPB 12/2%.
  • Figure 7 is a SEM image of the surface of a bleached Caucasian hair tress treated with the conditioning compositio additive in Example 2f and treated 5 times with following washing cycle: 0.1 grams per gram hair clarifying shampoo containing
  • Figure 8 is an image of light microscope of an emulsion containing 1 % polymer of Example 2d in combination with 3 % cetearyi alcohol,
  • Figure 9 is an image of light microscope of an emulsion containing 1 % polymer of Example 2c in combination with 3 % cetearyi alcohol.
  • inventive concept(s) is not limited in its application to the details of construction and the arrangement of the components set forth in the following description or illustrated in the drawings, experimentation and/or results.
  • inventive concepts is capable of other embodiments or of being practiced or carried out in various ways.
  • the language used herein is intended to be given the broadest possible scope and meaning; and the embodiments are meant to be exemplary - not exhaustive.
  • the phraseoiogy and terminology empioyed herein is tor the purpose of description and should not be regarded as limiting.
  • compositions and/or methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure, While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill In the art that variations may foe applied to the compositions and/or methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit and scope of the invention. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the inventive concept(s) as defined by the appended claims.
  • the term "about” is used to indicate that a value includes the inherent variation of error for the device, the method being employed to determine the value, and/or the variation that exists among the study subjects.
  • the use of the term “at least one” will be understood to include one as well as any quantity more than one, including but not limited to, 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 100, etc.
  • At least one may extend up to 100 or 1000 or more, depending on the term to which it is attached; in addition, the quantities of 100/1000 are not to be considered limiting, as higher limits may also produce satisfactor results, in addition, the use of the term "at least one of X, Y and 2" will be understood to include alone, Y alone,, and Z .alone, as well as any combination of X, Y and Z,
  • the presently disclosed and claimed inventive concept(s) relates to a conditioning composition additive for providing immediate and prolonged benefit to a keratin surface.
  • the conditioning composition additive comprises a hydrophoblcaily modified poly(acryiamido ⁇ --propySii1methylammoniurn chloride) ⁇ polyAPTAC), and solvent.
  • the solvent comprises water.
  • hydrophobic ally modified po!yAPTAC can be present in an amount of from about 0.1 wt % to about 20 wt% of the total weight of the conditioning composition additive.
  • the hydrophobicaiiy modified polyAPTAC solutions wit relatively low concentrations ( ⁇ 10 wt ) can provide immediate and prolonged benefits to keratin surfaces in terms of conditioning or colour retention after washing with a cleansing product like shampoo, !n one non-limiting embodiment, the concentration of the hydrophobically modified poiyAPTAC in water may be about 1.0 wt%.
  • Typical concentration of polyAPTAC polymer in solutions as the conditioning composition additive are around 1 wf%, which can be adjusted from about 0.1 wt.% up to about 10 wt% depending on the viscosit of a final solution, in one non-limiting embodiment, the hydrophobicaiiy modified poiyAPTAC can be present in an amount of from about 0,25 wt. % to about 5 wt% of the total weight of the conditioning composition additive.
  • the conditioning composition additive can be applied to hair in a range of about 0.01 - 0.5 gram of hydrophobically modified polyAPTAC solution as an additive per grarn of hair. This is similar to the application of conditioners, which can be leave on (typical application dosage ⁇ 0.2 gram per gram hair) or rinse off ⁇ typical application dosage G.1 gram / gram of hair).
  • the hydrophobically modified polyAPTAC described in this presently disclosed and claimed inventive concept(s) are wafer soluble.
  • the hydrophobicaiiy modified polyAPTAC in the conditioning composition additive can have a cationic charge density of about 1 to about 8 meq/g.
  • the hydrophobielly modified poiyAPTAC has a cationic charge density in the range of from about 3 to about 7 moq/g. in ⁇ another non-limiting embodiment, the hydrophobically modified poiyAPTAC has a cationic charge density in the range of about 4 to about 6 meq/g.
  • the hydrophobically modified poiyAPTAC can be made by polymerizing acrylamido-N-propyftrimefhylaiTsrnonium chloride (APTAC) with at least one hydrophobic co-monomer.
  • the hydrophobic co-monomers can be added at different amounts to provide various levels of hydrophobieity to the hydrophobicaiiy modified polyAPTAC.
  • the hydrophobic co-monomer can be any ethylenicaliy unsaturated monomer.
  • co- monomers in the presently disclosed and claimed inventive eoneept(s) may be seiected from the group consisting of sodium acrylate, acrylic acid, alkyl acrylate, alkyl methacyria!e, alkyl ethoxylate (meth)acrylate, ethylene glycol behenyl ether
  • the a!ky acrylate ca be stearyl acrylate.
  • Th hydrophobic co-monomer comprises about 1,5 to about 15 percents by weight based on the total weight of the hydrophobicaiiy modified polyAPTAC,
  • the molecular weight of polymers in this presently disclosed and claimed inventive concepts can be determined by using standard analytical measurements, such as size exclusion chromatography (SEC), in one non-limiting embodiment, the hydrophobicaliy modified poiyAPTAC has a molecular weight in the range of from about 100,000 to about 1,000,000 g/mo!. in another non-limiting embodiment, the
  • hydrophobieaiiy modified poiyAPTAC has a molecular weight in the range of from about 200,000 to about 500,000 g/moi
  • the hydrophobicaliy modified poiyAPTAC in the conditioning composition additive can be produced by using any kind of radical polymerization reaction such as solution, emulsion, bulk and precipitation polymerization process.
  • radical polymerization reaction such as solution, emulsion, bulk and precipitation polymerization process.
  • additional monomers can be added in the polymerization-
  • the additional monomers can be selected from the group consisting of cationic, anionic,, amphoteric and zwitterionjc monomers.
  • the hydrophobicaliy modified poiyAPTAC can form copolymers with vinyl monomers, such as vinyl pyrroiidone (VP), aorylate, acrylamide, and vinyiaicohoi.
  • the hydrophobicaliy poiyAPTAC can also be combined with any other polymers, : such as anionic, cationic, non-ionic, amphoteric or zwitterionic polymers.
  • the hydrophobicaliy modified poiyAPTAC in the presently disclosed and claimed inventive concept(s) may be combined with a substantive polymer, for example, but by no way of limitation, a polymer based on a celSulosic or galactomannan backbone.
  • the substantive polymer may be used in combination with the hydrophobicaliy modified poiyAPTAC to stabilize the emulsions and acting as a rheoiogy modifier.
  • the substantive polymers can be cationic polysaccharides based on hydroxyefhyl cellulose or galactomannan.
  • the substantive polymers can be a hydrophobieaiiy modified hydroxyethylcellulose.
  • the hydrophobieaiiy modified hydroxyethy!celiu!ose can be in the range of about 0.1 wt . % to about 20 wt%.
  • the hydrophobieaiiy modified hydroxyethy!celiu!ose can be in the range of about 0.1 wt . % to about 20 wt%.
  • the substantive polymers can be a hydrophobieaiiy modified hydroxyethylcellulose.
  • the hydrophobieaiiy modified hydroxyethy!celiu!ose can be in the range of about 0.1 wt . % to about 20 wt%.
  • the hydrophobieaiiy modified hydroxyethy!celiu!ose can be in the range of about 0.1 wt . % to about 20 wt%.
  • hydrophobieaiiy modified hydroxyeihyioel!uiose can be in the range of about 1 wt% to about 5 wt%.
  • the hydrophobicaliy modified poiyAPTAC can be delivered as a polymer solution or in combination with a fatty alcohol.
  • This conditioning composition additive can show excellent conditioning performance as leave-on and, especially, as rinse -off conditioner.
  • the hydrophobicaliy modified poiyAPTAC shows improved conditioning performance over cationic surfactants.
  • the hydrophobicaliy modified poiyAPTAC solutions on their own can provide these benefits, without the heed to add cationic surfactants, amphoteric surfactants, fatty alcohols, silicones, proteins, etc..
  • the presently disclosed and claimed inventive concepts also relates to a conditioning composition comprising the conditioning composition additive for providing immediate and prolonged benefit to a keratin surface and a personal care active ingredient,
  • the conditioning composition additive of the presently disclosed and claimed inventive .concept (s) when incorporated into a conditioning composition provides immediate and long lasting performance
  • the benefits which may be extended using the conditioning composition additive include conditioning, detangling, hydrophobscity, improved sensory properties and colo lasting after multiple washes with cleansing systems like shampoos, conditioning shampoos, shower geis, etc and with styling applications
  • the benefits, which may be extended using the conditioning composition additive include, moisturizing, bydrophobieity or waterproofing, UVA and or UVB protection,
  • the conditioning composition additive is combined with a personal care active ingredient to provide a benefit to the formulation. Due to the cationic nature of the additive, it can be used to deposit other ingredients to the hair and the skin. Examples of other ingredients can include, but are limited to. silicones, emollients, and fragrances, oil-soluble active ingredients such as vitamins, antioxidants and UV-filters,
  • Examples of the cationic surfactants mentioned in the presently disclosed and claimed inventive conceptfs) can be, but are not limited to,, cetrimonium chloride, behentrimonium chloride and stearamidopropyl dimethylamine,
  • the presently disclosed and claimed inventive concept(s) also relates to a method for providing immediate and prolonged benefit to a keratin surface.
  • the method comprises applying a conditioning composition to the keratin surface.
  • the conditioning composition comprises a conditioning composition additive and a personal care active ingredient,
  • the conditioning composition additive and the persona! care active ingredient are the same as those described previously.
  • a Mutek charge analyzer was used to determine the cattonic charges of polymers.
  • the aqueous sample was placed in the measuring cell. Once the PCD was turned on, th piston of the ceil oscillated and caused a high flow rate, Any charged material adsorbed to the cell wail was separated from its counter-ions by the. flow to create a streaming current. Two electrodes In the cell picked up this current and displayed it.
  • the titration module automatically selected the titrant which was charged oppositely to the sample (cationic sample - anionic titrant) and added it to the sample until 0 mV was reached. As a result the consumption of titrant in ml was indicated on the display as well as the charge demand in meq/g.
  • a portion of the hair tress was stretched on a speciaily designed plate so that the fibers were suspended together in space to form a "single" surface.
  • a droplet of deionized water was delivered from a syringe onto the fiber surface.
  • the monomers and co-monomers were polymerized in an aqueous media by a discontinuous process.
  • the polymerization was an adiabatic reaction.
  • Example 1a contained a cationic polymer in combination with cationic surfactants.
  • Example 1 contained only cationic surfactants. From Table 1 above, it is evident that both of the examples have good initial conditioning properties, but if is also evident that, cationic surfactants don't provide long-lasting conditioning,
  • the poiyAPTAC homopolymers were tested as 1 wi% in 2.45% fatty alcohol and 0.6.5% cationic surfactants.
  • a reference having 2,45% fatty alcohol and 0.65% cationic surfactant was used.
  • the conditioner was applied on damaged hair (0.2 grams per gram of bleached hair, 1 hour bleached) and wet comb energies were measured with Instron after the rinse with water and after 1 , 3 and 5 times of washing with 0,1 grams pe gram hair shampoo ⁇ shampoo: 12/2 SLES/CAPB), The test results are provided in Table 3:
  • Example 2f was poiyAPTAC with a cationic charge of 4.8 meq/g and Mw 500,000 Dalton, Even at very low dosages it is resulting superior comb energy results compared to the fully formulated, silicone-containtng conditioner.
  • Example 2d and 2f were compared to Example 1 d (Comparative) containing 1% Polyquatemium-55, 0.65% cationic surfactant and 2.45% fatty alcohol.
  • Poiyquaternium-55 was an example of a cationic polymer.
  • the conditioners were applied on damaged hair 0.2 grams per gram of bleached hair (1 hour bleached) and wet comb energies were measured after 1 , 3 and 5 times of washing with 0.1 grams per gram hair shampoo (shampoo : 12/2 SLES/CAPB), Table 5
  • the polyAPTAC homopoiymer can also be used in combination with cationjc surfactants, but it has been surprisingly found that the comb energy values without additional cationjc surfactant are even lower.
  • Example 2f was compared to the formulation containing Example 8a of 1 % polyAPTAC homopoiymer with w 500,000 Daiton and 3% fatty alcohol.
  • the improved performance after multiple washes of the conditioning systems containing the polyAPTAC homopoiymer is also of value for preventing color fading in hair colors.
  • Hair tresses were treated with a red color known for its fading issue.
  • the hair color used was a permanent color from L'Oreai Garnier Nutrisse Crerne level 3. The process used was as follows;
  • Example 2f does indeed demonstrate substantial improvement in coior retention after multiple washes for this color system when compared to a commercial conditioner developed especially for color protection purposes.
  • Example 2f does indeed demonstrate substantial improvement in color retention afte multiple washes for this color system when compared to a hair without condiiioner treatment and a conditioner included in the dye package.
  • Table 8 When comparing the results of Table 8 with Table 7 it can be seen that the method of application ' had an influence on the results.
  • the conditioner was applied before shampooing, the total color retention after multiple washes was improved.
  • polyAPTAC homopoiymer of Example 2f was used by 1 wt.% active with water added to 100%.
  • a simple polymer solution comprising the polyAPTAC
  • FIGS 1 and 2 are photographs of a water droplet on the surface of the hair tress treated with the polymer solution of Example 2f.
  • Figure 2 presents a tress which was washed 5 times with siiicone-free shampoo after applying the polymer solution onto the tress. From Figures 1 and 2, it can be clearly seen that the treated hair tress is very hydrophobic in nature as the water droplet on the surface of the tress exhibited a high contact angle,
  • Figure 3 is a photograph of water droplets applied to bleached Caucasian hair treated with a commercial conditioner. From Figure 3, it can be clearly seen that the hai tresses treated with a commercial conditioner did not impart the same degree of hydrophobicity as was observed in the treated hair tress of Figures 1 and 2. in the hair tresses treated with a commercial conditioner, the water droplets exhibited low contact angles with the hair tress surface and were absorbed or at least immediately spread over the tress after applying the water droplet.
  • the polyAPTAC homopolymerof Example 21 was used by 1 wt%. active in conjunction with cetearyl alcohol at 2.45 wt% and with a cationic surfactant, at 0.65 wt% with water added to 100%.
  • the -simple conditioner formula was then applied to hair at 0.2 g/g bieached Caucasian hair and rinsed off. After drying at RT it washed 5 times with a clarifying shampoo base (12 wt% St.£ : , : S, 2 wt% CAPB) and after the fifth time the hair tress was evaluated for retained hydrophobicity.
  • Figure 4 is a photograph of a water droplet on the hair tress, Figure 4 dearly demonstrates that the polyAPTAC homopolymer of Example 2f provided the treated hair tress with long lasting hydrophobicity after 5 washes with shampoo.
  • the polyAPTAC homopolymer of Example 2f was used by 1 wt% active in conjunction with cetearyl alcohol at 2.45 wt.% and with a cationic surfactant at 0.65 wt% with water added to 100%.
  • the simple conditioner formula was then applied to hair at 0,2g g bleached Caucasian hair and rinsed off. After drying at RT, it was washed 5x with 0,1 grams per gram of hair clarifying shampoo base (12 wt% SLEaS, 2 wt% CAPB) and the surface of the treated hair tress was studied by using Scanning Electron Microscopy.
  • the polyAPTAC homopolymer of Example 2f was used by 1 wt% active in conjunction with cetearyl alcohol at 2.45 wt% and with a cationic surfactant at 0,65 wt% with water added to 100%,
  • the simple conditioner formula was then applied to hair at 0.2 g/g bleached Caucasian hair and rinsed off. After drying at RT, it was treated 5 times with a washing cycle with 0.1 grams per gram of hair a clarifying shampoo base (12 wt% SLE 2 S, 2 wt% CAPB) and afterwards 0.2 grams per gram of hair and the surface of the treated hair tress was studied by using Scanning Electron Microscopy (SEM) and Atomic Fluorescence Microscopy (AF ),
  • Example 2f when used as a conditioner is able to deposit on the hair surface. A widespread filmy deposition can be clearly seen.
  • Example 2f when used as a conditioner is able to smoother) the damaged hair surface. Cuticles are aligned on the hair surface. From Figure 6 it can be seen that the effect is long-lasting. After 5 washes with clarifying shampoo the cuticles lie smoothly on the hair surface forming a homogenous layer.
  • the po!yAPTAG homopolymer of Example 2f was Used by 1 wt% active in conjunction with cetearyl alcohol at 2.45 wt% and with a cationic surfactant at 0.65 wt% with water added to 100%.
  • the simple conditioner formula was then applied io hair at 0.2 g/g medium bleached Caucasian hair and rinsed oft. After drying at RT, it was washed 5x with a clarifying shampoo base (12 wi% SLEjS, 2 wt% CAPB). The contact angle of the treated tresses was measured before the first wash and after 2 washes. The test results are given in Tab!e 12.
  • a trained panel of experts can evaluate the sensory properties of the treated hair tresses and the results are correlating with measured values e.g. comb energy values.
  • Example 2f The polymer of Example 2f was used by 1 wt% active in conjunction with cetearyl alcoho! at 2.45 wt% and with a cationic surfactant at 0.65 wt% with water added to 100%.
  • the simple conditioner formula was then applied to hair at 0.2 g/g bleached Caucasian hair and rinsed off. After drying at RT, it was treated 5 times with a washing cycle with 0.1 grams per gram of hair a clarifying shampoo base (12 wt% SLE a S. 2 wt% CAPB) and afterwards 0.2 grams per gram of hair, For every evaluation, 3 tresses were prepared. The sensory properties of the tresses were evaluated after first and fifth washing cycle. A washing cycle simu!ated a real-life situation.
  • Table 13 shows the results of the sensory evaluation of the wet tresses treated with Example 2f inse-off conditioner 0.2 g/g hair.
  • Example 2f inse-off conditioner 0.2 g/g hair.
  • siiicone-free shampoo (12 wt% SLE 2 S, 2 wt% CAPB) was used 0.1 g/g hair.
  • the tresses were given a number based on their performance.
  • a ranking of 1 was the worst and 5 was the best value.
  • Example 7a The poSyAPTAC homopolymer of Example 2f was tested at 1 wt% in 2.5 % fatty alcohol and 0,7 % cation ic surfactants.
  • the cation ic surfactants used for this Example were cetrimonium chloride (Example 7a), behentrimonium chloride (Example 7b) and sfearamidopropyl dimethylamme (Example 7c).
  • homopoiymer/surfactantconditioner composition was applied on damaged hair (0.2 grams per gram of bleached hair, 1 hour bleached) and wet comb energies ware measured with Texture Analyzer after rinse with water and after 1 , 3 and 5 times of washing with 0.1 grams per gram hair shampoo (shampoo: 12/2 SLES/CAPB).
  • the test results are provided in Table 14:
  • the polyAPTAC was hydrophobicaliy modified using different levels of hydrophobic co-monomers.
  • the levels of the hydrophobic co-monomers used in this Example were 1.5 % by weight (Example 8a), 3% by weight (Example 8b) and 5% by weight (Example 8c), Sfearyl acrylate was used as hydrophobic co-monomer in each of the polyAPTAC modified.
  • the molecular weights of these examples were 1 ,000(000 Dalton,
  • the resultant hydrophobicaiiy modified polymers were: tested as a 1 wt% in 2,45 % fatty alcohol and 0, ⁇ 5 % cationic surfactants.
  • a conditioner chassis without additional cattonic polymer was tested and compared to the conditioner samples containing the hydrophobicaiiy modified polyAPTAC. All. of the conditioner samples were, applied on damaged hair (0.2 grams per gram of bleached hair, 1 hour bleached) and the wet comb energies of the conditioned hair samples were measured with Texture Analyzer after the rinse with water and after 1 , 3 and 5 times of washing with 0.1 grams per gram hair shampoo (shampoo: 12 2 SLES/CAPB). The test results are provided in Table 15:
  • hydrophobicaiiy modified polymer results very low comb energy values showing also excellent long lasting benefits.
  • hydrophobicaiiy modified polyAPTAC using different levels Of hydrophobic co-monomers were also shown in this example.
  • Stearyl acrylate was used as hydrophobic co-monomer.
  • the levels of sfearyl acrylate used were 1.5 % by weight (Example 9a) s 3% by weight (Example 9b), 5% by weight (Example 9c) and 10% by weight (Example 9d),
  • the resultant hydrophobicaiiy modified polymers were tested as a 1 wf% in 3 % fatty alcohol.
  • a polyAPTAC homopoiymer in fatty alcohol was used. All of these polymers had molecular weights of about 500,000 Dalton.
  • a conditioner chassis without additional cationic polymer was tested and compared to the conditioner example containing the polyAPTAC homopoiymer and hydrophobicaiiy modified polyAPTAC, All of the conditioner samples were applied on damaged hair (0,2 grams per gram of bleached hair, 1 hour bleached) and the wet comb energies of the conditioned hair samples were measured with Texture Analyzer after the rinse with water and after 1, 3 and 5 times of washing with 0,1 grams per gram hair shampoo (shampoo: 12/2 SLES/CAPB). The test results are provided in Table 16:
  • hydrophobtcaily modified polymer results very low comb energy values showing also excellent long lasting benefits. It is also evident that hydrophobic modification is reducing the initial wet comb energy values compared to the homopoiymer. The higher the level of hydrophobic modification is, the lower the initial wet comb energy values are, [0099] ⁇ -18 Behenyl Methacryiate (BEM) was used as a hydrophobic co-monomer as levels 2.5% by weight (Example 9e), 5% by weight (Example 9f) and 10% by weight (Example g). The resultant hydrophobiqaliy modified polymers were tested as a 1 wt% in 2.45 % fatty alcohol 0.65 wt% eationic surfactant. As a reference, a polyAPTAC homopoiymer was tested as 1 wt% in 2.45% fatty alcohol and 0.65 t% cationic surfactant All of these polymers had molecular weights of about 500,000 Daiton.
  • a conditioner chassis without additional cationic polymer was tested and compared to the conditioner examples containing the polyAPTAC homopoiymer and the hydrophobicaSly modified polyAPTAC.
  • Ail of the conditioner samples were applied on damaged hair (0.2 grams per gram of bleached hair, 1 hour bleached) and the wet comb energies of the conditioned hair samples were measured with Texture Analyzer after the rinse with water and after 1, 3 and 5 times of washing with 0.1 grams per gram hair shampoo (shampoo: 12/2 SLES/CAPB), The test results are provided in Table 7; Table 17
  • hydrophobica!ly modified polymer results very low comb energy values showing also excellent long lasting benefits. It is also evident that hydrophobic modification is reducing the initial wet comb energy values compared to the homo.pojymer. The higher the level of hydrophobic modification is, the lower the initial wet comb energy values are.
  • Table 18 shows the results demonstrating the influence of the bleaching on the contact angle.
  • hydrophobica!ly modified polyAPTAC of Examples 9a - 9d were used by 1 wt% active in conjunction with cetearyl alcohol at 3 wt% and with water added to 100%.
  • a polyAPTAC homopoiymer (MW 500,000) was used as a reference.
  • the simple conditioner formula was then applied to hair at 0,2 g/g medium bleached Caucasian hair and rinsed off. The test results are given in Table 19.
  • the hydrophobically modified polyAPTAC polymer of Example 8a was used by 1 wt% active in conjunction with cetearyl alcohol at 2.45 wt% and with a cationic surfactant at 0,65 wt% with water added to 100 wt%.
  • the simple conditioner formula was then applied to hair at 0.2 g/g medium bleached Caucasian hair and rinsed off. After drying at RT, it. was washed 2x with a clarifying shampoo base (12 wt% SLEaS, 2 wt% CAPB). The contact angle of the treated tresses was measured before the first wash and after 2 washes.
  • the formula was compared to the reference consisting of fatty aieohol in combination with eationic surfactant and to the formula containing polyAPTAC homopoiymer (MW 1 ,000,000), The test results are given in Table 20.
  • Example 8a is improving the hydrophobidty of the hair surface even after several washes with non-conditioning shampoo compared to the reference and the formula containing polyAPTAC homopoiymer.
  • Example . 11 Emulsion stabilization
  • a typscai conditioner formulation is an oll-in-water (o/w) emulsio consisting of primary emuisifier, co-emulsifier such as fatty alcohols and eationic surfactants such as cetrimonium chloride or behentnmonium chloride.
  • a polyAPTAC homopoiymer doesn't have any emulsifying properties and for that reason eationic surfactants cannot be fully replaced by polyAPTAC homopoiymer.
  • Hydrophobic modification of polyAPTAC which is presented in the Examples 9a to 9d improved the emulsion stabilization properties of the eationic polymer.
  • Figure 8 is presented typical structure of the conditioner consisting of 1 t% polyAPTAC homopoiymer ⁇ MW 1,000,000 ⁇ in combination with 3 wt% fatty aicoho!.
  • Figure 9 is presented the hydi phobically modified pQiyAPTAC of Example 9c in combination with 3 % fatty alcohol. St can be clearly seen that hydrophobic modification has improved the emulsion stabilization properties.
  • Example 9e outperforms the commercial product. The performance is even sustained after 3 washes,
PCT/US2013/025531 2012-02-13 2013-02-11 Conditioning composition additive for providing immediate and long lasting benefits to keratin substrates WO2013122861A2 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
ES13705697.4T ES2672494T3 (es) 2012-02-13 2013-02-11 Aditivo de composición acondicionadora para proporcionar beneficios inmediatos y de larga duración a sustratos de queratina
KR1020147025169A KR102041898B1 (ko) 2012-02-13 2013-02-11 케라틴 기재에 즉각적이고 장기간 유지되는 이점을 제공하기 위한 컨디셔닝 조성물 첨가제
BR112014019623-0A BR112014019623B1 (pt) 2012-02-13 2013-02-11 Composição aditiva de condicionamento para o fornecimento benefícios de longa duração e imediatos para substratos de queratina
JP2014556775A JP6189868B2 (ja) 2012-02-13 2013-02-11 ケラチン物質に即時の及び長期継続する利益を提供するためのコンディショニング組成物用添加剤
IN6546DEN2014 IN2014DN06546A (pt-PT) 2012-02-13 2013-02-11
MX2014009704A MX345955B (es) 2012-02-13 2013-02-11 Aditivo de composicion acondicionadora para proveer beneficios duraderos a los sustratos de queratina.
EP13705697.4A EP2814575B1 (en) 2012-02-13 2013-02-11 Conditioning composition additive for providing immediate and long lasting benefits to keratin substrates
RU2014137019A RU2623909C2 (ru) 2012-02-13 2013-02-11 Добавка для кондиционирующей композиции, обеспечивающая быстрые и долговременные благоприятные воздействия на кератиновые субстраты
CN201380019742.2A CN104487139B (zh) 2012-02-13 2013-02-11 用于向角蛋白基体提供即刻和长期益处的调理组合物添加剂

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201261598031P 2012-02-13 2012-02-13
US61/598,031 2012-02-13

Publications (2)

Publication Number Publication Date
WO2013122861A2 true WO2013122861A2 (en) 2013-08-22
WO2013122861A3 WO2013122861A3 (en) 2014-03-20

Family

ID=47747846

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2013/025531 WO2013122861A2 (en) 2012-02-13 2013-02-11 Conditioning composition additive for providing immediate and long lasting benefits to keratin substrates

Country Status (11)

Country Link
US (1) US20130209388A1 (pt-PT)
EP (1) EP2814575B1 (pt-PT)
JP (1) JP6189868B2 (pt-PT)
KR (1) KR102041898B1 (pt-PT)
CN (1) CN104487139B (pt-PT)
BR (1) BR112014019623B1 (pt-PT)
ES (1) ES2672494T3 (pt-PT)
IN (1) IN2014DN06546A (pt-PT)
MX (1) MX345955B (pt-PT)
RU (1) RU2623909C2 (pt-PT)
WO (1) WO2013122861A2 (pt-PT)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018007332A1 (en) 2016-07-06 2018-01-11 Unilever Plc Personal cleansing compositions
WO2018087103A1 (en) 2016-11-09 2018-05-17 Unilever Plc Hair treatment compositions comprising a homopolymer of (3-acrylamidopropyl) trimethyl ammonium chloride
WO2019115156A1 (en) 2017-12-13 2019-06-20 Beiersdorf Ag A hair cleansing composition
WO2019121428A1 (en) 2017-12-21 2019-06-27 Unilever Plc Personal cleansing compositions
WO2020254320A1 (en) 2019-06-21 2020-12-24 Unilever N.V. Personal cleansing compositions
WO2020254318A1 (en) 2019-06-21 2020-12-24 Unilever Plc Cleansing composition

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10064805B2 (en) * 2014-05-02 2018-09-04 Hercules Llc Personal care composition for a keratin substrate comprising conditioning and/or styling polymer
DE102014209720B4 (de) * 2014-05-22 2016-09-22 Henkel Ag & Co. Kgaa Verfahren zur Ermittlung der Wirksamkeit einer Haarbehandlungssubstanz sowie Haltevorrichtung zur Durchführung des Verfahrens
JP2018507242A (ja) * 2015-03-03 2018-03-15 ザ プロクター アンド ギャンブル カンパニー マイクロカプセルを含む毛髪コンディショニング組成物
EP3337444B1 (en) * 2015-08-17 2020-10-07 Hercules LLC Synergistic conditioning and/or styling compositions comprising polyquaternium-37 and polyaptac
CN109562042B (zh) 2016-03-14 2023-02-21 Isp投资有限公司 一种用于角蛋白基质的包含调理、护色和定型聚合物的个人护理组合物
US10357668B2 (en) 2016-03-31 2019-07-23 L'oreal Inhibiting color fading with layer-by-layer films
WO2017172516A1 (en) * 2016-03-31 2017-10-05 L'oreal Inhibiting color fading with layer-by-layer films
US10383810B2 (en) 2016-03-31 2019-08-20 L'oreal Inhibiting color fading with layer-by-layer films
AU2018381369B2 (en) 2017-12-06 2023-11-30 Kao Corporation Composition
CN111448348B (zh) 2017-12-06 2023-06-02 花王株式会社 布帛处理组合物
US11401350B2 (en) 2017-12-06 2022-08-02 Kao Corporation Polysaccharide derivative
CN111465733B (zh) 2017-12-06 2023-06-06 花王株式会社 去污剂
US11642301B2 (en) * 2018-12-31 2023-05-09 L'oreal Systems, kits, and methods for treating hair with compositions containing ionic polymers
JP7397136B1 (ja) * 2022-08-26 2023-12-12 大日精化工業株式会社 繊維保持具および繊維測色方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3929973A1 (de) * 1989-09-08 1991-03-14 Henkel Kgaa Haarpflegemittel
WO1994001076A1 (de) * 1992-07-03 1994-01-20 Henkel Kommanditgesellschaft Auf Aktien Haarbehandlungsmittel
EP1064927A1 (fr) * 1999-06-25 2001-01-03 L'oreal Composition cosmétique détergente comprenant une silicone et un polymère amphotère à chaines grasses et utilisation
US6489286B1 (en) * 1996-01-29 2002-12-03 Johnson & Johnson Consumer Companies, Inc. Personal cleansing compositions
WO2003101410A1 (en) * 2002-06-04 2003-12-11 The Procter & Gamble Company Conditioning shampoo composition containing select cationic conditioning polymers
DE102004045253A1 (de) * 2004-09-17 2006-04-13 Henkel Kgaa Kationische Copolymere und ihre Verwendung in haarkosmetischen Zubereitungen
EP1021471B1 (en) * 1997-03-31 2007-08-29 Calgon Corporation Ampholyte polymers for use in personal care products
US20120076747A1 (en) * 2009-07-02 2012-03-29 Hercules Incorporated Cationic synthetic polymers with improved solubility and performance in phosphate surfactant-based systems and use in personal care and household applications

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4234413A1 (de) * 1992-10-13 1994-04-14 Henkel Kgaa Haarbehandlungsmittel
JPH08505601A (ja) * 1992-09-29 1996-06-18 ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチェン 毛髪後処理製剤
US6110451A (en) * 1998-12-18 2000-08-29 Calgon Corporation Synergistic combination of cationic and ampholytic polymers for cleansing and/or conditioning keratin based substrates
DE102004017431A1 (de) * 2004-04-08 2005-10-27 Wella Ag Verwendung von N-Hydroxyalkyl-O-benzylchitosanen zur Haarbehandlung
US8796196B2 (en) * 2010-02-26 2014-08-05 Hercules Incorporated Polysaccharide products with improved performance and clarity in surfactant-based aqueous formulations and process for preparation

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3929973A1 (de) * 1989-09-08 1991-03-14 Henkel Kgaa Haarpflegemittel
WO1994001076A1 (de) * 1992-07-03 1994-01-20 Henkel Kommanditgesellschaft Auf Aktien Haarbehandlungsmittel
US6489286B1 (en) * 1996-01-29 2002-12-03 Johnson & Johnson Consumer Companies, Inc. Personal cleansing compositions
EP1021471B1 (en) * 1997-03-31 2007-08-29 Calgon Corporation Ampholyte polymers for use in personal care products
EP1064927A1 (fr) * 1999-06-25 2001-01-03 L'oreal Composition cosmétique détergente comprenant une silicone et un polymère amphotère à chaines grasses et utilisation
WO2003101410A1 (en) * 2002-06-04 2003-12-11 The Procter & Gamble Company Conditioning shampoo composition containing select cationic conditioning polymers
DE102004045253A1 (de) * 2004-09-17 2006-04-13 Henkel Kgaa Kationische Copolymere und ihre Verwendung in haarkosmetischen Zubereitungen
US20120076747A1 (en) * 2009-07-02 2012-03-29 Hercules Incorporated Cationic synthetic polymers with improved solubility and performance in phosphate surfactant-based systems and use in personal care and household applications

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018007332A1 (en) 2016-07-06 2018-01-11 Unilever Plc Personal cleansing compositions
EA036392B1 (ru) * 2016-07-06 2020-11-05 Юнилевер Н.В. Очищающие композиции для личной гигиены
US10888513B2 (en) 2016-07-06 2021-01-12 Conopeo, Inc. Personal cleansing compositions
WO2018087103A1 (en) 2016-11-09 2018-05-17 Unilever Plc Hair treatment compositions comprising a homopolymer of (3-acrylamidopropyl) trimethyl ammonium chloride
WO2019115156A1 (en) 2017-12-13 2019-06-20 Beiersdorf Ag A hair cleansing composition
WO2019121428A1 (en) 2017-12-21 2019-06-27 Unilever Plc Personal cleansing compositions
WO2020254320A1 (en) 2019-06-21 2020-12-24 Unilever N.V. Personal cleansing compositions
WO2020254318A1 (en) 2019-06-21 2020-12-24 Unilever Plc Cleansing composition

Also Published As

Publication number Publication date
KR20140131355A (ko) 2014-11-12
MX345955B (es) 2017-02-28
CN104487139A (zh) 2015-04-01
BR112014019623B1 (pt) 2019-05-07
CN104487139B (zh) 2017-02-22
IN2014DN06546A (pt-PT) 2015-06-12
KR102041898B1 (ko) 2019-11-08
BR112014019623A8 (pt) 2017-07-11
BR112014019623A2 (pt-PT) 2017-06-20
JP6189868B2 (ja) 2017-08-30
US20130209388A1 (en) 2013-08-15
RU2014137019A (ru) 2016-04-10
EP2814575A2 (en) 2014-12-24
ES2672494T3 (es) 2018-06-14
JP2015506984A (ja) 2015-03-05
EP2814575B1 (en) 2018-04-11
MX2014009704A (es) 2014-09-08
WO2013122861A3 (en) 2014-03-20
RU2623909C2 (ru) 2017-06-29

Similar Documents

Publication Publication Date Title
EP2814575A2 (en) Conditioning composition additive for providing immediate and long lasting benefits to keratin substrates
EP3235839B1 (en) Copolymer and oily gelling agent
JP5374163B2 (ja) パーソナルケア用低分子量両性ポリマ
JP5978539B2 (ja) シャンプー製剤
JP5998445B2 (ja) 毛髪化粧料
US20030161804A1 (en) Self-adhesive cationic or amphoteric free-radical polymers and cosmetic use thereof
EP2895141B1 (en) Hair care polymer
JP5804665B2 (ja) 毛髪化粧料
JP2016003185A (ja) 化粧料組成物
AU2019245317A1 (en) Hair styling compositions comprising polygalactomanans, and method for using the same
US9566231B2 (en) Aqueous hair cleansing agent
EP2039344A2 (fr) Composition cosmétique comprenant un copolymère cationique et un polymère associatif anionique et procédé de traitement cosmétique
WO2015052021A1 (en) Bodycare compositions
US10765617B2 (en) Personal care compositions comprising copolymers of cationic monomers and acryloyl lactam based monomers, process for the same and method of use
JP2002523532A (ja) カチオン性ポリマーとその使用
EP1335964A2 (en) Use of high solids solution of a cationic copolymer in personal care formulations and personal care formulations obtained therefrom
JP7446861B2 (ja) 保湿剤
JP2015040207A (ja) 低分子量両性共重合体を含む毛髪処理用組成物
MX2014012590A (es) Composicion cosmetica y agente acondicionador.
JP4894240B2 (ja) ポリマー及び化粧料組成物
AU2002224828B2 (en) Use of high solids solution of a cationic copolymer in personal care formulations and personal care formulations obtained therefrom
AU2002224828A1 (en) Use of high solids solution of a cationic copolymer in personal care formulations and personal care formulations obtained therefrom

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: 13705697

Country of ref document: EP

Kind code of ref document: A2

ENP Entry into the national phase

Ref document number: 2014556775

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: MX/A/2014/009704

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 2013705697

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 20147025169

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2014137019

Country of ref document: RU

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

Ref document number: 13705697

Country of ref document: EP

Kind code of ref document: A2

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112014019623

Country of ref document: BR

ENP Entry into the national phase

Ref document number: 112014019623

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20140808