Improved compositions and methods for hair coloring
阅读说明：本技术 用于毛发染色的改进组合物和方法 (Improved compositions and methods for hair coloring ) 是由 B·兰达 S·阿布拉莫维奇 于 2019-01-22 设计创作，主要内容包括：本文提供了用于涂覆或染色角蛋白纤维(例如人的头发)的方法、组合物和试剂盒。根据示例性实施方式,一种涂覆哺乳动物毛发的方法包括：(a)提供油相,所述油相包括至少一种反应性可缩合固化成膜的氨基硅酮预聚物,(b)在使所述油相经过预处理期间以获得预处理的油相后,将所述预处理的油相用包括水的水相乳化,从而获得预处理的水包油乳液,(c)在所述哺乳动物毛发的各毛发的外表面上施用所述预处理的水包油乳液,(d)在所述预处理的水包油乳液的所述预聚物发生部分缩合固化从而在各毛发的外表面上形成至少部分固化的氨基硅酮涂层后,任选地洗涤毛发。(Provided herein are methods, compositions, and kits for coating or dyeing keratin fibers (e.g., human hair). According to an exemplary embodiment, a method of coating mammalian hair comprises: (a) providing an oil phase comprising at least one reactive condensation curable film-forming amino silicone prepolymer, (b) after subjecting the oil phase to a pre-treatment period to obtain a pre-treated oil phase, emulsifying the pre-treated oil phase with an aqueous phase comprising water to obtain a pre-treated oil-in-water emulsion, (c) applying the pre-treated oil-in-water emulsion on the outer surface of each hair of the mammalian hair, (d) optionally washing the hair after partial condensation curing of the prepolymer of the pre-treated oil-in-water emulsion to form an at least partially cured amino silicone coating on the outer surface of each hair.)
1. A method of coating mammalian hair, the method comprising:
(A) providing an oil phase comprising at least one reactive condensation curable film-forming aminosilicone prepolymer, the oil phase satisfying at least one of:
(i) the at least one reactive condensation curable film-forming aminosilicone prepolymer includes at least one reactive condensation curable film-forming aminosilicone monomer having a molecular weight of at most 1000 g/mol;
(ii) the oil phase further comprises a non-amino crosslinker suitable for or selected for curing the prepolymer, the non-amino crosslinker having a molecular weight in the range of up to 1000 g/mol;
(iii) (iii) the oil phase according to (i) and/or (ii) further comprises at least one of a silicone oil, an amino silicone oil, a pigment dispersant or a reactive hydrophobic inorganic filler; and
wherein the oil phase comprises at least 0.01 wt.%, at least 0.05 wt.%, at least 0.1 wt.%, at least 0.15 wt.%, at least 0.2 wt.%, at least 0.25 wt.%, at least 0.5 wt.%, at least 0.75 wt.%, or at least 1 wt.% water, based on the weight of the oil phase;
(b) emulsifying the pre-treated oil phase with an aqueous phase comprising water after subjecting the oil phase to a pre-treatment period to obtain a pre-treated oil phase, thereby obtaining a pre-treated oil-in-water emulsion;
(c) applying the pre-treated oil-in-water emulsion on the outer surface of individual hairs of the mammalian hair;
(d) optionally washing the hair with a rinse solution to remove any excess of the pre-treated oil-in-water emulsion after partial condensation curing of the pre-polymer of the pre-treated oil-in-water emulsion to form an at least partially cured aminosilicone coating on the outer surface of the individual hairs;
(f) optionally, applying an aqueous dispersion comprising a plurality of polymer particles formed from a hydrophilic polymeric material having neutralized acid moieties over the at least partially cured aminosilicone coating, the plurality of polymer particles being dispersed in the aqueous dispersion, thereby producing an overlying polymer layer adhered to the exterior surface of the aminosilicone coating, and optionally washing the hair with a rinse solution to remove any excess of the aqueous dispersion.
2. A method of coating mammalian hair, the method comprising:
(A) providing an oil phase comprising at least one reactive condensation curable film-forming aminosilicone prepolymer which upon condensation curing forms a cured aminosilicone coating, the oil phase satisfying at least one of:
(i) the at least one reactive condensation curable film-forming aminosilicone prepolymer includes at least one reactive condensation curable film-forming aminosilicone monomer having a molecular weight of at most 1000 g/mol;
(ii) the oil phase further comprises a non-amino crosslinker suitable for or selected for curing the prepolymer, the non-amino crosslinker having a molecular weight in the range of up to 1000 g/mol; and
(iii) (iii) the oil phase according to (i) and/or (ii), wherein at least one of the following is a water-rich reactant: the reactive condensation curable film-forming aminosilicone prepolymer, the reactive condensation curable film-forming aminosilicone monomer, the non-amino crosslinker, or optionally any one of silicone oil, aminosilicone oil, pigment dispersant or reactive hydrophobic inorganic filler further contained therein; and
(b) pretreating the oil phase during a pretreatment period, thereby obtaining a pretreated oil phase having at least 0.01 wt.%, at least 0.05 wt.%, at least 0.1 wt.%, at least 0.15 wt.%, at least 0.2 wt.%, at least 0.25 wt.%, at least 0.5 wt.%, at least 0.75 wt.%, or at least 1 wt.% water, based on the weight of the pretreated oil phase;
(c) emulsifying the pre-treated oil phase with an aqueous phase to obtain a pre-treated oil-in-water emulsion;
(d) applying the pre-treated oil-in-water emulsion on the outer surface of individual hairs of the mammalian hair;
(e) optionally washing the hair with a rinse solution to remove any excess of the pre-treated oil-in-water emulsion after partial condensation curing of the pre-polymer of the pre-treated oil-in-water emulsion to form an at least partially cured aminosilicone coating on the outer surface of the individual hairs;
(f) optionally, applying an aqueous dispersion comprising a plurality of polymer particles formed from a hydrophilic polymeric material having neutralized acid moieties over the at least partially cured aminosilicone coating, the plurality of polymer particles being dispersed in the aqueous dispersion, thereby producing an overlying polymer layer adhered to the exterior surface of the aminosilicone coating, and optionally washing the hair with a rinse solution to remove any excess of the aqueous dispersion.
3. The method of claim 1 or 2, wherein the volume ratio of oil phase to aqueous phase in the oil phase or pre-treated oil phase, optionally without aqueous phase, is at least 9:1, at least 9.5:0.5, or at least 9.75: 0.25.
4. The method of claim 2 or 3, wherein the water-rich reactant is present and is a reactant during the pre-treatment with a pre-treatment aqueous solution so as to produce a pre-treated reactant after the incubation.
5. The method of claim 4, wherein the pre-treated reactant is a reactant during the pre-treatment incubated with an aqueous pre-treatment solution.
6. The method of claim 4 or 5, wherein the reactants being incubated are substantially dry reactants comprising, based on the weight of the reactants, less than 1% by weight water, or less than 0.5% by weight, or less than 0.1% by weight, or less than 0.05% by weight, or less than 0.01% by weight water.
7. The method of any one of claims 4 to 6, wherein the aqueous pretreatment solution is added to the pretreated reactant in an amount of 10 wt% or less, 5 wt% or less, or 1 wt% or less, based on the weight of the reactant or substantially dry reactant, and wherein the aqueous pretreatment solution is added to the pretreated reactant in an amount of at least 0.1 wt%, at least 0.2 wt%, or at least 0.3 wt%, based on the weight of the reactant or substantially dry reactant.
8. The method of any one of claims 1 to 7, wherein the pre-treated oil phase is incubated with the aqueous pre-treatment solution during the pre-treatment, and wherein the aqueous pre-treatment solution is added to the pre-treated oil phase in an amount of 2.5 wt% or less, 1.0 wt% or less, or 0.5 wt% or less by weight of the oil phase, and wherein the aqueous pre-treatment solution is added to the pre-treated oil phase in an amount of 0.01 wt% or more, 0.05 wt% or more, or 0.1 wt% or more by weight of the oil phase.
9. The method of any one of claims 4 to 8, wherein the pH of the aqueous pretreatment solution is in the range of 0.5 to 2.5, 0.5 to 2.0, 0.7 to 1.4, or 0.9 to 1.2; wherein the aqueous pretreatment solution further comprises an acid, optionally a volatile acid; wherein the acid comprises at least 30 wt.%, at least 50 wt.%, or at least 80 wt.% of the weight of the aqueous pretreatment solution; the acid is optionally present in the aqueous pretreatment solution in an amount of less than 99% by weight.
10. The method of any one of claims 1 to 9, wherein the pretreatment period is 24 hours or less, 4 hours or less, 2 hours or less, 1 hour or less, 30 minutes or less, 20 minutes or less, 10 minutes or less, or 5 minutes or less.
11. The method of any one of claims 1 to 10, wherein the pre-treatment is performed at a temperature in the range of 15 ℃ to 60 ℃, 20 ℃ to 30 ℃, or 20 ℃ to 25 ℃.
12. The method of any one of claims 4 to 7, wherein the at least one pretreated reactant is prepared from a dried reactant selected from the group consisting of: a reactive condensation curable film-forming aminosilicone prepolymer, amino and non-amino silicone oils, amino and non-amino crosslinkers suitable or selected for curing the reactive aminosilicone prepolymer, a reactive filler and a pigment dispersant.
13. The method according to any one of claims 1 to 12, wherein the first amino silicone prepolymer of the at least one reactive condensation curable film-forming amino silicone prepolymer has at least 3 silanol and/or hydrolysable groups (3+ SiOH) so as to form a three-dimensional network, wherein in the oil phase or the pre-treated oil phase a first concentration of the 3+ SiOH first amino silicone prepolymer is at least 15%, at least 20%, at least 30%, at least 40%, at least 50% or at least 60% by weight of the oil phase or the pre-treated oil phase, and wherein the first concentration is at most 95%, at most 90%, at most 85%, at most 80%, at most 75%, or at most 70% by weight of the oil phase or the pre-treated oil phase.
14. The method of any of claims 1 to 13, wherein the oil phase or the pre-treated oil phase comprises at least one of an amino silicone oil, a non-amino silicone oil, or a reactive condensation curable film-forming amino silicone prepolymer having no more than 2 silanol and/or hydrolyzable groups (2-SiOH) per molecule, the combined concentration of the one or more reactants being in the range of 1% to 65%, 3% to 40%, or 5% to 30% by weight of the oil phase or the pre-treated oil phase; and optionally allowing the viscosity of the oil phase or the pre-treated oil phase, measured at 23 ℃, to not exceed 2,000 mPa-s, not to exceed 500 mPa-s or not to exceed 100 mPa-s.
15. The method of any one of claims 1 to 14, wherein in the oil phase or the pretreated oil phase, the concentration of terminal condensation curable aminosilicone prepolymer having a single silanol or hydrolysable group (1-SiOH) is at most 5%, at most 2%, at most 1%, by weight of the oil phase or the pretreated oil phase, or wherein the oil phase is free of the terminal prepolymer.
16. The method of any of claims 1-15, wherein the concentration of non-amino crosslinker within the oil phase or the pretreated oil phase is at most 35 wt.%, at most 30 wt.%, at most 20 wt.%, at most 15 wt.%, at most 10 wt.%, or at most 5 wt.% to provide a surface Zeta potential of the oil-in-water emulsion of greater than zero, or at least +1mV, at least +2mV, at least +3mV, at least +5mV, at least +7mV, or at least +10 mV.
17. The method of any one of claims 1 to 16, wherein the total concentration of organic solvents in the oil phase or the pretreated oil phase is at most 10 wt.%, at most 5 wt.%, at most 2 wt.%, or at most 1 wt.%, based on the weight of the oil phase or the pretreated oil phase, or wherein the oil phase or the pretreated oil phase does not contain any organic solvents.
18. The process of any one of claims 1 to 17, wherein the total concentration of water-miscible co-solvents in the aqueous phase is at most 10 wt.%, at most 5 wt.%, at most 2 wt.%, or at most 1 wt.%, by weight, or wherein the aqueous phase is free of any of the co-solvents.
19. The method of any one of claims 1 to 18, wherein the oil-in-water emulsion or pre-treated oil-in-water emulsion further comprises a solid hydrophobic reactive inorganic filler disposed or dispersed in the oil phase or the pre-treated oil phase, the filler being selected or adapted to facilitate curing of the condensation curable film-forming aminosilicone prepolymer, the filler optionally being a pre-treated reactant, wherein the solid hydrophobic reactive inorganic filler comprises, consists essentially of or consists of a hydrophobic fumed silica having an average particle size (Dv50) in the range of 5 to 500nm, 5 to 250nm, 20 to 200nm, 40 to 300nm, 60 to 250nm or 60 to 200 nm; and wherein the concentration of the solid hydrophobic reactive inorganic filler disposed or dispersed in the oil phase or the pretreated oil phase ranges from 0.2 wt% to 12 wt%, from 0.2 wt% to 10 wt%, from 0.2 wt% to 8 wt%, from 0.4 wt% to 10 wt%, from 0.4 wt% to 8 wt%, from 0.6 wt% to 10 wt%, from 0.6 wt% to 8 wt%, from 0.8 wt% to 8 wt%, or from 0.8 wt% to 6 wt%, based on the weight of the oil phase; the reactive filler is optionally present in the oil-in-water emulsion or the pretreated oil-in-water emulsion in an amount ranging from 0.005 wt.% to 0.5 wt.%, 0.005 wt.% to 0.3 wt.%, based on the weight of the emulsion.
20. The method of any one of claims 1 to 19, wherein the oil-in-water emulsion or pretreated oil-in-water emulsion has a surface Zeta potential of greater than zero or at least +1mV, at least +2mV, at least +3mV, at least +5mV, at least +7mV, at least +10mV, at least +15mV, at least +20mV, at least +30mV, at least +40mV, or at least +60 mV; optionally, at most +100mV or at most +80mV, the surface Zeta potential being measured at the natural pH of the oil-in-water emulsion.
21. The method of any one of claims 1 to 20, wherein at the pH of the aqueous dispersion, the oil-in-water emulsion or pretreated oil-in-water emulsion has a first surface Zeta potential (ζ 1) and the aqueous dispersion has a second Zeta potential (ζ 2), wherein the Zeta potential difference (Δ ζ) at the pH is defined as Δ ζ ═ ζ 1- ζ 2, and wherein Δ ζ in millivolts (mV) satisfies at least one of:
(i) Δ ζ is at least 10mV, at least 15mV, at least 20mV, at least 25mV, at least 30mV, at least 40mV, or at least 50 mV;
(ii) Δ ζ is in a range of 10 to 80, 10 to 70, 10 to 60, 15 to 80, 15 to 70, 15 to 60, 20 to 80, 20 to 70, 20 to 60, 25 to 80, 25 to 70, 25 to 60, 30 to 80, 30 to 70, 30 to 60, 35 to 80, 35 to 70, or 35 to 60 mV;
(iii) the first surface Zeta potential (Zeta 1) is greater than zero (Zeta 1>0) with the pH in the range of 4 to 11, 4 to 10.5, 4 to 10, 6 to 11, 6 to 10.5, 6 to 10, 7 to 11, 7 to 10.5, or 7 to 10.
22. A method as claimed in any one of claims 1 to 21 wherein the at least one reactive condensation curable film-forming aminosilicone prepolymer comprises a reactive aminosilicone monomer having a solubility in water at 23 ℃ of less than 1%, less than 0.5% or less than 0.1% by weight.
23. The method according to any one of claims 1 to 22, wherein the at least partially cured aminosilicone coating self-terminates on an outer surface of the individual hairs.
24. The method of any one of claims 1 to 23, wherein the aqueous dispersion comprising the plurality of polymeric particles is applied onto the at least partially cured aminosilicone coating, and wherein acid moieties constitute at least 8 wt%, at least 10 wt%, at least 12 wt%, at least 15 wt%, at least 16 wt%, at least 17 wt%, at least 18 wt%, at least 19 wt%, at least 20 wt%, at least 21 wt%, or at least 22 wt% based on the weight of the hydrophilic polymeric material; and optionally, comprises at most 30 wt.%, at most 28 wt.%, at most 26 wt.%, or at most 23 wt.%, based on the weight of the hydrophilic polymeric material.
25. The method of any one of claims 1 to 24, wherein the aqueous dispersion comprising the plurality of polymer particles is applied on the at least partially cured aminosilicone coating, wherein the aqueous dispersion comprises a volatile base, optionally selected from the group of ammonia (NH3), monoethanolamine, diethanolamine, triethanolamine or morpholine, and wherein the method further comprises volatilizing the volatile base associated with the overlying pigmented polymer layer to acidify, mostly or predominantly acidify, or fully acidify the neutralized acid moieties.
26. The method of any one of claims 1 to 25, wherein the aqueous dispersion comprising the plurality of polymer particles is applied on the at least partially cured aminosilicone coating, and wherein the method further comprises converting the hydrophilic polymeric material into its conjugate acid sufficiently so as to obtain a hydrophobic polymeric material after application of the aqueous dispersion on the at least partially cured aminosilicone coating.
27. The method of any one of claims 1 to 26, wherein the aqueous dispersion comprising the plurality of polymeric particles is applied on the at least partially cured aminosilicone coating, and wherein the polymeric material having the neutralized acid moieties comprises, consists essentially of, or consists of one or more neutralized copolymers selected from the group of neutralized olefin-acrylic acid copolymers, neutralized olefin-methacrylic acid copolymers, and neutralized acrylamide/acrylate copolymers.
28. The method of any one of claims 1 to 27, wherein the aqueous dispersion comprising the plurality of polymer particles is applied on the at least partially cured aminosilicone coating, and wherein the hydrophilic polymer material is self-dispersible in water in the absence of dispersants and all other additives in water in a pH range of 7.5 to 11.
29. The method of any one of claims 1 to 28, wherein the aqueous dispersion comprising the plurality of polymer particles is applied on the at least partially cured aminosilicone coating, and wherein the hydrophilic polymeric material has a solubility of at least 2%, at least 5%, at least 10% or at least 15% by weight, or wherein the solubility is in the range of 2 to 30%, 5 to 30%, 10 to 30% or 15 to 30% by weight at pH 10.
30. The method of any one of claims 1 to 29, wherein the partial condensation curing is effected at a temperature of at most 38 ℃, at most 36 ℃, at most 34 ℃, or at most 32 ℃, and optionally at least 15 ℃.
31. The method of any of claims 1-30, wherein the washing is performed within 30 minutes, within 20 minutes, within 15 minutes, within 10 minutes, within 5 minutes, within 3 minutes, within 2 minutes, or within 1 minute after application of the pre-treated oil-in-water emulsion has been completed, and wherein the rinse liquid is (i) water, or (ii) a cationic rinse liquid containing a cationic surfactant, or (iii) a rinse liquid free of non-cationic surfactants, degreasers, and/or swelling agents capable of degreasing and swelling, respectively, the at least partially cured aminosilicone coating.
32. The method of any one of claims 1 to 31, wherein the washing is performed, and wherein after the washing, further curing occurs only or substantially only by moisture or ambient moisture.
33. The method of any of claims 1 to 32, wherein the total concentration of reactive condensation curable aminosilicone component in the oil phase or the pretreated oil phase is at least 45 wt%, at least 55 wt%, at least 60 wt%, or at least 65 wt%, and optionally in the range of 50-100 wt%, 50-95 wt%, 50-90 wt%, 50-85 wt%, 50-80 wt%, 55-95 wt%, 55-85 wt%, 60-95 wt%, 60-85 wt%, 65-95 wt%, 65-90 wt%, or 70-95 wt%, by weight on a pigment-free basis.
34. The method of any of claims 1-33, wherein the condensation-curable aminosilicone prepolymer comprises reactive groups selected from the group consisting of alkoxysilane reactive groups, silanol reactive groups, and combinations thereof.
35. The method of any one of claims 1 to 34, wherein the oil phase or the pre-treated oil phase, excluding all inorganic components and any pigments, has no glass transition temperature, and wherein the viscosity of the oil phase or the pre-treated oil phase, measured in a suitable rheometer at 23 ℃, is in the range of 2-1,000 millipascal-seconds (mPa-s), 2-500 mPa-s, 2-300 mPa-s, 2-200 mPa-s, 5-1,000 mPa-s, 5-500 mPa-s, 5-300 mPa-s, 7-500 mPa-s, 7-300 mPa-s, or 7-200 mPa-s.
36. A method as claimed in any one of claims 1 to 35 wherein the at least one reactive condensation curable film-forming aminosilicone prepolymer, optionally a pre-treated reactant, is liquid at 23 ℃.
37. The method of any one of claims 1 to 36, wherein the amine value or weight average amine value of at least one of the following is in the range of 3-1,000, 3-500, or 3-200: a) the reactive condensation curable film-forming amino silicone prepolymer, b) all of the reactive condensation curable film-forming amino silicone prepolymer, c) a pigment dispersant, and d) all of the oil phase or a pretreated oil phase.
38. The method of any one of claims 1 to 37, wherein aminosilicone oil is present in the oil phase or the pretreated oil phase, and wherein the total concentration of aminosilicone oil in the oil phase or the pretreated oil phase is at most 40 wt.%, at most 35 wt.%, at most 30 wt.%, at most 20 wt.%, at most 15 wt.%, at most 10 wt.%, or at most 5 wt.% by weight; and optionally in a range of 1 to 40%, 5 to 40%, 10 to 40%, 20 to 40%, 1 to 30%, 5 to 30%, 10 to 30%, 15 to 30%, 20 to 35%, or 20 to 30% by weight.
39. The method of any one of claims 1 to 38, wherein the total concentration of the following components by weight in the oil phase or the pretreated oil phase is at least 90 wt.%, at least 93 wt.%, at least 95 wt.%, at least 97 wt.%, or at least 98 wt.%: the prepolymer, the non-amino crosslinking agent, the reactive hydrophobic inorganic filler, the amino silicone oil, and the silicone oil, including any pigment particles and a dispersant for the pigment particles.
40. The method of any one of claims 1 to 39, the aqueous phase further comprising an oil-in-water emulsifier, optionally non-ionic, having an HLB value in the range of from 12 to 18, from 12 to 17, from 12 to 16, from 12 to 15, or from 13 to 16.
41. The process according to any one of claims 1 to 40, wherein the total concentration of water and any emulsifier in the aqueous phase is at least 90 wt%, at least 95 wt%, at least 97 wt%, at least 99 wt% by weight.
42. The method according to any one of claims 1 to 41, wherein the mammalian hair to which the pretreated oil-in-water emulsion is applied is dried or unwetted mammalian hair, or is pre-dyed hair.
43. The method of any one of claims 1 to 42, wherein at least one of the oil phase, the pre-treated oil phase, or the polymeric particles of the hydrophilic polymer having neutralized acid moieties (if present), further comprises or encapsulates a pigment, optionally a plurality of submicron pigment particles, wherein the oil phase or the pre-treated oil phase further comprises a dispersant in which the submicron pigment particles are dispersed, optionally in a range of 25 to 400, 50 to 200, or 75 to 125 weight percent based on the weight of pigment; and wherein at least one of the oil phase, the pre-treated oil phase, or the polymeric particles of hydrophilic polymeric material having neutralized acid moieties (if present) comprises or encapsulates at least 0.1 wt.%, at least 1 wt.%, at least 5 wt.%, or at least 10 wt.%, based on the weight of oil phase or polymeric material, respectively, of a pigment in the oil phase and/or the aqueous dispersion, the pigment optionally being present at no more than 20% of the weight of the polymeric material of the oil phase and/or the aqueous dispersion.
44. The method of any one of claims 43, wherein the aqueous phase of the oil-in-water emulsion comprises the pigment in an amount of up to 20 wt.%, up to 10 wt.%, up to 5 wt.%, or up to 2 wt.% by weight in the aqueous phase, or wherein the aqueous phase is free of the pigment.
45. The method of any one of claims 43 or 44, wherein the pretreated oil-in-water emulsion comprises or encapsulates a first pigment, wherein the aqueous dispersion comprising the plurality of polymeric particles comprising or encapsulating a second pigment, the first and second pigments being the same or different, is applied on the at least partially cured aminosilicone coating.
46. A kit for producing a reactive cosmetic composition for coating the outer surface of mammalian hair, the kit comprising:
a ] an aminosilicone coating subsection comprising:
(a) a first compartment comprising an oil phase comprising a first compartment reactant which is at least one of an amino silicone oil and a non-amino silicone oil, and optionally, a solid hydrophobic active inorganic filler disposed in the oil phase;
(b) a second compartment comprising a formulation comprising at least one second compartment reactant which is:
(i) at least one reactive condensation curable film-forming aminosilicone monomer having a molecular weight of at most 1000 g/mol; and
(ii) a non-amino crosslinking agent; and optionally also the presence of a further additive,
(iii) at least one of the amino silicone oil and the non-amino silicone oil;
(c) a compartment comprising a reactant which is at least one reactive condensation curable film-forming aminosilicone prepolymer that forms an aminosilicone coating upon condensation curing, the prepolymer comprising at least one of a reactive condensation curable film-forming aminosilicone polymer and a reactive condensation curable film-forming aminosilicone oligomer;
(d) a compartment containing a pre-treated aqueous solution;
the filler is selected or adapted to promote curing of the condensation curable film-forming aminosilicone prepolymer; the non-amino crosslinker is suitable for or selected to cure the prepolymer;
wherein the compartment comprising at least one reactive condensation curable film-forming aminosilicone prepolymer is (a) a third compartment; (B) the second compartment; (C) at least one of the first compartments such that the first compartment is substantially free of the solid hydrophobic reactive inorganic filler;
wherein at least one of said reactant, said first compartment reactant and said second compartment reactant is pretreated by adding said pretreated aqueous solution to the respective compartment; and, optionally,
b ] an overlying polymer film subsection comprising:
an aqueous dispersion comprising a plurality of polymer particles formed from a hydrophilic polymeric material having neutralized acid moieties, the plurality of polymer particles being dispersed in the aqueous dispersion.
Technical Field
The present invention relates to a composition for coating or dyeing keratin fibres such as mammalian hair. Methods of making and using the same, as well as kits capable of making such compositions and performing such methods, are also disclosed.
Background
Natural hair color is due to two types of melanin: pigmentation of hair follicles caused by eumelanin and pheomelanin. In general, if more eumelanin is present, the hair will be darker in color; if less eumelanin is present, the color development is lighter. The level of melanin changes over time, resulting in a change in hair color.
With age, melanin production in the roots of human hair decreases, leading to lightening of hair and eventually stopping production. Once melanin production ceases, newly growing hairs appear gray or white when light is reflected therethrough.
Hair coloring is one practice to alter the color of hair. The primary reason for doing so is cosmetic (e.g., for masking white hair, for changing to a more stylish or desirable color, or for restoring the original hair color after bleaching for color change, such as by hairdressing methods or solarization). Dyeing of hair can be achieved by using a dyeing composition comprising chemical, organic, herbal or natural dyes. Stains are generally divided into two categories: a) soluble dyes, which can penetrate into the hair (but can also remain on the outside) and can be reacted to induce the desired coloring effect, and b) water-insoluble pigments, which are generally limited to external coloring of the hair fibers in view of their size.
Depending on the duration of the effect, the staining may be permanent, semi-permanent, not fully permanent (semi-permanent) or temporary.
Permanent hair dyeing typically involves penetrating a direct dye or an oxidative dye precursor deep into the hair shaft, typically by first removing any existing melanin, requiring bleaching, and then sealing the dye into the hair cortex. Permanent dyeing also requires an oxidizing or coupling agent to develop the color sufficiently. After washing with the shampoo for at least 30 times, the color is not washed off by the shampoo. However, such permanent dyeing can seriously damage the hair.
Semi-permanent hair dyeing compositions are also known as deposit-only hair dyes. They are chemically milder than permanent hair coloring compositions, penetrate only partially into the hair shaft, and do not generally remove the natural pigments of the hair. After about 10 to 30 shampoo washes, the semi-permanent hair color washes away.
Incomplete permanent hair coloring compositions are chemically milder than permanent or semi-permanent hair coloring compositions, with only a small portion penetrating into the hair shaft. The incompletely permanent dyeing composition remains on the hair only for 4 to 10 shampoo washes.
Permanent, semi-permanent or incomplete permanent dyeing processes are known to damage keratin fibers. In addition, some methods can cause health problems and some compositions can be carcinogenic.
The temporary hair coloring composition does not penetrate into the hair shaft but remains on the outer surface of the hair shaft. Such a dyeing composition can be easily washed off with a single shampoo and, in advantageous cases, can withstand up to 2-3 shampoos.
There is a need for a dyeing composition for dyeing keratin fibres such as hair which has reduced permeability and reduced impact on the integrity of the dyed fibres compared to known dye set compositions, while providing durable dyeing of the fibres.
There is also a need for dyeing compositions for dark keratin fibers, wherein such dyeing compositions provide lighter colors than natural keratin fibers, wherein such dyeing compositions are used without bleaching the keratin fibers.
Disclosure of Invention
Provided herein are methods, compositions, and kits for coating or dyeing keratin fibers (e.g., human hair). According to an exemplary embodiment, a method of coating mammalian hair comprises: (a) providing an oil phase comprising at least one reactive condensation curable film-forming aminosilicone prepolymer. The oil phase satisfies at least one of:
(i) the at least one reactive condensation curable film-forming aminosilicone prepolymer includes at least one reactive condensation curable film-forming aminosilicone monomer having a molecular weight of at most 1000 g/mol;
(ii) the oil phase further comprises a non-amino crosslinker suitable for or selected for curing the prepolymer, the non-amino crosslinker having a molecular weight in the range of up to 1000 g/mol;
(iii) the oil phase according to (i) and/or (ii) further comprises at least one of a silicone oil, an amino silicone oil, a pigment dispersant or a reactive hydrophobic inorganic filler.
The oil phase comprises at least 0.01 wt.%, at least 0.05 wt.%, at least 0.1 wt.%, at least 0.15 wt.%, at least 0.2 wt.%, at least 0.25 wt.%, at least 0.5 wt.%, at least 0.75 wt.%, or at least 1 wt.% water, based on the weight of the oil phase; the method further comprises (b) emulsifying the pre-treated oil phase with an aqueous phase comprising water after subjecting the oil phase to a pre-treatment period to obtain a pre-treated oil phase, thereby obtaining a pre-treated oil-in-water emulsion. The method further comprises (c) applying the pre-treated oil-in-water emulsion to the outer surface of each of the mammalian hair. The method further comprises (d) optionally washing the hair with a rinse solution to remove any excess of the pre-treated oil-in-water emulsion after partial condensation curing of the pre-polymer of the pre-treated oil-in-water emulsion to form an at least partially cured aminosilicone coating on the outer surface of each hair. Optionally, the method can further comprise (f) applying an aqueous dispersion comprising a plurality of polymer particles formed from a hydrophilic polymeric material having neutralized acid moieties over the at least partially cured aminosilicone coating, the plurality of polymer particles being dispersed in the aqueous dispersion, thereby producing an overlying polymeric layer (overlying polymeric layer) adhered to the exterior surface of the aminosilicone coating. Optionally, the method may further comprise washing the hair with a rinse solution to remove any excess aqueous dispersion.
Drawings
Some embodiments of the present disclosure are described herein with reference to the accompanying drawings. This description, together with the drawings, makes apparent to those skilled in the art how to practice some embodiments of the disclosure.
The drawings are for illustrative purposes and are not intended to show structural details of the embodiments in more detail than is necessary for a fundamental understanding of the present disclosure. For purposes of clarity, some of the objects depicted in the drawings are not drawn to scale.
In the figure:
fig. 1A is a schematic illustration of a single keratin fiber in the presence of some emulsion droplets containing a reactive aminosilicone prepolymer, according to some embodiments;
FIG. 1B is a schematic diagram showing how a portion of the emulsion droplets of FIG. 1A migrate to and are disposed on the fibers.
FIG. 1C schematically shows how emulsion droplets further accumulate on the outer surface of the fiber;
FIG. 1D schematically shows how emulsion droplets merge to form a continuous film on the outer surface of the fiber;
fig. 1E schematically shows a top view of the surface of uncoated mammalian hair at magnification, showing the hair scale.
Fig. 1F schematically shows, at magnification, a side view of a longitudinal section along the surface of a coated mammalian hair, including upstanding hair flakes.
Fig. 2A schematically shows how polymer particles of neutralized polymer with acid moieties migrate to the aminosilicone film on the outer surface of the fiber.
Fig. 2B schematically shows how polymer particles further accumulate on the outer surface of the aminosilicone membrane;
figure 2C schematically shows how the polymer particles coalesce to form a continuous layer on the outer surface of the aminosilicone membrane;
FIG. 2D schematically illustrates how a neutralizing agent evaporates from a polymer layer, thereby changing the properties of the polymer material;
fig. 2E schematically shows how an aminosilicone film under a polymer layer adheres to the outer surface of the underlying fibers;
FIG. 3A is a schematic plot showing the percentage of hydroxyl groups present in an exemplary pretreatment composition as a function of the duration of pretreatment of a reactive oil phase;
fig. 3B is a schematic plot showing the degree of staining achievable by an exemplary oil-in-water emulsion as a function of the duration of pretreatment of its reactive oil phase;
fig. 3C is a schematic plot showing the degree of dye persistence achievable by an exemplary oil-in-water emulsion as a function of the duration of pretreatment of its reactive oil phase;
fig. 3D is a schematic plot showing viscosity levels exhibited by exemplary oil-in-water emulsions as a function of the duration of pretreatment of their reactive oil phase;
FIG. 4 is a schematic graph in which plots similar to FIGS. 3A-3D are shown on a single plot, each plot representing the degree of hydrolysis, staining, permanence, and stickiness in a modified embodiment; and
figure 5 depicts a simplified schematic of a process for preparing a composition including a pretreatment composition according to various embodiments of the present teachings.
Detailed Description
The present disclosure relates to compositions for dyeing or cosmetically treating keratin fibers, including mammalian hair, such as human or animal hair, and in particular to oil-in-water emulsions comprising an oil phase comprising a reactive condensation curable aminosilicone prepolymer capable of forming an aminosilicone coating on the outer surface of hair fibers. The aminosilicone coating in turn can be used as a substrate for aqueous dispersions comprising polymer particles, including micelles of hydrophilic polymer material optionally encapsulating pigment particles. The invention relates more particularly to a method for pre-treating the oil phase, in order to improve, among other things, the properties of the oil-in-water emulsion emulsified therewith, the properties of the resulting aminosilicone coating and the properties of the subsequent layer of polymeric material.
Overview of Hair coating Process
Before explaining the pretreatment method in detail, an overview of an innovative coating or dyeing process using reactive condensation curing aminosilicones to form a first layer coating is provided with reference to fig. 1. For simplicity, the various stages of the process are shown on a single side of an individual hair fiber. The driving force is required to form an aminosilicone coating ("AS coating") on the outer surface of the
It is believed that after the hydrophobic reaction phase droplets reach the fiber surface, these droplets displace any water or air disposed thereon, as schematically provided by arrows 16 in fig. 1B, and some of the positively charged amine-based functional groups in the aminosilicone species are driven sufficiently close to link or otherwise associate with some of the negatively charged functional groups disposed on the fiber surface (see fig. 1B).
Within a short time, typically most minutes, an initial aminosilicone film is formed on the fiber surface, having an exemplary thickness of about 500 nanometers (typically in the range of 100nm-2,000 nm). Advantageously, the membrane may be self-terminating. Without wishing to be bound by theory, it is believed that after the initial aminosilicone monolayer is formed, successive droplets of aminosilicone-containing liquid continue to be attracted by the negative charge of the fiber surface, even "through" the first (and intermediate) layer 12' of aminosilicone, but are repelled by the positive charge of the amine-based moieties therein. Initially, the net force of the attractive and repulsive forces is positive, so that the aminosilicone-containing droplets continue to be attracted to the fiber surface where the aminosilicone collects, as shown in fig. 1C. The aggregation of the aminosilicone on the fiber is electrostatically driven to continue as long as the net force of the attractive and repulsive forces remains positive.
As the thickness of such an aggregate increases, the negatively charged fiber surface is distanced from the large number of positively charged droplets located at or near the aggregated aminosilicone, thereby reducing the attractive forces thereon. In addition, the overall positive charge of the aminosilicone aggregates increases with increasing mass of the aggregates, so that the repulsion force continues to increase. After the net force approaches zero, the net flux of the aminosilicone-containing droplets to the fiber surface is essentially zero, thereby achieving self-termination. FIG. 1C schematically shows self-terminating aggregates of positively charged aminosilicones on the surface of negatively charged fibers. Once the migration of the charged species reaches such a point: i.e. the repulsive force between the stabilizing layer on the hair fibre and the bulk of the droplets overcomes the previous attractive force and the film self-terminates. In other words, when self-termination is achieved, no more material can accumulate on the hair fibres.
The self-termination of the process advantageously prevents the endless accumulation of material once the driving gradient is no longer present, which usually results in an uncontrolled thickness of the coating. In extreme cases, the deposition of material without rest can result in the collection of inseparable clumps of hair that are of no practical use. In more tolerable cases, although the material is not prevented from gathering, the application can be interrupted and the hair fibres bridged by the liquid can be separated in such an undesired process by frequent vigorous combing, such a detangling process often leading to a poor appearance and/or a reduced mechanical resistance/adherence of the coloured coating (if any). Advantageously, the self-terminating process according to the teachings of the present invention results in a coating of reasonable thickness, allowing the coated hair to remain separated into individual fibers without sticking together. The thickness of the coating can be controlled by the size of the emulsion droplets (e.g., droplets with a Dv50 of 1-2 μm, which are easily formed by vigorous manual shaking, will produce a coating thickness of 0.5-1 μm).
Over time, the aminosilicone aggregates encapsulating the fiber surface may coalesce to form an AS film or coating (fig. 1D). According to some embodiments, the average particle size (Dv50) of emulsion droplets formed when the reactive condensation curable amino functional silicone prepolymer is in an emulsion is from 200nm to 100 μm, from 200nm to 50 μm, from 200nm to 25 μm, or from l μm to 20 μm, or from 200nm to 1 μm, or from 0.5 μm to 5 μm, or from 0.7 μm to 3 μm, or from 1 μm to 2.5 μm, or from 1 μm to 10 μm. The size of the droplets and/or the homogenization of the size of the droplet population can be varied by selecting any desired emulsification method, adjusting, for example, the energy input in the process and its duration. Low energy methods (e.g., manually shaking the mixture) are sufficient to provide uniformly sized droplets in the range of 1-5 μm. A moderate energy process (e.g., using a planetary centrifugal mill) can provide a more homogeneous population, the size of which can be adjusted by length and speed (e.g., in short, providing droplets in the range of 10-20 pm). High energy methods (e.g., using a sonicator) can rapidly provide droplets in the submicron range.
Advantageously, because hair fibers wetted by the positively charged aminosilicone coating repel each other, there are no liquid bridges between adjacent fibers, thereby preventing hair aggregation and keeping the fibers individual. When the partial condensation cure is sufficiently rapid, the outermost layer of the aminosilicone coating may be sufficiently firm (form a hard shell-like barrier) prior to drying to help the fibers remain as distinct individual hairs.
Without wishing to be bound by theory, it is believed that prepolymers with relatively low MW (relatively low viscosity) have better prospects for adequate wetting of hair fibers than prepolymers with relatively high MW (relatively high viscosity).
Thus, once the composition ingredients are brought sufficiently close to the fibers due to electrostatic bonding, other mechanisms (e.g., acid: base hydrogen bonding or even covalent bonding) become available to attach the aminosilicone molecules to the hair surface. It is believed that such a process, in combination with the ongoing condensation curing of the prepolymer molecules, can provide (a) adhesion to the underlying fibers ("adhesion") and (b) "cohesion" of the aminosilicone film.
Although not shown in the figures, the pigment particles optionally applied in combination with the aminosilicone composition according to the present disclosure are advantageously entrapped in a growing network of a prepolymer whose curing is done in situ on the hair fibers. It is believed that such entrapment improves the adhesion of the pigment particles to the hair fibres and ensures that their retention time on the hair fibres is longer than given by the mere physical deposition in the presence of the non-reactive polymer. When using a pigment dispersant in a separate preliminary step to reduce the size and/or disperse the pigment into the particles, it is believed that the pigment particles are first partially encapsulated by the pigment dispersant, which in turn forms an interface with the surrounding amino silicone matrix. In this case, it is preferable to pretreat the pigment dispersant rather than the pigment particles. Further, the pretreatment of the pigment dispersant is preferably performed after the pigment dispersion.
Although not shown in the figures, it is believed that the
It has surprisingly been found that the use of an AS formulation (e.g. an oil-in-water emulsion) having an alkaline pH (at least 9.0, at least 9.5 or at least 9.75, and typically 9.0-11.5, 9.0-11.0, 9.5-11.5, 9.5-11.0 or 9.5-10.7) may significantly enhance the adhesion of the AS film to the hair surface. Without wishing to be bound by theory, it is believed that at such alkaline pH, cuticle scales 30 (as schematically shown in the top view of fig. 1E) of the
It is also believed that the basic pH of such oil-in-water emulsions further increases the charge difference between the coated hair fibers and the droplets of reactive amino silicone prepolymer. At basic pH, the prepolymer of the composition (cationic according to its amine functionality) is positively charged, whereas at similar pH, the hair fiber surface is negatively charged. It will be appreciated that, in accordance with these principles, the anionic and nonionic polymers will not be so electrostatically driven towards the hair fibres that their intended adhesion to the hair fibres (if any) is correspondingly reduced (e.g. at most allowing physical deposition or hydrophobic: hydrophobic interactions).
Although electrostatic attraction is essential to being able to achieve initial adhesion of the film, it has been found that there may be significant other obstacles that must be overcome to enable initial attraction to cause adhesion and subsequently maintain and strengthen the adhesion.
One such obstacle involves transporting a substance containing an interactive moiety (e.g., an amino or silanol moiety) to the interface with the outer surface of the fiber. It has been found that this transport can be strongly influenced or controlled by the extent to which the fibres are wetted by the droplets of the amino silicone-containing reaction phase in the emulsion. More specifically, the surface tension of the reaction phase is preferably controlled so that the liquid phase sufficiently wets the hydrophobic surface of the fiber. It has further been found that in some embodiments, the viscosity of the formulation, and more particularly the viscosity of the reactive phase, should preferably be low enough to facilitate the transport of such materials to the fiber surface.
It is believed that despite the various advantages of using tacky polymeric materials, such materials may be significantly unsuitable for achieving permanent hair coloring in terms of their less tacky monomeric and/or oligomeric counterparts.
Furthermore, it has been found that even if all these conditions are met, the electrostatic attraction between negatively charged functional groups located on the fiber surface and positively charged amine-based functional groups that have been transported to the fiber surface, as well as any other attractive interactions, may not be sufficient to overcome the various types of steric hindrance. For example, large polymer structures may not be properly dispatched to locations on the fiber surface due to other such structures (even much smaller structures) that already occupy locations on the fiber surface. Even in the absence of such interference, in this manner, the electrostatic attraction decreases significantly with distance, failing to draw the polymer structure closer to the fiber surface, or failing to achieve any significant or sufficient association between the charged functional groups, such that large polymer structures may not be aligned with the fiber surface. In some cases, even if such associations are formed, they may not be sufficient to hold the large polymer structure in place when subjected to shear and/or drag forces (e.g., during shampooing). Large polymer structures may have very little surface area available to the fiber surface (located close enough to the fiber surface), which further impairs the ability of the joint to withstand such shear and drag.
According to some embodiments, the reactive condensation curable amino-functional silicone prepolymer has an average molecular weight in the range of about 100 to about l00,000. Typically, the MW of the monomers is in the range of about 100 to about 1,000, the average MW of the oligomers is in the range of about 200 to about 2,000, and the average MW of the polymers is in the range of at least about 2,000, and in certain embodiments, up to 50,000.
It has been found that the strength of the initial AS to hair fibre attachment can generally be correlated to an increase in the amine number of one or more aminosilicone substances disposed in the reactive phase of the emulsion. However, it is clear that the accessibility of each amine group also needs to be considered (e.g. due to steric hindrance, etc.). It has been found that in order to create sufficient electrostatic attraction and/or association with the fibers, the amine value or average (e.g., weight average) amine value of these one or more aminosilicone materials should be at least 3 or at least 4, and more typically at least 5, at least 6, at least 8, or at least 10, and/or in the range of 3-200, 5-500, 10-1,000, 10-400, 10-300, or 25-250. While aminosilicone prepolymers are primarily considered in relation to amine number, it should be borne in mind that aminosilicone oils lacking condensation cure groups may also contribute to the overall and average amine number of the reactive oil phase.
The amine number of the aminosilicone prepolymer, aminosilicone oil or any other aminosilicone material is generally provided by the manufacturer, but may be independently determined by standard methods, such as those described in ASTM D2074-07. It can be provided in terms of milliliters of 0.1N HCl needed to neutralize 10g of the material under study.
According to aspects of the present disclosure, an aqueous dispersion comprising a polymeric material having neutralized acid moieties may be applied to an underlying AS film to produce an overlying polymeric film covering such AS film. In some embodiments, the polymeric material has acid moieties that can be neutralized, for example, including, by way of non-limiting example, carboxylic acid groups present in acrylic acid and methacrylic acid moieties.
In many embodiments, the polymeric material may comprise, consist essentially of, or consist of: neutralized olefin-acrylic acid copolymers (e.g., Ethylene Acrylic Acid (EAA) copolymers), or neutralized olefin-methacrylic acid copolymers (e.g., ethylene-methacrylic acid (EMAA) copolymers) or neutralized acrylamide/acrylate (AAA) copolymers. In some embodiments, the polymeric material may comprise, consist essentially of, or consist of an acrylic copolymer having both neutralized acrylic acid and neutralized methacrylic acid moieties.
Such a polymer layer, which may comprise pigment particles, may provide the (coloured) film structure with various advantageous properties, including abrasion resistance, resistance to intercalation by chemicals (e.g. soap and shampoo), etc.
Furthermore, it has been found that such copolymers can be advantageously used AS pigment dispersants, thereby avoiding or at least alleviating the need for specialized dispersants (e.g., AS is often necessary when dispersing pigments in AS coatings). Thus, more pigment can be loaded into the overlying polymer film, thereby increasing the optical density (dyeability) for a given film thickness. Such specialized dispersants may also compromise the cohesion of the overlying polymer film, and/or the adhesion of the overlying polymer film to the underlying AS coating and/or water resistance. Such specialized dispersants also (often disadvantageously) lower the softening point temperature and/or glass transition temperature of the polymer layer.
The formation of this polymer layer over and encapsulating the AS film requires a driving force. Without wishing to be bound by theory, it is believed that in various methods of the present disclosure, the initial driving force for delivering the polymeric material having neutralized acid moieties to the external AS surface includes or consists essentially of electrostatic attraction between positively charged amine-based functional groups located on and within the AS membrane and negatively charged functional groups (e.g., carboxyl moieties) located in the dispersed
Since, as mentioned above, the application of the aminosilicone coating by the polymer particles is believed to be driven in part by their respective charges during this process, another method of describing the critical conditions that are advantageous for the method of the present invention relies on the initial surface Zeta potential of the materials due to their interaction with each other. At the pH of the applied aqueous dispersion, the mammalian hair fibers pre-coated with the amino silicone coating have a first surface Zeta potential (ζ 1) and the aqueous dispersion has a second Zeta potential (ζ 2). At the pH, the difference between the two values (also referred to as Zeta difference (Δ ζ)) is defined as Δ ζ ═ ζ 1- ζ 2, each of ζ 1, ζ 2, and Δ ζ being provided in millivolts (mV). In some embodiments, Δ ζ is at least 10mV, at least 15mV, at least 20mV, at least 25mV, at least 30mV, at least 40mV, or at least 50 mV. In some embodiments, Δ ζ is in a range of 10 to 80mV, 10 to 70mV, 10 to 60mV, 15 to 80mV, 15 to 70mV, 15 to 60mV, 20 to 80mV, 20 to 70mV, 20 to 60mV, 25 to 80mV, 25 to 70mV, 25 to 60mV, 30 to 80mV, 30 to 70mV, 30 to 60mV, 35 to 80mV, 35 to 70mV, or 35 to 60 mV. The first surface Zeta potential (Zeta 1) of the aminosilicone coating is greater than zero (Zeta 1>0) at a pH of the aqueous dispersion in the range from 4 to 11, from 4 to 10.5, from 4 to 10, from 6 to 11, from 6 to 10.5, from 6 to 10, from 7 to 11, from 7 to 10.5 or from 7 to 10.
The surface Zeta potential of a material is typically measured in the liquid phase. The Zeta potential of the solid coating can be measured using a flow current detector in a Zeta potential analyzer adapted to flow water through a tube in which the sample is placed. The results obtained by this method reflect to some extent the Zeta potential of the same particles in suspension. Conversely, the Zeta potential of the aminosilicone oil-in-water emulsion is considered to be predictive of the surface Zeta potential of the aminosilicone coating produced thereby.
Once the Zeta potential difference (Δ ζ) between the two surfaces is substantially zero or zero, the application of the aminosilicone coating by the overlying polymer layer is self-terminating.
Over time, the aggregation of the dispersed polymer particles on the AS membrane undergoes coalescence to form the
The waiting time after application may be at most 10 minutes or at most 5 minutes, more typically at most 3 minutes, at most 2 minutes, at most 1.5 minutes or at most 1 minute. The thickness of the polymer overcoat can be about 100-5,000nm, more typically 150-2,000nm, and more typically 150-1,000nm or 150-600 nm.
As schematically shown, the outer surface of the outer polymer coating facing and contacting the majority of the aqueous dispersion contains negatively charged moieties. It is advantageous to neutralize these moieties on the outer surface, for example, by a volatile base (e.g., ammonia) typically present in aqueous dispersions containing polymeric materials having neutralized acid moieties. Such an operation may result in a conjugated acid coating (as schematically shown at 32 in fig. 2D) of the polymeric material that exhibits improved water resistance and/or improved mechanical properties, particularly after the volatile base has evaporated.
Excess neutralizing agent is preferably avoided in order to evaporate more rapidly thereby accelerating, inter alia, the acid conjugation of the neutralized portion of the hydrophilic material back to the natural hydrophobic polymer, forming a water resistant polymer layer, and reducing tack. In addition, an excess of neutralizing agent (e.g., base) can block the silanol groups of the aminosilicone of the first coating by hydrogen bonding with the first coating, limiting the accessibility of such hydroxyl groups to the amine moieties of other aminosilicones, thus delaying the condensation cure of the aminosilicone coating. In other words, an excess of base in the second coating inhibits curing of the first coating.
To avoid excess neutralizing agent, the amount of a particular base to be added to a particular polymeric material (having a particular content of acid moieties) can be estimated based on the desired degree of neutralization. In addition, the amount of base in the neutralized dispersion can be monitored. For example, pH can be monitored by pH using a pH meter. In one embodiment, the amount of neutralizing agent in the neutralized dispersion is monitored by conductivity. Base was added or the dispersion was allowed to evaporate until the conductivity was less than 3 milliSiemens (milliSiemens).
It may be desirable to produce one or more additional coating layers on top of the outer coating polymer layer. Additional aminosilicone-containing formulation (typically an emulsion) is added. In an alkaline medium, this neutralizes the acid groups on the outer surface of the polymeric overcoat to form negatively charged moieties so that positively charged amine moieties can be electrostatically attracted to and subsequently attached to these negatively charged moieties.
In the long term (e.g. 12 to 36 hours, unless special pre-treatment is performed), it is advantageous that additional bonding between the hair fibres and the aminosilicone film takes place. Fig. 2E provides a schematic cross-sectional view of a
For example, a polymer (or film formed from a reactive prepolymer) may be considered to have fully cured when its glass transition temperature no longer changes over time (in other words, has reached a substantially stable value), indicating that no further crosslinking is occurring. Alternatively and additionally, the aminosilicone polymer (or film produced therefrom) is fully cured when the prepolymer is in a curable fluid and the number of siloxane bonds that can be formed under appropriate curing conditions is not substantially changing over time. The number of siloxane bonds in the cured aminosilicone polymer can be assessed by conventional analytical methods, for example by Fourier Transform Infrared (FTIR) spectroscopy.
Amino silicone coating
Hereinafter, unless the context clearly indicates otherwise, the oil phase or reactive oil phase (and similar variants) encompass or refer to a reactive oil phase that has been pretreated in accordance with the teachings of the present invention. Similarly, (reactive) aminosilicone oil-in-water emulsions encompass or relate to emulsions whose oil phase has been pre-treated according to the teachings of the present invention.
Prepolymers generally refer to materials (e.g., uncured/curable monomers, oligomers, and/or polymers) that can be crosslinked through crosslinkable groups (also referred to as reactive groups) to form larger macromolecules by a technique known as a curing process. As used herein, prepolymers are considered reactive (still capable of participating in polymerization or curing) when they lack the glass transition temperature (Tg) when initially in the oil phase. There are various curing methods depending on the chemical composition of the prepolymer to be crosslinked, its reactive groups and curing co-factors (crosslinking agents, curing accelerators or catalysts, etc.).
Although the reactive aminosilicone prepolymer lacks an initial Tg, once added to the emulsion and applied to the hair fibers and sufficiently cured, a network is formed and, in order for the at least partially cured aminosilicone film to behave like a flexible elastomer lacking brittleness, the prepolymer is preferably cured to form a 3D network with a Tg of less than about 25 ℃ (i.e. a Tg between-100 ℃ and +20 ℃), typically not more than +10 ℃ or 0 ℃, possibly less than-5 ℃, less than-l 5 ℃ or less than-25 ℃; and optionally in the range between-80 ℃ and-20 ℃ or between-70 ℃ and-30 ℃. However, brittleness can also be avoided by using very thin coatings (e.g., a thickness of one micron or less). In this case, films of cured polymers having a Tg above about 25 ℃ may also be used. Cured films with a relatively higher Tg have a higher crosslink density than cured films with a relatively lower Tg. Cured films with higher Tg/crosslink density are expected to be more resistant to abrasion, swelling, or chemical attack (e.g., alcohol resistance).
Typically, the condensation curable aminosilicone prepolymer forms a phase that is water-separated, i.e., substantially immiscible with water. Such different phases may also be referred to as "oil phases", reactive oil phases or similar variants. For reasons that will be described in further detail below, in some embodiments, the reactive oil phase may include at least one of a silicone oil, an amino silicone oil, a cross-linking agent, a 3D network former, pigment particles, and a pigment dispersant in addition to the reactive amino silicone prepolymer. All substances present in the oil phase may be referred to as "reactants" even in the absence of any particular ability to react or interact with other molecules of the oil phase.
The present disclosure relates to silicone prepolymers that are condensation curable, i.e., they carry crosslinkable groups capable of reacting with each other to form siloxane bonds by condensation, while releasing molecules of alcohol, oxime or water in the process. Although there are various condensation curable reactive groups, they may be divided into silanol groups for convenience and hydrolyzable groups (e.g., alkoxy groups) that form silanol groups upon hydrolysis. Condensation curable aminosilicone prepolymers can be classified not only by the chemical nature of their reactive groups, but also by the number of reactive groups per molecule. For simplicity, condensation curable amino silicone prepolymers having a single reactive group per molecule (whether silanol or hydrolyzable group) can be represented as 1-SiOH, molecules having two reactive groups as 2-SiOH, and molecules having three or more reactive groups as 3+ SiOH. Condensation curable aminosilicone prepolymers having two or more groups may have different groups for each reactive moiety.
Although condensation-curable aminosilicone prepolymers having a single reactive group (1-SiOH) can participate in the polymerization (curing) via their sole condensation-curing group, they are generally regarded as terminating this process in terms of network development. Thus, when a three-dimensional (3D) network of aminosilicone films is desired, condensation curable aminosilicone prepolymers having a single condensation cure reactive group per molecule in the prepolymer mixture should be kept present in low amounts and preferably avoided. The same principle applies analogously to any other material present in the oil phase. Preferably, the reactants should not function in a manner equivalent to polymerization termination or cure inhibition. In some embodiments, the concentration of the aminosilicone prepolymer having a single condensation cure reactive group per molecule and/or any reactants capable of inhibiting cure is at most 7 wt%, at most 5 wt%, at most 2 wt%, or at most 1 wt%, based on the weight of the oil phase. In some embodiments, the oil phase is free of the 1-SiOH prepolymer or terminating reactant.
Aminosilicone prepolymers having two condensation-curing reactive groups per molecule (2-SiOH) can participate in network formation in a more meaningful manner than the 1-SiOH counterparts described above. Preferably, such networks should not rely solely on linear chain extension to enable the formation of sufficiently cohesive 3D matrices within and between such chains of the prepolymer undergoing curing. By analogy, a reactant capable of interacting with two different groups (typically on different molecules, but not exclusively) may be referred to herein as "bifunctional". An example of a difunctional reactant that is not an aminosilicone prepolymer may be a non-amino crosslinker. In some embodiments, the concentration of the aminosilicone prepolymer having two condensation cure reactive groups per molecule and/or the concentration of any difunctional reactant is at most 30 wt%, at most 20 wt%, at most 10 wt%, or at most 5 wt% based on the weight of the oil phase. In some embodiments, the oil phase is free of the 2-SiOH prepolymer and/or difunctional reactant. Reactive polymer-forming condensation curable aminosilicone prepolymers having at least three condensation cure reactive groups (e.g., three silanol and/or hydrolyzable groups) advantageously promote the formation of three-dimensional networks. Similarly, "trifunctional" reactants that accelerate or otherwise enhance 3D network formation are preferred over less functionalized counterparts. Examples of such "trifunctional" reactants include certain crosslinking agents and reactive fillers. In some embodiments, the polymer-forming aminosilicone first reactant comprises at least one reactant having at least three condensation cure reactive groups per molecule and/or a 3D network former.
Condensation curable amino functional silicones are also characterized by the presence of amino groups attached to the silicone prepolymer backbone through carbon atoms. These amino groups (at the terminal or pendant ends) can also be linked or interacted with other molecules through nucleophilic reactions or interactions, such as, but not limited to, on carboxylic acid, anhydride, or epoxy functional molecules or substrates. Thus, while some of the silicone prepolymers disclosed herein are referred to as "reactive" or "condensation curable" amino-functional silicones, the term is not intended to limit the curing process by only condensing condensation curable reactive groups, amino groups can also be cured by "non-condensation" processes, thereby forming, for example, nitrogen-carbon bonds. The product of such a curing process is a network of crosslinked oligomers or polymers called elastomers or elastomeric networks (rubber-like) depending on their viscoelastic properties. Although elastomers generally refer to cured polymers having a glass transition temperature below typical environmental values, thin coatings of "elastic" polymers having a Tg above such environmental values and which for all practical purposes behave as regular elastomers can be tolerated. Thus, because the cured aminosilicone coatings resulting from the process of the present invention are thin, both elastomers (e.g., Tg <30 ℃) and elastomeric networks (e.g., Tg >30 ℃) are suitable. Since such cured networks (preferably three-dimensional networks to enhance cohesion) can form continuous films, prepolymers that participate in such formation, alone or in combination with other film forming agents (e.g., crosslinking agents, 3D network formers), can also be referred to as film forming prepolymers.
The amino-functionalized silicone prepolymers (or "aminosilicones") of the present disclosure may be considered to be positively charged or capable of being positively charged under appropriate chemical circumstances (e.g., at a pH above the isoelectric point of hair). The charge of a particular material can be deduced from its chemical structure and the type of protonation it can undergo. It can be evaluated as the material is dispersed or dissolved in water or in any other aqueous environment relevant to the operating conditions of the material under study. In the context of the present invention, the aminosilicone prepolymer is used (alone or in combination with other reactants) in the form of an oil-in-water emulsion.
In some embodiments, the oil-in-water emulsion has a surface Zeta potential of greater than zero or at least +1mV, at least +2mV, at least +3mV, at least +5mV, at least +7mV, at least +10mV, at least +15mV, at least +20mV, at least +30mV, at least +40mV, or at least +60 mV; optionally, at most +100mV or at most +80 mV.
In some embodiments, the surface Zeta potential of the oil-in-water emulsion is greater than zero and less than 90mV, or is in the range of 1-50mV, 1-30mV, 1-20mV, 1-15mV, 2-100mV, 2-30mV, 3-100mV, 3-50mV, 3-30mV, 3-20mV, 5-100mV, 5-50mV, 5-30mV, 5-20mV, 7-100mV, 10-80mV, 15-80mV, 20-80mV, or 20-60 mV.
In some embodiments, the surface Zeta potential of the oil-in-water emulsion is measured at pH 9. In other embodiments, the surface Zeta potential is measured at the natural pH of the oil-in-water emulsion (about pH 10). If the solids content of the oil-in-water emulsion is too high, the Zeta potential can be determined for a diluted sample comprising 2 wt.% or less of the solids-based material.
Such materials may be characterized in part by their amine number, which represents the number of amino groups per molecule (or per given weight of aminosilicone material, whether film-forming or not). In some embodiments, at least one and optionally all of the reactive condensation curable film-forming aminosilicone prepolymers disposed in the reactive oil phase have an amine number or weight average amine number in the range of from 3 to 1,000, 3 to 500, or 3 to 200. In some embodiments, the entire reactive oil phase exhibits an amine number in the range of 3 to 1,000, 3 to 500, or 3 to 200.
In some embodiments, the condensation-curable aminosilicone prepolymer is water-insoluble or substantially water-insoluble, in which case the prepolymer may also be said to be hydrophobic. In some embodiments, the solubility of the prepolymer is 5 wt% or less, 2 wt% or less, 0.5 wt% or less, or 0.wt% or less, relative to the weight of the aqueous composition in which it is present. Solubility can be assessed visually, and the composition is typically at 23 ℃. If the material forms a clear solution in water, it is water soluble at or below the threshold concentration. When the material is a macromolecule (e.g., a polymer), the polymer is said to be water soluble if the micelles formed therefrom are not detectable and the water carrier remains transparent. In contrast, the material (or prepolymer) is insoluble if not soluble in water (e.g., forms a visually perceptible dispersion or emulsion).
In some embodiments, the reactive condensation curable film-forming aminosilicone prepolymer has at least three condensation curable reactive groups per molecule and a solubility in water of less than 1 wt% (at 23 ℃). In some embodiments, a reactive condensation curable film-forming aminosilicone prepolymer having at least three condensation curable reactive groups per molecule includes a reactive condensation curable aminosilicone monomer having a solubility in water of less than 1% by weight (at 23 ℃).
As noted above, the aminosilicone prepolymers used in the compositions and methods of the present invention are reactive and condensation curable. While the presence or absence of a glass transition temperature allows the reaction potential of a material or mixture to be evaluated, viscosity may provide an alternative indication that is generally more readily available or evaluable. Aminosilicone materials having relatively high viscosities, particularly materials that are solid at temperatures associated with the performance of the method of the present invention (e.g., at ambient temperatures of about 23 ℃), are significantly or fully crosslinked. Even if not fully crosslinked, aminosilicones having too high a viscosity are considered to be unable to participate in further crosslinking under the conditions (e.g., temperature, time of duration, etc.) associated with the method of the present invention. For similar reasons, aminosilicone materials having a relatively high molecular weight (MW, which in the case of polymers, in view of possible homogenization, usually refers to the weight average molecular weight of the material) may also be less reactive or cure more slowly than aminosilicone prepolymers having a lower MW.
The molecular weight of the aminosilicone prepolymer may depend on the number of identical or different repeating units in the prepolymer. Only one unit of the prepolymer is monomeric. Prepolymers with several repeating units are oligomers. Larger prepolymers may be defined as polymers. In the absence of chemical information, these three main types of prepolymers can be distinguished by chemical structure or, optionally, by molecular weight. The molecular weight or weight average molecular weight MW of the material is typically provided by the manufacturer, but can be independently determined by known analytical methods, including, for example, gel permeation chromatography, High Pressure Liquid Chromatography (HPLC), or matrix assisted laser desorption/ionization time of flight mass spectrometry MALDI-TOF MS.
In some embodiments, the aminosilicone prepolymer consists of or consists essentially of one or more aminosilicone monomers (including mixtures thereof). Aminosilicone monomers are capable of faster condensation curing than their oligomeric or polymeric counterparts given that aminosilicone monomers have smaller size/are more accessible to reactive groups. Such monomers can form three-dimensional (3D) networks with higher crosslink density. In some embodiments, when the aminosilicone prepolymer is predominantly monomeric, the reactive oil phase may further comprise a silicone oil and/or an aminosilicone oil. In some embodiments, the condensation curable aminosilicone monomer has an amine number of at least 200, at least 220, at least 240, at least 275, at least 325, or at least 400. In some embodiments, the amino silicone monomer has an amine number of at most 1,500, at most 1,250, at most 1,150, at most 1,050, or at most 1,000. In some embodiments, the amine number of the aminosilicone monomer is in the range of 200 to 1,500, 220 to 1,250, 200 to 1,150, 200 to 1,100, 220 to 1,250, or 220 to 1,150.
In some embodiments, the aminosilicone prepolymer consists of, or consists essentially of, one or more aminosilicone oligomers (including mixtures thereof). The aminosilicone oligomer is capable of faster condensation cure than the polymer counterpart, while providing a softer coating than the monomer alone. Such oligomers can form 3D networks with a degree of crosslinking lower than that of the monomer and higher than that of the polymer. In some embodiments, when the aminosilicone prepolymer is primarily an oligomer, the reactive oil phase may further include a silicone oil, an aminosilicone oil, a non-amino crosslinker, and/or a reactive filler.
In some embodiments, the condensation curable aminosilicone oligomer has an amine number of at least 20, at least 40, at least 60, at least 75, at least 85, at least 100, at least 125, at least 150, at least 200, or at least 250. In some embodiments, the aminosilicone oligomer has an amine number of at most 600, at most 500, at most 450, or at most 400. In some embodiments, the amine number of the aminosilicone oligomer is in the range of 20 to 600, 40 to 600, 60 to 500, 60 to 400, or 75 to 500.
In some embodiments, the aminosilicone prepolymer consists of, or consists essentially of, one or more aminosilicone polymers (including mixtures thereof). Aminosilicone polymers are capable of providing flexible 3D networks with low crosslink density suitable for soft substrates such as hair. In some embodiments, when the aminosilicone prepolymer is primarily a polymer, the reactive oil phase may further include a non-amino crosslinker, a silicone oil, an aminosilicone oil, and/or a reactive filler.
In some embodiments, the condensation curable aminosilicone polymer has an amine number of at least 2, at least 5, at least 10, at least 15, at least 25, at least 40, at least 75, at least 100, or at least 125. In some embodiments, the aminosilicone polymer has an amine number of at most 200, at most 180, at most 160, or at most 140. In some embodiments, the amine number of the aminosilicone polymer is in the range of 2 to 200, 5 to 200, 10 to 200, 25 to 200, 5 to 150, or 10 to 135.
It has been found that mixing different types of prepolymers or mixing at least one specific type of prepolymer with additional non-reactive silicones allows tailoring of the properties of the cured film that can be produced therefrom by capturing the advantages of each type while reducing their respective disadvantages. For example, while the following observations may depend on the specific compounds of each subtype, it is generally observed that the use of monomers alone may result in the formation of coatings that are too brittle, while the use of polymers alone may be too slow to cure completely or result in coatings that lack sufficient cohesiveness. Therefore, in order to reduce brittleness, it may be desirable to reduce the degree of crosslinking between the prepolymers. This effect can be achieved, for example, by adding a larger prepolymer (typically a condensation curable aminosilicone polymer). Alternatively or additionally, amino silicone oils and/or non-amino silicone oils may be added. Such molecules can reduce crosslink density, reducing brittleness.
Too much of such larger prepolymers and silicone oils may reduce the crosslink density and may also impair various mechanical properties of the film or coating. In addition, too much non-amino silicone oil can reduce the positive charge density of the amino groups, thereby interfering with the electrostatic attraction mechanism, and/or weakening or disrupting the self-termination mechanism of the film.
In some embodiments, the aminosilicone prepolymer is comprised of a mixture of at least two types of prepolymers selected from the group consisting of condensation curable aminosilicone monomers, aminosilicone oligomers, and aminosilicone polymers. For example, the prepolymer mixture may include condensation-curable aminosilicone monomers (e.g., due to their fast cure speed), condensation-curable aminosilicone oligomers (e.g., due to their ability to control crosslink density), and condensation-curable aminosilicone polymers (e.g., due to their contribution to coating flexibility).
In some embodiments, the condensation-curable aminosilicone monomer is present in an amount greater than the amount of condensation-curable aminosilicone oligomer in the mixture of prepolymers. In some embodiments, the condensation-curable aminosilicone monomer is present in an amount greater than the amount of condensation-curable aminosilicone polymer. In some embodiments, the condensation-curable aminosilicone monomer is present in an amount greater than the total amount of condensation-curable aminosilicone oligomer and polymer.
With respect to viscosity, the aminosilicone prepolymer having a lower viscosity is not only expected to be more reactive and/or more flowable than the more viscous counterpart, but also to better wet the hair fibers after it is applied to the hair fibers.
In some embodiments, the oil phase, excluding all inorganic content, has no glass transition temperature. In some embodiments, the condensation curable film-forming aminosilicone prepolymer is liquid at 23 ℃.
According to some embodiments, the reactive condensation curable aminosilicone prepolymer satisfies at least one, at least two or at least three of the following structural characteristics:
a) the prepolymer includes reactive groups selected from the group consisting of alkoxysilane reactive groups, silanol reactive groups, and combinations thereof;
b) the prepolymer has no glass transition temperature;
c) the prepolymer is not solid at 23 ℃;
d) the viscosity of the prepolymer, measured in a suitable rheometer at 23 ℃, is in the range of from 1 to 2,000 millipascal-seconds (mPa · s, also known as cps), l0 to 2,000mPa · s, 2 to 1,000mPa · s, 2 to 500mPa · s, 5 to l00 mPa · s, 10 to 20,000mPa · s, 10 to 15,000mPa · s, 20 to 15,000mPa · s, 30 to 15,000mPa · s, 40 to 10,000mPa · s, or 50 to 10,000mPa · s;
e) the prepolymer is capable of wetting the hair;
f) the prepolymer is a film-forming prepolymer;
g) the prepolymer includes a primary amine;
h) the amine number of the prepolymer is in the range of 3 to 1,000, 3 to 500, or 3 to 200;
i) the prepolymer includes a terminal amino moiety;
j) the prepolymer includes pendant amino moieties;
k) the prepolymer is miscible in the reactive oil phase, which comprises, in addition to the prepolymer, at least one of a different prepolymer, a non-reactive silicone oil, a non-reactive amino silicone oil, a cross-linking agent and a pigment dispersant;
l) the refractive index of the prepolymer is within ± 10% of the refractive index of a reactive oil phase comprising at least one of different prepolymers, non-reactive silicone oils, non-reactive amino silicone oils, cross-linking agents, hydrophobic fumed silicas, and pigment dispersants;
m) the prepolymer is hydrophobic;
n) a solubility of the prepolymer in water at 23 ℃ (e.g., about pH7) of less than 51 wt.%, less than 2 wt.%, less than 1 wt.%, less than 0.5 wt.%, or less than 0.25 wt.%;
o) the prepolymer is a linear or branched polymer;
p) the prepolymer is a linear or branched oligomer;
q) the prepolymer is a monomer; and
r) the ratio of Amine Number (AN) to viscosity (Vise., in mPas) of the prepolymer, when multiplied by 1000, is at least 40, at least 100, at least 200 or at least 500, which can be expressed mathematically as l000 × (AN/Visc.) > 40, and so on.
Although it has been disclosed that silicone materials which are solid at 23-25 ℃ are suitable for improving the lubricity of hair, when they are applied in particulate form, it is evident that such solids are non-reactive and cannot participate in the intended formation of a continuous layer, which can be achieved by coalescence of droplets of a fluid of silicone material at the same temperature. The solid silicone particles are believed to act as drag reducers in a manner similar to mechanical bearings.
In some embodiments, the prepolymer has no glass transition temperature and a solubility in water (pH 7) at 23 ℃ of less than 1 wt%, less than 0.5 wt%, or less than 0.25 wt% based on the weight of the aqueous composition.
In some embodiments, the prepolymer has no glass transition temperature and a viscosity, measured at 23 ℃, in the range of 1 to 2,000 mPas, 10 to 2,000 mPas, 2 to 1,000 mPas, 2 to 500 mPas, 5 to 100 mPas, 10 to 20,000 mPas, 10 to 15,000 mPas, 20 to 15,000 mPas, 30 to 15,000 mPas, 40 to 10,000 mPas, or 50 to 10,000 mPas.
In some embodiments, the prepolymer has no glass transition temperature and has a reactive group selected from the group consisting of an alkoxysilane reactive group, a silanol reactive group, and combinations thereof.
In some embodiments, the prepolymer has an amine value in the range of 3 to 1,000, 3 to 500, or 3 to 200, and a viscosity in the range of 1 to 2,000 mPas, 10 to 2,000 mPas, 2 to 1,000 mPas, 2 to 500 mPas, 5 to 100 mPas, 10 to 20,000 mPas, 10 to 15,000 mPas, 20 to 15,000 mPas, 30 to 15,000 mPas, 40 to 10,000 mPas, or 50 to 10,000 mPas, as measured at 23 ℃.
In some embodiments, the amine number of the prepolymer is in the range of 3 to 1,000, 3 to 500, or 3 to 200, and the solubility in water at 23 ℃ is less than 1 weight percent, less than 0.5 weight percent, or less than 0.25 weight percent based on the weight of the aqueous composition.
In some embodiments, the prepolymer has an amine number in the range of 3 to 1,000, 3 to 500, or 3 to 200 and is miscible in the reactive oil phase, which in addition to the prepolymer, includes at least one of a different prepolymer, a non-reactive silicone oil, a non-reactive amino silicone oil, a cross-linking agent, and a pigment dispersant.
In some embodiments, the prepolymer has no glass transition temperature; having a reactive group selected from the group consisting of an alkoxysilane reactive group, a silanol reactive group, and combinations thereof; and which has a viscosity, measured in a suitable rheometer at 23 ℃, in the range 1-2,000 mPas, 10-2,000 mPas, 2-1,000 mPas, 2-500 mPas, 5-100 mPas, 10-20,000 mPas, 10-15,000 mPas, 20-15,000 mPas, 30-15,000 mPas, 40-10,000 mPas or 50-10,000 mPas.
In some embodiments, the amine number of the prepolymer is in the range of 3 to 1,000, 3 to 500, or 3 to 200; the solubility of the prepolymer in water at 23 ℃ is less than 1 wt%, less than 0.5 wt%, or less than 0.25 wt% based on the weight of the aqueous composition; and the prepolymer is miscible with the reactive oil phase, the reactive oil phase comprising, in addition to the prepolymer, at least one of a different prepolymer, a non-reactive silicone oil, a non-reactive amino silicone oil, a cross-linking agent, and a pigment dispersing agent.
In some embodiments, the prepolymer has no glass transition temperature; having a reactive group selected from the group consisting of an alkoxysilane reactive group, a silanol reactive group, and combinations thereof; wherein the viscosity measured at 23 ℃ is in the range of 1-2,000 mPas, 10-2,000 mPas, 2-1,000 mPas, 2-500 mPas, 5-100 mPas, 10-20,000 mPas, 10-15,000 mPas, 20-15,000 mPas, 30-15,000 mPas, 40-10,000 mPas or 50-10,000 mPas; and has an amine number in the range of 3 to 1,000, 3 to 500, or 3 to 200.
In some embodiments, the prepolymer has no glass transition temperature; having a reactive group selected from the group consisting of an alkoxysilane reactive group, a silanol reactive group, and combinations thereof; and which has a viscosity, measured at 23 ℃, in the range of 1-2,000 mPas, 10-2,000 mPas, 2-1,000 mPas, 2-500 mPas, 5-100 mPas, 10-20,000 mPas, 10-15,000 mPas, 20-15,000 mPas, 30-15,000 mPas, 40-10,000 mPas or 50-10,000 mPas; and having an amine number in the range of 3 to 1,000, 3 to 500, or 3 to 200; and has a solubility in water at 23 ℃ of less than 1 wt%, less than 0.5 wt%, or less than 0.25 wt% based on the weight of the aqueous composition.
According to some embodiments, suitable reactive condensation curable aminosilicone prepolymers may be selected from the group comprising: ATM 1322 bis [ methyldiethoxysilylpropyl ]]Amine, diethoxydimethylsilane, DMS-S12,SIVO 210、1146、KF-857、GP-145、GP-34、GP-397、GP-657、GP-846、KF-862、OFX 8630、OFX 8822、SIB1824.5、SF 1706、
According to some embodiments, the oil-in-water emulsion (which may be in one formulation or resulting from a combination of sub-formulations) further comprises a cosmetically acceptable oil which is miscible with the at least one prepolymer and/or miscible with the cross-linking agent, and/or miscible with the cure condensation accelerator or catalyst, including but not limited to silicone oils.
A cosmetically acceptable oil, more generally any cosmetically acceptable ingredient and similarly cosmetically acceptable compositions or formulations, refers to such materials suitable for use in contact with keratin fibers, particularly human hair, without undue toxicity, instability, allergic response, and the like.
Above and as further detailed herein, some properties of the aminosilicone prepolymers suitable for use in the present disclosure are considered for the individual materials. However, since the reactive oil phase may comprise more than one aminosilicone prepolymer and may also comprise additional reactants, the recommended properties of such a mixture should also be noted. One skilled in the art will readily appreciate that, while certain specific properties may be permissible or otherwise undesirable for an isolated material, mixing the material in an oil phase may provide different tolerances. Since the reactants of the oil phase may include solid inorganic particles (e.g. pigment particles, 3D network formers) that may affect certain measurements, the fact that they may be ignored for certain determinations does not mean that these inorganic particles are not present in the complete oil phase that is emulsified for application to hair fibres.
In some embodiments, the reactive oil phase comprising at least one of the condensation curable aminosilicone prepolymer, the non-reactive silicone oil, the non-reactive aminosilicone oil, the liquid hydrophobic crosslinker, and the pigment dispersant is free of a glass transition temperature. In some embodiments, the viscosity of the reactive oil phase comprising at least one of the condensation curable amino silicone prepolymer, the non-reactive silicone oil, the non-reactive amino silicone oil, the crosslinker, the reactive filler, the pigment, and the pigment dispersant is in the range of 1 to 2,000mPa · s, 2 to 1,000mPa · s, 2 to 500mPa · s, 2 to 400mPa · s, 2 to 300mPa · s, 2 to 200mPa · s, or 2 to 50mPa · s, measured in a suitable rheometer at 23 ℃.
In some embodiments, the solubility in water of the reactive oil phase comprising at least one of the condensation curable aminosilicone prepolymer, the non-reactive silicone oil, the non-reactive aminosilicone oil, the liquid hydrophobic crosslinker, and the pigment dispersant at 23 ℃ is less than 51 wt%, less than 2 wt%, less than 1 wt%, less than 0.5 wt%, less than 0.25 wt% based on the weight of the total aqueous composition.
When it is desired to assess the solubility of the oil phase, but the oil phase is emulsified or any other mixed form, the oil may be separated (e.g., by centrifugation) by any suitable method known to those skilled in the art. Any desired properties of the oil phase thus extracted can then be assessed by any suitable standard method (e.g., solubility, glass transition temperature, chemical analysis).
Since solvents such as organic solvents may, inter alia, change the solubility of the material, the use of such solvents should be avoided in order to maintain a suitable oil-in-water emulsion and/or a suitable partitioning of the components of the oil-in-water emulsion between the water phase and the oil phase.
As used in this specification and the claims section that follows, the term "organic solvent" in or in relation to the oil phase refers to an organic liquid disposed in the oil phase that contains at least one solute (e.g., prepolymer or reactant), and which is not actively involved in bonding within the polymer, nor in bonding of the aminosilicone membrane to the surface of mammalian hair.
As used herein in the specification and in the claims section that follows, the term "co-solvent" in or in relation to an aqueous phase refers to an organic liquid that is at least partially miscible in the aqueous phase, the organic liquid being further characterized in that it increases the solubility of at least one component disposed in the oil phase in the aqueous phase. In extreme terms, a water-miscible cosolvent may result in substantial "dissolution" of the entire oil phase in the aqueous phase.
By way of non-limiting example, the organic solvent may include volatile C1-C6 alkanols, such as ethanol; volatile C5-C7 alkanes, such as hexane; esters of liquid C1-C20 acids and volatile C1-C5 alcohols (e.g., methyl acetate); volatile ketones that are liquid at room temperature, such as acetone; volatile hydrocarbon-based oils such as C8-C16 alkanes (e.g., isododecane); volatile ethers or glycol ethers, such as dimethoxymethane or diethylene glycol monomethyl ether; and mixtures thereof.
By way of non-limiting example, the water-miscible co-solvent may include volatile C1-C6 alkanols, such as ethanol; esters of liquid C1-C20 acids and volatile C1-C8 alcohols (e.g., methyl acetate); volatile ketones that are liquid at room temperature, such as acetone; and mixtures thereof.
It is believed that such solvents, in addition to compromising the efficacy of the oil phase and/or preventing the formation of emulsions, also reduce or delay condensation cure if present in the same phase as the condensation curable aminosilicone prepolymer.
In some embodiments, the total concentration of organic solvent in the oil phase of the emulsion is at most 10%, at most 5%, at most 2%, or at most 1% by weight. In some embodiments, the oil phase does not contain any organic solvent.
In some embodiments, the total concentration of water-miscible co-solvents in the aqueous phase of the emulsion is at most 10%, at most 5%, at most 2%, or at most 1% by weight. In some embodiments, the aqueous phase does not contain any such co-solvent.
In some embodiments, the total concentration of organic solvent in the oil phase and water-miscible co-solvent in the water phase of the emulsion is at most l 0%, at most 5%, at most 2%, or at most 1% by weight of the oil-in-water emulsion. In some embodiments, the oil-in-water emulsion is substantially free of organic solvents and water-miscible co-solvents.
As used herein in the specification and in the claims section that follows, the term "solubility" in reference to a component or mixture of components (component) and a solvent or mixture of solvents (solvent) refers to the solubility of the component in the solvent at the natural pH, i.e., the natural pH is the natural pH achieved by adding the component to the solvent alone in the absence of other components and in the absence of any pH adjusting agent. In the specific case of water solubility, this definition assumes an initial pH of 7 for water.
In contrast to dyes, pigments are generally insoluble in water. In some embodiments, the pigment particles optionally dispersed in the reactive oil phase of the emulsion are insoluble therein.
In some embodiments, the concentration of condensation curable aminosilicone prepolymer having 3 or more silanol and/or hydrolysable groups per molecule in the oil phase is at least 15%, at least 20%, at least 30%, at least 40%, at least 50%, or at least 60% by weight of the oil phase. In some embodiments, the concentration of the 3-SiOH prepolymer is at most 95%, at most 90%, at most 85%, at most 80%, at most 75%, or at most 70%. In some embodiments, the concentration of the aminosilicone prepolymer in the oil phase is in the range of 20-95%, 20-85%, 30-95%, 30-85%, 40-95%, 40-85%, 40-75%, 45-95%, 45-85%, 50-95%, 50-85%, 55-95%, 55-85%, 55-75%, 60-95%, 60-90%, 60-85%, or 60-80%.
In some embodiments, the non-amino crosslinking agent is present in the oil phase. In such embodiments, the combined concentration of aminosilicone prepolymer and non-amino crosslinker in the oil phase ranges from 35-95%, 40-85%, 40-75%, 45-95%, 45-85%, 50-95%, 50-85%, 55-95%, 55-85%, 55-75%, 60-95%, 60-90%, 60-85%, or 60-80% by weight of the oil phase.
In some embodiments, the concentration of the non-amino crosslinking agent within the combined concentration is limited by the following conditions: the oil-in-water emulsion has a surface Zeta potential of greater than zero (>0) or at least +1mV, at least +2mV, at least +3mV, at least +5mV, at least +7mV or at least +10 mV.
In some embodiments, the total concentration of the amino silicone oil, the non-amino silicone oil, and any condensation curable amino silicone prepolymer having less than three condensation cure reactive groups per molecule in the oil phase ranges from 3% to 65%, 3% to 60%, 3% to 55%, 3% to 50%, 3% to 45%, 3% to 40%, 7% to 40%, 10% to 50%, 15% to 45%, 15% to 40%, 20% to 45%, 25% to 50%, 30% to 45%, 30% to 60%, 35% to 50%, or 35% to 60% by weight. In some embodiments, the total concentration of the above-mentioned different components of the oil phase is such that the viscosity of the oil phase, measured at 23 ℃, does not exceed 2,000 mPa-s, does not exceed 500 mPa-s or does not exceed 100 mPa-s.
In some embodiments, the oil-in-water emulsion further comprises a solid hydrophobic reactive inorganic filler disposed or dispersed within the oil phase, the filler being selected or adapted to promote curing of amino silicone prepolymers that are condensation curable to a film. Such film reinforcing fillers may also be referred to as reactive fillers. Advantageously, the reactive reinforcing filler is a hydrophobic 3D network former, which contributes to increasing the cohesion of the aminosilicone film.
The reinforcing filler may be generally selected from the group of fumed silica, precipitated silica, magnesia, alumina (e.g., Ah03 ° 3H20), black amorphous carbon (carbon black, channel black, or lamp black). The reinforcing filler may be selected to suit a particular dyeing. For example, if a relatively large amount of reinforcing filler is required, the use of black filler should be avoided if the size range of the black filler may affect a relatively shallow chroma. Conversely, if a darker shade is desired, a black reinforcing filler may be advantageous.
Suitable reactive fillers may be selected from hydrophobic fumed silicas, the surface of which is at least partially covered with siloxane groups or other groups having hydrophobic properties, such groups typically being reactive with silanol functional units on the silica. Thus, in such a case, the hydrophobic fumed silica may be referred to as a silanol-blocked silica, and surface treatment of the silanol-functional blocked fumed silica may be achieved by one or more of HDMS, polysiloxanes, cyclic polysiloxanes, silazanes, aminosilanes, and silicone oils. The blocking treatment need not be complete, some residual silanol groups are permissible, and even desirable to ensure or promote at least partial cure. When hydrophobic fumed silica is present, it is typically disposed in the oil phase of an oil-in-water emulsion of the condensation curable silicone.
In some embodiments, the reactive filler comprises, consists essentially of, or consists of hydrophobic fumed silica.
In some embodiments, the solid hydrophobic reactive inorganic filler has an average particle size (Dv50) in a range of 5 to 500nm, 5 to 250nm, 10 to 200nm, 20 to 200nm, 40 to 300nm, 60 to 250nm, or 60 to 200 nm.
In some embodiments, the concentration of the solid hydrophobic reactive inorganic filler disposed or dispersed in the oil phase ranges from 0.2% to 12%, 0.2 to 10%, 0.2 to 8%, 0.4 to 10%, 0.4 to 8%, 0.6% to 10%, 0.6% to 8%, 0.8% to 8%, or 0.8% to 6% by weight. In some embodiments, the concentration of the solid hydrophobic reactive inorganic filler in the oil-in-water emulsion ranges from 0.005% to 0.5%, 0.005% to 0.3% by weight.
In some embodiments, the refractive index of the solid hydrophobic reactive inorganic filler (optionally, fumed silica filler) is within ± 10%, ± 7%, ± 5%, or ± 3% of the refractive index of the oil phase (excluding any pigment particles disposed in the oil phase).
According to some embodiments, the pH of the oil-in-water emulsion is at least 4.0, at least 5.5, at least 7.0, at least 8.5, at least 10; and optionally up to 11.0. In some embodiments, the pH of the oil-in-water emulsion is in the range of 4.0 to 12.0, 5.5 to 12.0, 7.0 to 11.0, or 8.5 to 11. A pH value higher than the isoelectric point of the hair fibers to be coated can negatively charge the fibers and/or positively charge the amino functional groups of the aminosilicone prepolymer. In the case of human hair, the isoelectric point is reported to be between about pH 2.5 (e.g., damaged hair) and about pH 3.5-3.7 (e.g., virgin hair). As detailed below, as a first step in forming the coating, it is contemplated that the charge gradient between the surface of the hair fiber and the prepolymer of the composition allows for the formation of electrostatic adhesion between the two. In particular embodiments, the oil-in-water emulsion is at a basic pH of at least 7.5, at least 8.0, at least 9.0, or at least 9.5, and at most 11.
When using a composition with a pH above the isoelectric point of the fibres (e.g. >4, preferably >7), the hair surface will be negatively charged. In some embodiments, the reactive condensation curable amino-functional silicone prepolymer is positively charged when dispersed (e.g., emulsified) in a carrier. For example, the aminosilicone prepolymer may be positively charged at pH 4.0 until it reaches its isoelectric point (typically in the range of pH 10-12). Interestingly, protonation of amine groups above acidic pH (assuming sufficient concentration) can maintain the composition in the alkaline pH range even in the absence of a dedicated pH buffer. It should be noted that at relatively high pH (>9), the scales are sufficiently charged to repel each other, resulting in open channels to the hair shaft. The erection of the scale increases the surface area of the hair fibers, increasing the contact surface with the reactive aminosilicone prepolymer emulsion. As the carrier evaporates, the pH of the coating gradually decreases and the scales return to their original position, during which a portion of the aminosilicone membrane may become entrapped, further enhancing its adhesion to the hair by mechanical interlocking.
According to some embodiments, the oil-in-water emulsion is applied to the hair for a sufficient time to form a gradient that drives sufficient droplets to dewet and form a continuous coating on the fibers. In one embodiment, the application time is between 5 seconds and 10 minutes, or between 10 seconds and 2 minutes, or 1 minute or less. According to some embodiments, the length of time to enable partial curing is between 5 seconds and 30 minutes, or between 1 minute and 15 minutes. While partial curing may begin when the oil-in-water emulsion is applied, partial curing may continue once excess emulsion is removed (e.g., before rinsing the hair fibers).
In some embodiments, the at least partially cured film self-terminates on the outer surface of each hair.
In some embodiments, the partial condensation cure is carried out or occurs at a temperature of at most 38 ℃, at most 36 ℃, at most 34 ℃, at most 32 ℃, at most 30 ℃, or at most 28 ℃ and optionally at least 15 ℃. In some embodiments, shampooing is performed within 30 minutes, within 20 minutes, within 15 minutes, within 10 minutes, within 5 minutes, within 3 minutes, within 2 minutes, or within 1 minute after application of the oil-in-water emulsion has been completed.
In some embodiments, after shampooing, curing occurs further only by, or substantially only by, humidity or ambient humidity.
In some embodiments, all further curing continues within at least half a day, within at least one day, within at least two days, at least three days, at least five days, or within at least one week of said shampooing, in the absence of any non-cationic surfactant added to the hair.
In some embodiments, the hair can be treated with a hair formulation comprising a cationic surfactant within at least half a day, within at least one day, within at least two days, at least three days, at least five days, or within at least one week of shampooing.
In some embodiments, the rinse liquid is (i) water, or (ii) a cationic rinse liquid containing a cationic surfactant, or (iii) a rinse liquid free of a non-cationic surfactant, a degreasing agent, and/or a swelling agent, the degreasing agent and the swelling agent being capable of degreasing and swelling, respectively, the at least partially cured film.
In some embodiments, the cationic surfactant is a cosmetically acceptable primary, secondary, tertiary, or quaternary ammonium compound or polymer.
In some embodiments, the total concentration of the reactive condensation curable aminosilicone component in the oil phase is at least 45%, at least 55%, at least 60%, or at least 65% by weight on a pigment-free basis. In some embodiments, the total concentration of reactive components is in the range of 50-100%, 50-95%, 50-90%, 50-85%, 50-80%, 55-95%, 55-85%, 60-95%, 60-85%, 65-95%, 65-90%, or 70-95%.
In some embodiments, the aminosilicone prepolymer includes reactive groups selected from the group consisting of alkoxysilane reactive groups, silanol reactive groups, and combinations thereof.
In some embodiments, the at least one reactive condensation curable film-forming aminosilicone prepolymer has a solubility in water of less than 0.5% or less than 0.25% by weight.
In some embodiments, the total concentration of amino silicone oil in the oil phase is at most 40%, at most 35%, at most 30%, at most 20%, at most 15%, at most 10%, or at most 5% by weight.
In some embodiments, the total concentration of amino silicone oil in the oil phase ranges from 1% to 40%, 5% to 40%, 10% to 40%, 20% to 40%, 1% to 30%, 5% to 30%, l 0% to 30%, 15% to 30%, 20% to 35%, or 20% to 30% by weight.
In some embodiments, the total concentration of non-amino silicone oil in the oil phase is at most 15%, at most 12%, at most 10%, at most 7%, or at most 5% by weight, such that the surface Zeta potential of the oil-in-water emulsion is greater than zero or is at least +1mV, at least +2mV, at least +3m V, at least +5m V, at least +7mV, or at least +10 mV.
In some embodiments, the total concentration of non-amino silicone oil in the oil phase ranges from 1% to 15%, 3% to 15%, 5% to 15%, 8% to 15%, 1% to 12%, 3% to 12%, 5% to 12%, 3% to 10%, 3% to 8%, or 2% to 5% by weight.
In some embodiments, the non-amino crosslinking agent comprises, consists essentially of, or consists of: reactive condensation curable film-forming non-amino silicone monomers.
In some embodiments, the non-amino crosslinking agent comprises, consists essentially of, or consists of: ethyl silicate, poly (dimethoxysiloxane) and poly (diethoxysiloxane).
In some embodiments, the total concentration of non-amino crosslinkers in the oil phase is at most 35%, at most 30%, at most 20%, at most 15%, at most 10%, or at most 5%, such that the surface Zeta potential of the oil-in-water emulsion is greater than zero or is at least +1mV, at least +2mV, at least +3mV, at least +5mV, at least +7mV, or at least +10 mV.
In some embodiments, the total concentration of prepolymer, non-amino crosslinker, solid hydrophobic reactive inorganic filler, amino silicone oil, and non-amino silicone oil, including any pigment particles and dispersants for the pigment particles, in the oil phase is at least 90%, at least 93%, at least 95%, at least 97%, at least 98%, or at least 95% by weight.
In some embodiments, the aqueous phase further comprises an oil-in-water emulsifier, optionally non-ionic, having an HLB value in the range of 12 to 18, 12 to 17, 12 to 16, 12 to 15, or 13 to 16. In some embodiments, the total concentration of water and any emulsifier in the aqueous phase is at least 90%, at least 95%, at least 97%, or at least 99% by weight.
In some embodiments, the aqueous phase further comprises a pH adjuster. In some embodiments, a pH adjusting agent is added to the aqueous phase such that the oil-in-water emulsion has a suitable pi-I and/or a suitable surface Zeta potential as described herein.
In some embodiments, the mammalian hair to which the oil-in-water emulsion is applied is dry or unwetted mammalian hair, or pre-dyed hair. In some embodiments, the mammalian hair to which the oil-in-water emulsion is applied is at least one of non-pre-defatted, non-pre-shampooed, and non-pre-bleached hair.
In some embodiments, the oil phase further comprises at least one pigment selected from a plurality of submicron pigment particles or a plurality of metallic pigments.
In some embodiments, the oil-in-water emulsion further comprises a dispersant in which the submicron pigment particles are dispersed.
In some embodiments, the aqueous phase comprises an amount of pigment in the oil phase of up to 20%, up to 10%, up to 5%, or up to 2% by weight. In some embodiments, the aqueous phase is free of the pigment.
In some embodiments, the at least partially cured film achieves permanence within 24 hours, and optionally within 12 hours, within 4 hours, within 2 hours, or within 1 hour after application of the oil-in-water emulsion to hair at a relative humidity of 30% to 50% and a temperature of 23 ℃. In particular embodiments, the persistence is achieved within 45 minutes, within less than 30 minutes, within less than 15 minutes, within less than 10 minutes, or within less than 5 minutes.
Pretreatment of reactive oil phase
Hydrolysis of various silicone-based molecules may be required prior to condensation curing of the aminosilicone layer. It has been found that the rate of condensation cure of the aminosilicone layer may be significantly affected or even controlled by the extent of this hydrolysis, and in particular that the hydrolysis in the film regions closest to the fibre surface may be diffusion controlled (i.e. limited by diffusion of water/moisture from the environment through the overlying film, if any), despite the thin (typically on the order of 0.5 microns) AS coating. It is believed that incomplete curing in the region of the film closest to the fiber surface may significantly impair dye durability: when mechanical shear, drag, or other forces are applied to the fibers, the weak bonds between the film and the fibers may be severed or otherwise compromised, resulting in degradation of the film and at least partial peeling from the fibers. Perhaps even more importantly, this incomplete solidification can allow shampoo, soap and other anionic and/or nonionic surfactant-containing materials to penetrate the fiber surface through the AS membrane, or through defects in the membrane to reach the fiber surface where they can successfully compete with the anionic functional groups of the fiber surface, thereby weakening the bond between the fiber and the AS membrane at the interface (similar to a "degreasing" operation). This degradation "window" can potentially be within one week after initial film formation due to the generally slow kinetics of the condensation cure reaction (i.e., including diffusion limitations), particularly at the fiber-AS interface. In the particular case of dyeing human hair, the kinetics can be particularly slow, since after initial application, the subject's hair is exposed to relatively low temperature environmental conditions.
It has further been found that in vitro partial condensation curing of one or more aminosilicone substances prior to application onto fibers can significantly improve various properties of the resulting aminosilicone films. This in vitro step may be referred to as pretreatment, and the time allowed for this step may be referred to as incubation time (incubation time), pretreatment time, or pretreatment period. The properties improved by a suitable pretreatment during a sufficient time include, in particular, the adhesion of the aminosilicone film. The extent of this partial hydrolysis and pre-curing should be sufficient to trigger the formation of a "reactive patch" (patch) while maintaining sufficient reactivity to attach to the fibers and effect further curing thereon. Without wishing to be bound by any particular theory, it is believed that the formation of the elastomeric network of the cured aminosilicone initially proceeds in an "exponential" manner. The rate of cure and the degree of pre-cure at any point in time of pre-treatment considered are in particular related to the amount of reactive condensable curing groups in the participating prepolymers, the amount of reactive prepolymers and the amount of pre-treatment solution in the reactants in the case of the pre-treated oil phase. For simplicity, network formation may be compared to chain reactions, which gain power over time at an early slower rate until a plateau is reached, at which time the cure rate is significantly reduced.
The "in vitro" curing process is virtually absent when the oil phase is emulsified rapidly after its preparation (without any specific pre-treatment) and the resulting oil-in-water emulsion is applied rapidly to the hair fibers (e.g., within less than 30 minutes). Thus, the in situ cure must be initiated from the substantially natural aminosilicone material. Thus, when polymerization proceeds at an initial relatively slow rate, partial condensation cure on the hair fibers begins with a lag phase of cure. The pre-treatment allows partial curing to reach the accelerated "exponential" stage of the network formation process. It is believed that after application of the oil-in-water emulsion prepared from the oil phase thus pre-treated, the reactive plaques generated in vitro can act as nuclei for sustained solidification in situ on the hair fibers. Thus, in situ curing can continue on the hair fibers rather than being initiated, thereby providing a higher level of starting point for the formation of a cohesive network.
The period of adequate pretreatment may depend on the oil phase to be pretreated. A 20% or more increase in the viscosity of the same oil phase compared to the initial viscosity of the oil phase at the start of the pretreatment may indicate a sufficient pretreatment period. The extent of this partial pre-curing should be sufficient to enable the peak of hydroxyl groups to be detected by FTIR analysis of the pre-treatment composition. At this stage of partial hydrolysis and pre-cure, the pretreatment composition contains no fully cured polymer in an amount detectable by the formation of the glass transition temperature, and therefore lacks a Tg. The in vitro pre-cure is sufficiently brief to prevent the formation of a 3D network with a detectable Tg. In some embodiments, the viscosity of the partially pre-cured pretreatment composition (independent of the viscosity of the isolated reactants of the initial mixture) is 100 mPa-s or less, or 50 mPa-s or less, or 25 mPa-s or less. In some embodiments, the viscosity of the partially pre-cured pretreatment composition is at least 1 mPa-s, or at least 5 mPa-s, or at least 10 mPa-s.
Pretreatment of the reactive oil phase further reduces the mass transfer limitations described above. It has been found that advantageously, such a prehydrolysis step may not affect the dyeing to a large extent as long as the condensation curing can be continued on the fibers. Therefore, such additional step does not substantially impair the target optical density, and the durability of the film and the time required to obtain such durability can be advantageously further improved.
It has been found that the cross-linking density and speed can be increased by using reactive silicones, and that the density and speed can be further increased by using suitable cross-linking agents for these reactive silicones. Crosslinking can contribute significantly to the three-dimensional bonding and strength of the polymer film. This is particularly important for reinforcing or anchoring the membrane to the surface of the fibres. Also, without wishing to be bound by theory, it is believed that the adhesion strength to the fiber (associated with "durability") can be significantly improved by the interaction and/or bonding between the silanol groups from the reactive silicone and various functional groups (e.g., -OH) on the fiber surface. In addition, the enhanced entanglement throughout the volume of the film improves the cohesive strength of the film and contributes (e.g., by steric hindrance) to the stability of the fiber-film bond. In some embodiments, reinforcing fillers for these reactive silicones are incorporated into the formulation. The reinforcing filler may comprise, consist essentially of (greater than 50% by weight or volume), or consist essentially of: three-dimensional reactive fillers (e.g., fumed silica). Fumed silica is hydrophobic in the sense that it is not self-dispersing in water. However, in the reactive AS-containing phase, the hydrophobic three-dimensional reactive filler is preferably selected and/or adapted so AS to be self-dispersible, at least to some extent (i.e., dispersed to an average particle diameter of submicron order (e.g., 200nm for D50 by volume) or less, in the reactive AS-containing phase), so that the hydrophobic three-dimensional reactive filler particles can easily serve AS nucleation centers to rapidly promote strong three-dimensional crosslinking. In this way, both the cohesion of the film and the adhesion to the fiber surface are improved in a relatively short time frame, and generally before the condensation cure is nearly complete.
It must be emphasized that the presence of such fillers in the formulation does not in itself represent any functionality as a three-dimensional reactive filler. For example, fumed silica can be used as a thickener in various industrial applications known in the art. In this case, and assuming that thickening is for an aqueous medium, fumed silica will naturally be hydrophilic. However, in order to be useful as a reactive three-dimensionally crosslinked filler, it is necessary to dispose the filler (e.g., hydrophobic fumed silica) in the reactive phase of the formulation (in this case, the aqueous phase containing the reactive aminosilicone material).
It has further been found that such fillers can be used to overcome or significantly mitigate mass transfer limiting kinetics throughout the condensation curing process. Generally, such fillers are characterized by a very high specific surface area. The total external and internal specific surface areas of porous solids (e.g., fumed silica) can be determined by measuring the amount of physisorbed gas according to the Brunauer-Emmett-teller (bet) method. The specific surface area may be determined according to ISO 9277, in one embodiment the specific surface area is at least 25m2/g, at least 50m2/g or at least 75m2/g, more typically at least 100m2/g, at least 110m2/g or at least 120m2/g, and/or in the range of 25-400m2/g, 60-400m2/g, 60-300m2/g, 80-400m2/g, 80-350m2/g, 80-300m2/g, 90-400m2/g, 90-350m2/g, 90-300m2/g or 100-350m 2/g. These packing materials may have a low concentration of adsorbed water (e.g., about 0.5%) uniformly distributed at the same time. Thus, this lower but evenly distributed and available water content can be used to partially bypass or circumvent the mass transfer limitations of water diffusing from the environment through the membrane to the fiber surface when the packing material is disposed in the reactive phase of the formulation.
This effect can be enhanced by using reactive filler materials with relatively high water concentrations (e.g., at room temperature, as close to the saturation point as practical, and/or with reactive filler materials with particularly high specific surface areas). Indeed, in some embodiments, a pre-treatment step has been introduced in which the solid reactive filler material is exposed to saturated water vapor to significantly increase its water concentration. A corresponding improvement in the durability of the film was observed.
It has also been found that water can additionally or alternatively be added to the liquid component of the reactive oil phase to achieve similar improvements. Referring to fig. 5, a method of introducing a known amount of a pretreatment solution (e.g., water) into the reactants of a condensation-curable aminosilicone emulsion, according to some embodiments, is illustrated. For the purposes of this description, the term "reactant" refers to any material that participates in the pretreatment, whether or not the material is reactive to the condensation cure of the final emulsion prepared using water-enriched or pretreated reactants. Thus, the term reactant may encompass reactive condensation curable amino silicone prepolymers, as well as amino silicone oils, non-amino silicone oils, crosslinkers, solid reactive fillers, and pigment dispersants that are present to some extent in the reaction oil phase. Depending on the initial amount of water in the supplied reactants, a preliminary optional drying step S101 may need to be performed. Such a step may help to better control the amount of pretreatment solution added to reactants that may have fluctuating natural water content, thereby reducing variations that may result from such natural content.
Various methods of drying the reactants (e.g., water-rich reactants) to remove excess water are known to those skilled in the art. The drying method can be chosen and adapted to the reactants to be dried. For example, a solid reactant (e.g., a reactive filler of hydrophobic fumed silica) can be dried in an oven to evaporate excess water. For liquid reactants such as reactive condensation curable amino silicone prepolymers, certain crosslinkers or silicone oils, excess water can be removed using molecular sieves having pores suitable for selective capture of water. After step S101 (if desired), the reactant is correspondingly dried substantially dry with minimal, if any, residual water. The dried or dried reactants are typically stored in a desiccator under a more extensive dry inert atmosphere or vacuum to ensure that the water content of each reactant (if any) is kept to a respective minimum before use. When less than 1 wt.% water, or less than 0.5 wt.%, or less than 0.1 wt.%, or less than 0.05 wt.%, or less than 0.01 wt.% water, based on the weight of the reactants, is included, the reactants are substantially dry.
In step S102, the dried reactants are supplemented with a known amount of water or any desired aqueous pre-treatment solution. The step S102 of controlling the addition of water may also be referred to as a humidification step, and the humidified reactant may also be referred to as a premix or a pretreated reactant. In some embodiments, the amount of water added exceeds the amount of water that the reactants typically absorb in their naturally supplied state (e.g., by at least 25% or more or even by at least one order of magnitude). For a particular pretreatment, the individual reactants of the pretreatment composition may be humidified. However, for pretreatment compositions according to other embodiments, more than one reactant may be humidified separately. The reactants, including at least one humidified reactant, are mixed in step S103 to form a pretreatment composition at time point 0. Alternatively, at least one of the humidified reactants may be separately humidified and pretreated to form a "pretreated" mixture after such separate pretreatments. Assuming that the amount of water added is sufficiently small, the pretreatment composition forms a homogeneous oil phase (no distinct detectable separation of the aqueous phase). The pre-treated oil phase was very clear (no turbidity) further confirming that the water addition was sufficiently low. The aqueous pretreatment solution is typically added gradually to the dried or dried reactants to achieve a more gradual and uniform adsorption of water, thereby reducing the risk of phase separation.
In some embodiments, the water (or aqueous pretreatment solution) comprises 10 wt% or less, or less than 5 wt%, or less than 4 wt%, or less than 3 wt%, or less than 1 wt% of the weight of the reactants; optionally at least 0.1 wt%, or at least 0.2 wt% or at least 0.3 wt% of the weight of the reactants. In some embodiments, the amount of water (or aqueous pretreatment solution) added to the reactants is 10 wt% or less, or less than 5 wt%, or less than 4 wt%, or less than 3 wt%, or less than 1 wt%, based on the weight of the reactants; optionally, the amount of water added is at least 0.1 wt%, or at least 0.2 wt% or at least 0.3 wt%, based on the weight of the reactants.
In some embodiments, the water (or aqueous pre-treatment solution) comprises 2.5 wt% or less, or less than 2 wt%, or less than 1 wt%, or less than 0.5 wt% of the oil phase weight; optionally, at least 0.01 wt%, or at least 0.05 wt% or at least 0.1 wt% of the oil phase weight. In some embodiments, the total amount of water (or aqueous pre-treatment solution) in the at least one reactant added to the oil phase is 2.5 wt% or less, or less than 2 wt%, or less than 1 wt%, or less than 0.5 wt%, based on the weight of the oil phase; optionally, the amount of water added to the at least one reactant is at least 0.01 wt%, or at least 0.05 wt% or at least 0.1 wt% based on the weight of the oil phase.
In some embodiments, in the oil phase or the pre-treated oil phase, the volume ratio of oil phase to water phase is at least 9: 1, at least 9.5: 0.5, or at least 9.75: 0.25; the oil phase or pre-treated oil phase is optionally completely free of aqueous phase.
It should be noted that the amount of the aqueous pretreatment solution added to the reactants is negligible compared to the amount of water or aqueous medium around the droplets after emulsification of the oil phase. It has been determined that the water phase of the emulsion contributes only slightly to the process initiated by the in vitro pretreatment. It is believed that the surrounding water can only interact with the outer surface of the oil droplets and that further diffusion towards the interior of the oil droplets is in fact very slow. For similar reasons, water present on the hair fibres or further added as a humectant does not function in a comparable manner to the pretreatment. In this particular case, it is further believed that the oil droplets tend to repel such water (making them unusable for film formation) after they are deposited onto the hair fibers. The presence of water in the oil phase is believed to mitigate the slow diffusion of such molecules from external/ambient sources.
The pretreatment composition of step S103 may then be incubated in step S104 for any predetermined amount of time. The incubation may be carried out at room temperature (about 23 ℃) or at any other temperature, typically not exceeding 50 ℃ when above ambient temperature. It is believed that the amount of water is sufficient to initiate hydrolysis of at least a portion of the hydrolyzable moieties of the associated reactants during the incubation period of the pretreatment composition. Although complete hydrolysis is not sought during the pretreatment stage, it is understood that even in this case the prepolymer may remain reactive toward condensation cure. The fact that the prepolymer is still reactive can be readily demonstrated by the fact that the pretreatment composition is still liquid and/or lacks a glass transition temperature.
After incubation, the pre-treated oil phase may be added to the desired aqueous phase (e.g., with or without the addition of an emulsifier) to perform the emulsification in step S105. After this step, the reactive condensation curable aminosilicone emulsion is ready for application. The actual application to the hair fibers S106 can generally be carried out within 30 minutes after emulsification.
Without wishing to be bound by any particular theory, it is believed that the trace amount of water (or aqueous pretreatment solution) present in the pretreatment composition (i.e., in the reactive oil phase) can promote hydrolysis of the hydrolyzable portion of the reactive reactants. This partial in vitro hydrolysis in turn may promote condensation curing of the hydrolyzed portion of the reactive reactant (i.e., the aminosilicone prepolymer). It has been found that triggering the in vitro condensation cure of the aminosilicone prepolymer once applied to the hair fibre accelerates its ongoing condensation and thus generally reduces the time required for complete cure. The incubation time of the pretreatment composition (which may depend on, for example, the temperature, the type of aqueous pretreatment solution, the amount and total amount of each reactant added, and the like) should be sufficient to provide such triggering, but short enough to ensure that the aminosilicone prepolymer applied after emulsification is still reactive and capable of condensation curing on the hair fibers after it is applied to the hair fibers.
Fig. 3A is a schematic diagram showing the change in hydroxyl group concentration over time in an in vitro pretreatment reaction of a reactive aminosilicone formulation (e.g., an oil-in-water emulsion), according to embodiments of the present disclosure. The times shown (along the X-axis) are qualitative and illustrative, as the absolute time may be slower or faster depending on the particular prepolymer, formulation ingredients, and operating parameters.
According to some embodiments of the present disclosure, the reaction is carried out in a pH range of 7.5 to 12, and more typically between 8 to 11, or between 8 to 10.5. It is believed that the initial increase in hydroxyl concentration results from the hydrolysis of the hydrolyzable groups (typically alkoxy, acyloxy and/or oxime) to form silanol groups. This initial rise may begin to level off as the rate of hydroxyl radical generation slows. The relatively slow curing reaction continues over time and the silanol groups polymerize through a condensation reaction to produce siloxane bonds (and release water). The condensation reaction consumes hydroxyl groups such that the hydroxyl group concentration decreases as the reaction time progresses.
Fig. 3B is a schematic illustrating the hair coloring effect of the partially reacted aminosilicone formulation of fig. 3A applied to hair fibers as a function of the in vitro reaction time of the pretreatment formulation prior to application of the partially reacted formulation to hair fibers. As further detailed herein, the resulting partially reacted aminosilicone formulation is then emulsified with water (with or without other additives, such as emulsifiers or pH adjusters) to produce a hair care emulsion that can be applied directly to hair fibers. As can be seen from the qualitative curve provided in fig. 3B, effective dyeing of the hair fibers can be obtained even at t ═ 0, which corresponds to no in vitro reaction of the reactive aminosilicone formulation prior to application of the formulation to the hair fibers. It has been found that a higher hair colouring effect can be maintained for a longer period of time before a relatively high degree of cross-linking is achieved. Then, as the degree of crosslinking is continuously increased, the hair dyeing effect may be reduced or significantly reduced. It is believed that the highly cross-linked material achieves poor hair wetting when the partially cured aminosilicone formulation is applied to hair, and that many of the polymer embedded pigments are simply washed off when excess material is removed. This state is represented, for example, by point a in fig. 3B.
This result obtained with highly crosslinked materials appears to be evidenced by the failure to obtain satisfactory initial dyeing of hair fibers with various disclosed non-reactive amino silicone based hair coloring formulations and methods. Such cross-linked silicones not suitable for use in the present teachings are generally referred to as silicone resins, and as explained, are characterized as having at least one of a high molecular weight, a high viscosity (or even solid at ambient temperature), or a glass transition temperature (Tg).
Moreover, even if a satisfactory initial dyeing is achieved, for example, by a formulation comprising a material that is not highly crosslinked enough to wet the hair fibre surface, such a formulation apparently does not exhibit durable dyeing properties (e.g. wash fastness). This state is represented, for example, by point B in fig. 3B. Point B is also shown in fig. 3C, which provides a schematic illustrating hair dye persistence versus in vitro reaction time of a partially reacted AS formulation prior to emulsification of the formulation and application to the hair fibers. Clearly, staining appeared satisfactory for in vitro reaction times at point B, but the persistence was low.
As provided in further detail herein, the dye durability is measured after removal of an excess applied formulation from the hair and subsequent allowing the applied formulation to cure on the hair fibers under ambient conditions (e.g., for 24 hours). Fig. 3C schematically shows the durability assessed by wash fastness of the stain 24 hours after application. As described below and in the examples, in some embodiments, the pretreatment of the reactive oil phase allows the persistence of the stain to develop at an earlier time point within 24 hours after staining.
AS substantially described above, it is believed that incomplete curing in the region of the membrane closest to the surface of the fiber significantly reduces dye durability due to mechanical forces at the interface between the AS membrane and the outer surface of the fiber and susceptibility to intercalation and chemical attack.
It must be emphasized that the various aminosilicone formulations considered "reactive" are in fact substantially non-reactive, since these formulations are already highly cross-linked before application, so that the degree of additional cross-linking occurring after application may be small (especially under ambient conditions) and may not be sufficient to achieve a satisfactory (initial) dyeing. Alternatively, the initial dyeing may be satisfactory, but the durability may be poor, or unsatisfactory.
Referring again to fig. 3C, it is evident from this qualitative curve that the dye durability of the hair fibers may not be satisfactory at t ═ 0, corresponding to the absence of an in vitro reaction of the reactive aminosilicone formulation prior to application of the formulation to the hair fibers. Although effective hair fibre dyeing can be achieved in a very short in vitro reaction time, it has been found that, AS mentioned, the hair dyeing durability may be unsatisfactory, in part because of the very low degree of cross-linking at the interface between the AS membrane and the outer surface of the fibre. As shown by the first shoulder C, as the level of crosslinking at the interface increases with time, the durability increases accordingly. As shown by the durability plateau D, the durability may plateau or substantially plateau as the level of crosslinking at the interface further increases over time.
Fig. 3D is a schematic diagram showing the hair tack of the partially reacted aminosilicone formulation of fig. 3A applied to hair fibers as a function of the in vitro reaction time of the formulation prior to application of the formulation to hair fibers.
It is believed that as the cross-linking increases, the viscosity of the hair decreases.
Thus, by controlling in vitro reaction times and operating conditions, methods as contemplated herein enable operation within an overlap of dyeing, viscosity, and durability "time windows" ("windows") to achieve sufficient hair dyeing (e.g., as characterized by optical density, etc.) and dyeing durability.
Furthermore, it has surprisingly been found that the pH of the pre-treatment solution of reactants used to humidify the in vitro reaction mixture can be controlled to accelerate the hydrolysis and condensation reactions, thereby reducing the viscosity almost immediately (e.g. at short in vitro reaction times of up to 10 minutes) and/or broadening the overlapping range of dyeability, viscosity and durability time windows. More specifically, the pH of the pretreatment solution should be at most 2.5, at most 2, more typically at most 1.8, at most 1.6, at most 1.4, or at most 1.2. The pH should range between 0.5 to 2.5, 0.5 to 2.0, 0.7 to 1.8, 0.7 to 1.6, 0.7 to 1.4, 0.7 to 1.2, 0.9 to 2.0, 0.9 to 1.7, 0.9 to 1.5, 0.9 to 1.3, or 0.9 to 1.2.
However, it has been found that typical acids used to lower the pH can contribute a "persistent" ionic content to the reaction mixture, which can ultimately impair the performance of the aminosilicone membrane.
Surprisingly, it has been found that by lowering the pH using a volatile acid (preferably concentrated acetic acid, e.g. containing at least 30%, at least 40%, at least 50%, at least 60% or at least 80% concentrated acetic acid), the pH of the pretreatment solution can be lowered sufficiently to advantageously adjust the time window of the in vitro reaction and can also be volatilized such that there is no residual ionic content in the acid. Thus, the necessary in vitro reaction time can be reduced, reaction control can be relaxed, and the robustness of the process can be improved, all without introducing contaminants through the acidifying agent.
Fig. 4 provides a schematic illustrating the degree of hydrolysis (detectable by hydroxyl/silanol concentration), hair coloring effect, hair stickiness, and hair coloring longevity of a reactive aminosilicone formulation based on the formulation of fig. 3A (or of the formulation using a pH adjusted aqueous pre-treatment solution) as a function of its in vitro reaction time (prior to application of the partially reactive formulation to hair fibers).
Thus, the duration of the pretreatment may depend, inter alia, on the type and onset of the desired result, as well as the type of pretreatment solution and its total concentration in the reactive oil phase, based on the presence of the reactants of the respective pretreatment. In some embodiments, the pretreatment period is no more than 24 hours, or less than 12 hours, less than 8 hours, less than 6 hours, or less than 4 hours. Advantageously, the pretreatment period may be 120 minutes or less, less than 90 minutes, less than 60 minutes, less than 30 minutes, less than 20 minutes, less than 10 minutes, or less than 5 minutes.
Since the rate of hydrolysis and/or (partial) condensation curing may depend on the temperature, the pretreatment period may be shortened as the pretreatment temperature is increased. Although the pretreatment may conveniently be carried out at ambient temperature, it may alternatively be carried out at an elevated temperature, typically not exceeding 60 ℃. In some embodiments, the pretreatment is performed at a temperature in the range of 15-50 ℃, 18-45 ℃, 20-40 ℃, 20-35 ℃, 20-30 ℃, or 20-25 ℃.
Thereafter, the reactive oil phase pretreated in accordance with the present teachings can be emulsified to prepare an oil-in-water emulsion of the reactive condensation curable aminosilicone prepolymer to meet the corresponding teachings in connection with an emulsion to be applied to hair fibers in accordance with the present disclosure.
According to some embodiments, the reactive condensation curable amino-functional silicone prepolymer is present in a concentration in the range of about 0.001 to 20 weight percent based on the total weight of the composition (e.g., oil-in-water emulsion), for example about 0.005 to 10 weight percent, about 0.005 to 5 weight percent, about 0.005 to 2.5 weight percent, or 0.01 to 1 weight percent based on the total weight of the composition.
According to some embodiments, the concentration of the reactive condensation curable amino-functional silicone compound is at least 45 wt%, at least 55 wt%, at least 60 wt%, or at least 65 wt%, and optionally in the range of 50-100 wt%, 50-95 wt%, 50-90 wt%, 50-85 wt%, 50-80 wt%, 55-95 wt%, 55-85 wt%, 60-95 wt%, 60-85 wt%, 65-95 wt%, 65-90 wt%, or 70-95 wt%, by weight of the oil phase.
According to some embodiments, the total concentration of amino silicone oil is at most 30 wt%, at most 20 wt%, at most 15 wt%, at most 10 wt%, or at most 5 wt% by weight of the oil phase.
According to some embodiments, the total concentration of non-amino silicone oil is at most 15 wt%, at most 12 wt%, at most 10 wt%, at most 7 wt%, or at most 5 wt% by weight of the oil phase.
According to some embodiments, the sub-micron pigment particles comprise an organic pigment, for example an organic pigment selected from the group consisting of perylene pigments, phthalocyanine pigments, quinacridone pigments and imidazolinone pigments.
According to some embodiments, the submicron pigment particles comprise an inorganic pigment, such as an inorganic pigment selected from the group consisting of titanium dioxide, cadmium sulfoselenide, iron oxide, bismuth vanadate, cobalt titanate, sodium aluminum sulfosilicate, mixed oxides of Fe-Mg-Ti, manganese ferrite, and metal or alloy pigments.
In some embodiments, submicron organic or inorganic pigments (or combinations thereof) are used as the color-imparting agent. Submicron pigments may also be referred to as light absorbing pigments or simply light absorbing pigments.
According to some embodiments, the sub-micron pigment is an organic or inorganic pigment selected from the group consisting of pigments approved by the european union for cosmetic use: CI 10006, CI 10020, CI 10316, CI 11680, CI 11710, CI11725, CI 11920, CI 12010, CI 12085, CI 12120, CI 12370, CI 12420, CI 12480, CI12490, CI 12700, CI 13015, CI 14270, CI 14700, CI 14720, CI 14815, CI 15510, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI15980, CI 15985, CI 16035, CI 16185, CI 16230, CI 16255, CI 16290, CI 17200, CI18050, CI 18130, CI 18690, CI 18736, CI 18820, CI 18965, CI 19140, CI 20040, CI20470, CI 21100, CI 21108, CI 21230, CI 26100, CI 27755, CI 40440, CI 42042082, CI 42042080, CI 42042042042080, CI 4204280, CI 4204204280, CI 42510, CI42080, CI 4280, CI 42042042048, CI 4280, CI 42048, CI 4280, CI 42048, CI 4280, CI 42048, CI 4280, CI42080, CI42, CI44090, CI 45100, CI 45190, CI 45220, CI 45350, CI 45370, CI 45380, CI 45396, CI45405, CI 45410, CI 45430, CI 47000, CI 47005, CI 50325, CI 50420, CI 51319, CI58000, CI 59040, CI 60724, CI 60725, CI 60730, CI 61565, CI 61570, CI 61585, CI62045, CI 6980, CI 69800, CI 71105, CI 73000, CI 73015, CI 73360, CI 73385, CI73900, CI 73915, CI 74100, CI 74160, CI 74180, CI 74260, CI 75100, CI 75120, CI75125, CI 1075130, CI 75135, CI 75170, CI 75300, CI 75470, CI 75810, CI 77000, CI77007, CI 77266, CI 77267 77268, CI 77268: 1. CI 77891, CI 77947, riboflavin, caramel, capsorubin, beetroot red, anthocyanins, bromothymol blue, bromocresol green, and acid red 195.
According to some embodiments, the submicron pigment is selected from the group consisting of the following U.S. approved organic pigments for cosmetic use:
15D&C Black No.2,D&C Black No.3,FD&C Blue No.1,D&C Blue No.4,D&CBrown No.1,FD&C Green No.3,D&C Green No.5,D&C Green No.6,D&C Green No.8,D&COrange No.4,D&C Orange No.5,D&C Orange No.10,D&C Orange No.11,FD&C Red No.4,D&C Red No.6,D&C Red No.7,D&C Red No.17,D&C Red No.21,D&C Red No.22,D&C RedNo.27,D&C Red No.28,D&C Red No.30,D&C Red No.31,D&C Red 20No.33,D&C RedNo.34,D&C Red No.36,FD&C Red No.40,Ext D&C Violet No.2,FD&C Yellow No.5,FD&CYellow No.6,D&C Yellow No.7,Ext.D&C Yellow No.7,D&C Yellow No.8,D&C YellowNo.10and D&C Yellow No.11。
in some embodiments, the pigments of the present compositions provide special visual effects in place of or in addition to the coloring effect and/or metallic appearance. By way of non-limiting example, special effects include fluorescent effects, sparkling effects, pearlescent effects (pearlescence effects), nacreous effects (nacreous effects), and phosphorescent effects. These effects may be visible under conventional lighting or may require (or further increase) special viewing conditions, e.g. in relation to lighting conditions, viewing angle, etc. For example, fluorescent pigments may become visible or may provide a fluorescent effect when exposed to Ultraviolet (UV) radiation. At the other end of the spectrum, upconverting pigments are luminescent materials capable of converting near infrared (NlR) light to Visible (VIS) light. Other colorants that provide less typical colorations also include, as non-limiting examples, thermochromic pigments or dyes that cause compositions containing them to change color as a result of temperature changes; and a pH-dependent pigment, the color of which is pH-adjusted.
Any of the above pigments may be further surface treated (e.g., with an organic agent) to further improve any desired properties of the pigment (e.g., visual effect, chemical stability, dispersibility, charge, adhesion to fibers, ability to interact with an aminosilicone matrix, etc.). Surface treatment techniques need not be described in detail herein, and surface-treated pigments are commercially available in the desired form (e.g., nonionic, cationic, anionic, or positively, negatively, or substantially uncharged). The surface treatment of the pigment particles may be a chemical coating, and may be, for example, a fatty acid such as oleic acid, stearic acid; adhesion promoting polymer coatings, such as acrylic polymers, silane polymers, or aminosilane polymers; and such chemical coatings known in the pigment art.
All such pigments, which are suitable for the substrate into which they are incorporated, can be used in all aspects and embodiments of the method for coloring hair of the present invention and kit thereof. In one embodiment, when pigments are desired in the aminosilicone coating, the pigment particles may be surface treated (e.g., by acid groups) to improve the interaction between the pigments and the aminosilicone prepolymer encapsulating them during formation of the aminosilicone 3D network on the hair fibers. However, such pigment treatments may be redundant or even undesirable because the pigments, when incorporated into the polymeric coating, are mixed differently in the polymeric material having neutralizable acid moieties. The color-imparting agents used in the present disclosure are pigments, which may optionally be combined with or replaced by dyes in certain cases (e.g., for slight coloration). However, even when dyes are used as color-imparting agents in compositions or pigment coatings, they are not oxidative dyes. In some embodiments, the compositions according to the present teachings are substantially free of oxidative dyes and any chemical agents conventionally used in combination with oxidative dyes, including, as non-limiting examples, couplers of dyes and oxidizing agents (e.g., hydrogen peroxide developers).
In some embodiments, the pigment is reduced in size and/or dispersed prior to incorporation into the reactive oil phase of the emulsions of the present invention. In this case, the size reduction and/or dispersion step may be carried out in the presence of a pigment dispersant. According to some embodiments, the pigment dispersant is present in the oil-in-water emulsion in an amount of from 25% to 400% by weight of the submicron pigment particles. In some embodiments, the dispersant and pigment particles are present in a relative weight to weight ratio in the range of 0.5: 1 to 2:1, 0.75: 1 to 1.5: 1, or 0.8: 1 to 1.2: 1.
According to some embodiments, a dispersant suitable for dispersing pigments is compatible with the condensation curable formulation. By compatible is meant, for example, that the pigment dispersant is miscible in the reactive oil phase of the formulation, that the pigment dispersant does not delay, reduce, or interfere with condensation curing, and that the pigment dispersant is stable (e.g., non-reactive) during pigment size reduction. Preferably, the pigment dispersant may have a positive charge.
Such dispersants may have a silicone backbone, such as silicone polyether dispersants and silicone amine dispersants. Suitable pigment dispersants include, for example, silicone amines such as BYK LPX 21879 from BYK, GP-4, GP-6, GP-344, GP-851, GP-965, GP-967 and GP-988-1 from Genesee Polymers; silicone acrylates, such as from Evonik902、922、1041 and1043; PDMS silicones with carboxyl functionality such as X-22162 and X-22370 from Shin-Etsu; silicone epoxies, such as GP-29, GP-32, GP-502, GP-504, 15GP-514, GP-607, GP-682 and GP-695 from Genese Polymers, or from Evonik1401、
In some embodiments, the amine value of the pigment dispersant, which is an amino silicone, is in the range of 3 to 1,000, 3 to 500, or 3 to 200.
Pigment dispersants having functional groups capable of reacting with the reactants of the reactive oil phase may advantageously further improve the aminosilicone 3D network formed therefrom, in addition to facilitating pigment dispersion itself. For example, the silicone epoxy pigment dispersant may advantageously interact with the amine moiety of the amino silicone prepolymer to further increase the cohesion of the colored amino silicone film.
In general, a material used in a composition according to the present teachings is said to be compatible with other materials if it does not hinder the activity of the other materials or reduce the activity to a degree that would significantly affect the intended purpose. For example, pigment dispersants are incompatible if, among other factors, they hinder the curing of condensation-curable aminosilicone prepolymers, or reduce or delay the curing to such an extent that the aminosilicone film does not adhere sufficiently and/or quickly to the substrate hair fibers, or are harmful to the pigment, and there are any similar undesirable effects. In some embodiments, compatibility may additionally mean that materials considered to be compatible have common characteristics, such as common silicone-based chemistry or similar physical parameters. For example, materials with similar refractive indices (RIs within ± 10% of each other) are considered to produce a sharper cured film compared to materials with relatively different Refractive Indices (RI) that may appear more hazy.
According to some embodiments, the plurality of pigment particles present in the reactive oil phase may be a mixture of different pigments, each pigment providing a different color or a different shade of the same color.
Depending on their morphology, particles (e.g., submicron (light absorbing) pigments, reinforcing fillers, etc.) may be characterized by any such representative measurement of their length, width, thickness, diameter, or their X, Y and Z dimensions. Typically, such dimensions are provided as an average of the population of particles and are provided by the manufacturer of such materials. These dimensions may be determined by any technique known in the art, such as microscopy and Dynamic Light Scattering (DLS). In DLS techniques, the particles approximate spheres with equivalent behavior, and the dimensions can be provided from the perspective of the hydrodynamic diameter. DLS also allows the size distribution of the population to be assessed. The same applies to droplets and may for example help to characterize all emulsion droplets which generally have a spherical shape. As used herein, particles having a size of, for example, 1 μm or less have at least one, and possibly two or even three, sizes equal to or less than 1 μm, depending on the shape. When referring to emulsion droplets, for example having a size of 5 μm or less, the droplets are understood to have an average diameter (Dv50) equal to or less than 5 μm.
Although not required, the particles or emulsion droplets of any particular species may preferably be uniform in shape and/or within a symmetric distribution with respect to the median of the population and/or within a relatively narrow size distribution for that particular species. Hereinafter, unless the context clearly indicates otherwise, the term "particle" refers to both solid particles (e.g., pigments, etc.) and liquid droplets (e.g., emulsion droplets, micelles, etc.).
The Particle Size Distribution (PSD) is said to be relatively narrow if at least one of the following two conditions applies:
A) the difference between the hydrodynamic diameter of 90% of the particles and the hydrodynamic diameter of 10% of the particles is equal to or less than 150nm, or equal to or less than 100nm, or equal to or less than 50nm, which can be expressed mathematically as follows: (D90-D10) is less than or equal to 150nm, and so on; and/or
B) The ratio between a) the difference between 90% and 10% of the hydrodynamic diameter of the particles and b) the hydrodynamic diameter of 50% of the particles is not more than 2.0, or not more than 1.5 or not more than 1.0, which can be expressed mathematically as follows: (D90-D10)/D50-2.0, and so on.
D10, D50 and D90 can be determined by the total number of particles, in which case they can be provided in the form of
As noted above, for some applications, such a relatively uniform distribution may not be necessary. For example, a population of submicron pigment particles having relatively non-uniform sizes may allow relatively smaller particles to reside in interstices formed by relatively larger particles in a coating formed therefrom, thereby providing, in combination, a relatively uniform coating.
A particle may be characterized by an aspect ratio in relation to its shape, which refers to the dimensionless ratio between the smallest dimension of the particle and the longest dimension or equivalent diameter in the largest plane orthogonal to the smallest dimension. The equivalent diameter (Deq) is defined by the arithmetic mean between the longest and shortest dimensions of the largest orthogonal plane. Particles having an approximately spherical shape and emulsion droplets therein are characterized by an aspect ratio of about 1: 1, wherein rod-shaped particles may have a high aspect ratio, whereas plate-shaped particles may even have an aspect ratio of at most 1: 100 or even more.
Such characteristic dimensions are usually provided by suppliers of such particles, andand a variety of representative particles may be evaluated by methods known in the art, such as microscopy, including, in particular, by optical microscopy for particles of several microns or down to an estimated size of about 200nm, by scanning electron microscopy SEM (SEM is particularly suitable for planar dimensions) for smaller particles having a size of less than 200nm, and/or by focused FIB ion beam (preferably for the thickness and length (long) dimensions of submicron particles, also referred to herein as nanoparticles or nanoscale particles), in selecting a representative particle or a set of representative particles that can accurately characterize a population (e.g., by diameter, longest dimension, thickness, aspect ratio, and similar particle characterization methods), it should be understood that more statistical methods may be required3/m]1/3Where m represents the number of particles in the field of view and the sum is taken over all m particles. As mentioned above, when such a method is a technique chosen for the scale of the particles to be studied or in view of their medium, such a measurement may be referred to as D50.
According to some embodiments, the sub-micron pigment comprises an average particle Dv50 of at most 1,000nm, at most 750nm, at most 500nm, at most 250nm, at most 150nm, or at most 100nm, and optionally, Dv10 of at least 10nm, at least 25nm, or at least 50 nm. In some embodiments, the submicron pigment particles range between a Dv10 of at least 10nm and a Dv90 of at most 2,500nm, or between a Dv10 of at least 25nm and a Dv90 of at most 1,500nm, or between a Dv10 of at least 50nm and a Dv90 of at most 1,000 nm.
According to some embodiments, the sub-micron pigment comprises predominantly the following particles: dv90 is at most 1,000nm, at most 750nm, at most 500nm, at most 250nm, at most 150nm or at most 100nm, and optionally Dv50 is at most 300nm, at most 250nm, at most 200nm, at most 150nm, at most 100nm or at most 75 nm. In some embodiments, the Dv10 of the submicron pigment particles is at least 10nm, at least 25nm, or at least 50 nm. In some embodiments, the submicron pigment particles range between a Dv10 of at least 10nm and a Dv90 of at most 1000nm, or between a Dv10 of at least 25nm and a Dv90 of at most 750nm, or between a Dv10 of at least 25nm and a Dv90 of at most 500 nm.
According to some embodiments, the compositions or kits disclosed herein further comprise a cross-linking agent, such as an organosilicon compound capable of reacting through all of the non-amino-reactive groups of the reactive silicone, and a cross-linking agent comprising a mercapto, epoxy or acrylate group capable of reacting through the amino-reactive groups of the reactive silicone. Typically, the crosslinking agent comprises at least three reactive groups for forming a network of oligomers and polymers, thereby creating an elastomeric network.
The organosilicon crosslinker must have hydrolyzable groups (Y).
After hydrolysis, the resulting silanol groups can undergo a condensation reaction with the reactive amino silicone prepolymer to give siloxane linkages.
The silicone crosslinker may comprise:
a tetrafunctional hydrolyzable group and consisting, for example, of a silane having Q units (SiO4/2), such as SiY4,
-or a trifunctional hydrolyzable group and consisting ofaSilane or siloxane oligomer composition of T units of SiO3/2, e.g. RaSiY3，
Or a difunctional hydrolyzable group and is of the formula RbSilane or siloxane oligomer composition of D units of 2SiO2/2, e.g. Rb2SiY2, provided that the crosslinker has a total of at least three hydrolyzable groups,
or monofunctional hydrolyzable groups having M units, provided that the crosslinker has a total of at least three hydrolyzable groups, wherein the hydrolyzable group (Y) may be selected from
Alkoxy (e.g., methoxy, ethoxy, propoxy, isopropoxy, methoxyethoxy, etc.),
oximes (e.g. methyl ethyl ketoxime),
Acyloxy (e.g., acetoxy),
wherein the Ra and Rb substituents are selected from
-C1-C6 or C1-C4 alkyl,
Alkenyl (vinyl, allyl, etc.), alkenyl (vinyl, allyl, etc.), (ii),
Aminoalkyl (monoamino, such as aminopropyl NH2(CH2) 3; diamino, such as aminoethylaminopropyl NH2(CH2)2NH (CH2) 3; or triamino)
Epoxy groups (e.g. glycidoxypropyl groups),
Acrylate groups (e.g. methacryloxypropyl) and,
Mercapto (e.g. mercaptopropyl),
According to some embodiments, the cross-linking agent may be a branched or linear polyorganosiloxane comprising at least one of Q units, T units, D units, and M units, provided that the total amount of hydrolyzable groups and/or silanol in the cross-linking agent is at least 3, such that a 3D network may be formed. When mixtures of crosslinking agents are used, at least one crosslinking agent in the mixture must contain a total of at least three hydrolyzable groups and/or silanol.
According to some embodiments, the cross-linking agent may be: ethyl silicates such as tetraethyl silicate (CAS number: 78-10-4); poly (diethoxysiloxane) oligomers, such as Evonik40 having a fully hydrolyzed silica content of about 40-42%;ethyl silicate 48(CAS number: 11099-06-2) having a silica content of about 48% after complete hydrolysis; poly (dimethoxysiloxane) (CAS number 25498-02-6); 3-epoxypropyloxypropyltrimethoxysilane of Evonik; carbodilite Emulsion E-05 with 40% multifunctional polycarbodiimide in anionic Emulsion; and Carbodilite V02-BIt has 100% multifunctional polycarbodiimide.
According to some embodiments, the crosslinking agent may be a reactive aminosilicone monomer, such as aminopropyltriethoxysilane (CAS number: 919-30-2), bis (triethoxysilylpropyl) amine (CAS number: 13497-18-2), or mixtures thereof.
According to some embodiments, the crosslinking agent is a non-amino silicone having a molecular weight of less than 1000g/mol, and thus comprises, consists essentially of, or consists of a reactive condensation curable film-forming non-amino silicone monomer. In some embodiments, the total concentration of non-amino crosslinkers is at most 35 wt.%, at most 30 wt.%, at most 20 wt.% 5%, at most 15 wt.%, or at most 10 wt.%, or at most 5 wt.%, based on the weight of the oil phase.
The term "consisting essentially of," as used herein in the specification and in the claims section that follows, generally with respect to a component in a formulation, means at least 50% by weight of the component.
According to some embodiments, the following in the oil phase: an amino silicone prepolymer which is reactive and can be condensed and cured to form a film; amino silicone oils and non-amino silicone oils; a non-amino crosslinking agent; and a reactive filler comprising any pigment particles and a dispersant for said pigment particles in a total concentration of at least 90, at least 93, at least 95, at least 97, at least 98 or at least 95 weight percent based on the weight of the total composition.
According to some embodiments, the oil-in-water emulsion is prepared in the presence of a non-ionic emulsifier having a Hydrophilic Lipophilic Balance (HLB) preferably on the Griffin scale of from 12 to 18, from 12 to 17, from 12 to 16, from 12 to 15, or from 13 to 16. The emulsion may be prepared by a variety of emulsification techniques known to those skilled in the art. Although manual agitation may be sufficient, various devices may be used, such as vortex mixers (vortex), overhead stirrers, magnetic stirrers, ultrasonic dispersers, high shear homogenizers, sonicators, planetary centrifuges, and the like, which generally provide a more uniform population of oil droplets in the aqueous phase. The emulsion can be easily applied after its preparation or within a period of time that remains suitably stable. For example, the emulsion may be applied as long as the oil droplets are within their desired size range and the emulsified aminosilicone prepolymer remains reactive. Since the thickness of the coating is believed to be proportional to the average diameter of the droplets, if a thin coating is desired, too large droplets should be avoided, while on the other hand too small droplets will not embed pigment particles of sufficient size to provide the desired visual effect. The time window may vary with the ingredients of the emulsion and their respective amounts, which is generally extended by the presence of the emulsifier. In some embodiments, the emulsion is applied to the hair fibers within at most 30 minutes, or at most 20 minutes, at most 10 minutes, or at most 5 minutes after emulsification.
According to some embodiments, the aqueous carrier comprises at least 60% water, or at least 65%, or at least 70%, or at least 75%, or at least 80%, or at least 85%, or at least 90%, or at least 95% by weight of water, based on the weight of the liquid carrier. In some embodiments, the total concentration of water and any emulsifier is at least 90 wt%, at least 95 wt%, at least 97 wt%, or at least 99 wt%, based on the weight of the aqueous phase.
In the case where the amount of pigment and/or its density is high, although the liquid carrier will contain primarily water, the water may comprise only 30% by weight of the total composition.
In some embodiments, the thickness, average thickness, or average thickness of the plurality of fibers of the cured aminosilicone coating is at least 20nm, at least 50nm, or at least 100nm, and optionally at most 3,000nm, at most 2,000nm, at most 1,200nm, at most 800nm, at most 500nm, at most 400nm, at most 300nm, at most 200nm, at most 150nm, or at most 120nm, and further optionally, in the range of 20nm to 3,000nm, 20nm to 1,000nm, 20nm to 500mn, 20nm to 300nm, 20nm to 200mn, 20nm to 150nm, 50nm to 150mn, 50nm to 500nm, 50nm to 350nm, 50nm to 250nm, or 50nm to 200 nm.
As used herein, the term "average thickness" in general with respect to one or more coatings or layers refers to the arithmetic average of the thicknesses measured for the one or more coatings or layers along the length of the fiber. As is well known in the art, each individual thickness measurement is made using Focused Ion Beam (FIB) techniques. For a single thickness measurement, ten equally spaced points along the entire length of the coated fiber are determined, and the arithmetic average of these ten measurements defines the average thickness associated with that single fiber.
The coated fibers of the present disclosure or made according to the present disclosure may exhibit coating thicknesses that are largely fairly consistent regardless of the specific topographical features of the hair fiber substrate. In addition, individual coated fibers may exhibit similar coating thicknesses. However, it should be appreciated that a more statistical approach to coating thickness may be better utilized to differentiate the present disclosure from the various teachings in the art. Thus, in some embodiments of the present disclosure, "a plurality of fiber average thicknesses" is defined as an "average thickness" as defined above for a single coated fiber, but is applied to and arithmetically averaged over a plurality of at least ten such coated fibers randomly selected from fibers that are coated together.
Polymeric overcoat
The polymer layer is formed from an aqueous dispersion comprising a plurality of polymer particles formed from a hydrophilic polymer material having neutralized acid moieties, the hydrophilic polymer material optionally encapsulating the pigment particles when the pigment is present in the aqueous dispersion.
The polymer particles dispersed in the aqueous dispersion have a certain hydrophilicity when applied to the hair fibres which have been previously coated with an aminosilicone coating, for which purpose the acid moieties thereof are neutralized in the presence of a neutralizing agent. However, prior to such neutralization of the neutralizable acid moieties, the polymeric material is hydrophobic. After application of the aqueous dispersion to the outer surface of the mammalian hair fibers pre-coated with the aminosilicone, the neutralizing agent is removed (e.g., by evaporation), resulting in an overlying polymer layer (optionally pigmented) that adheres to the outer surface of the aminosilicone coating (pre-coated on the mammalian hair fibers).
As used in this specification and the claims section that follows, the term "hydrophilic polymer" with respect to a polymeric material (e.g., a neutralized polymeric material) refers to a polymer having at least one of the following solubility characteristics: (i) a solubility in deionized purified water of at least 1% by weight, and more typically at least 1.5%, at least 2%, at least 3%, at least 5%, at least 10%, or at least 15% by weight at 23 ℃; and (ii) a solubility in deionized purified water adjusted to a pH of 10 of at least 1%, more typically at least 1.5%, at least 2%, at least 3%, at least 5%, at least 10%, or at least 15% by weight at 23 ℃. The solubility of the polymer was evaluated in the absence of pigments or any other possible additives.
Typically, the conjugate acid of the hydrophilic neutralized polymeric material is a hydrophobic polymeric material.
As used herein in the specification and in the claims section that follows, the term "solubility" in reference to a polymeric material refers to the amount of polymeric material that can be incorporated into the deionized water medium of (i) or (ii) above while maintaining the clarity of the deionized water medium.
As used herein in the specification and in the claims section that follows, the term "clarity" in relation to a solution is intended to include solutions having at least one, and typically two, of the following characteristics: (i) the solution is clear by naked eyes; (ii) any micelles placed therein have an average diameter or particle size (as determined by DLS) of at most 100 nm. More typically, such micelles have an average diameter or particle size of at most 80nm, at most 70nm, or at most 50 nm. The volatile base is removed from the aqueous dispersion, thereby re-acidifying the neutralized acidic moieties in the hydrophilic polymeric material to their conjugate acids. Thus, after such removal, a hydrophobic polymer material can be obtained.
Advantageously, an aqueous dispersion of basic pH, once applied to the hair fibers pre-coated with an aminosilicone membrane, can restore the positive charge of the aminosilicone membrane (e.g., by protonation of the amino groups). At the same time, the alkaline pH causes the polymeric material to take a high negative charge (e.g., by protonation of the carboxyl groups). Thus, the basic pH of the aqueous dispersion favors the development of a significant charge gradient at the beginning of the process of coating the aminosilicone membrane with the polymer particles, thereby providing a strong initial electrostatic drive.
In some embodiments, the neutralizable acid moieties of the hydrophobic polymeric material comprise at least 8%, at least 10%, at least 12%, at least 15%, at least 16%, at least 17%, at least 18%, at least 19%, at least 20%, at least 21%, or at least 22% by weight of the hydrophobic polymeric material. In some embodiments, the neutralizable acid moieties of the hydrophobic polymeric material comprise 8 to 30%, 10 to 30%, 12 to 28%, 12 to 26%, 15 to 30%, 15 to 28%, 15 to 26%, 17 to 22%, 17 to 23%, 18 to 30%, 18 to 28%, 18 to 26%, 20 to 30%, 20 to 28%, or 20 to 26% by weight of the hydrophobic polymeric material.
In some embodiments, the neutralizable and/or neutralizing acid moieties of the hydrophilic polymeric material comprise at least 8%, at least 10%, at least 12%, at least 15%, at least 16%, at least 17%, at least 18%, at least 19%, at least 20%, at least 21%, or at least 22% by weight of the hydrophilic polymeric material. In some embodiments, the neutralizable and/or neutralizing acid moieties of the hydrophilic polymeric material comprise 8 to 30%, 10 to 30%, 12 to 28%, 12 to 26%, 15 to 30%, 15 to 28%, 15 to 26%, 17 to 22%, 17 to 23%, 18 to 30%, 18 to 28%, 18 to 26%, 20 to 30%, 20 to 28%, or 20 to 26% by weight of the hydrophilic polymeric material. Such values are also reported in terms of weight percent of monomer having an acid moiety based on the total weight of the polymeric material (e.g., acrylic acid (wt% AA) in EAA copolymers or methacrylic acid (wt% MA) in EMAA). Such properties of polymeric materials are typically provided by the manufacturer, but may be evaluated by standard methods, such as described in ASTM D4094.
In some embodiments, the acid number of the polymeric material (prior to neutralization) is at least l00 mg KOH/g, at least 115mg KOH/g, at least 130mg KOH/g, or at least 145mg KOH/g. In some embodiments, the polymeric material has an acid number of at most 230mg KOH/g, at most 215mg KOH/g, at most 200mg KOH/g, or at most 185mg KOH/g. In some embodiments, the acid number is in the range of 100 to 230mg KOH/g, 115 to 215mg KOH/g, 130 to 200mg KOH/g, 130 to 185mg KOH/g, 145 to 185mg KOH/g, or 145 to 170mg KOH/g. Acid number (also known as acid number or neutralization number, used to estimate the number of carboxylic acid groups in a chemical compound, and corresponds to the mass (in milligrams) of potassium hydroxide (KOH) required to neutralize one gram of polymeric material). Acid numbers are typically provided by the manufacturer of such polymeric materials, or may be independently evaluated by standard methods, such as described in ASTM D974-04.
In some embodiments, the polymeric material is dispersed in the aqueous dispersion in an amount of at least 1 weight percent, at least 2 weight percent, or at least 5 weight percent based on the weight of the aqueous dispersion. In some embodiments, the polymeric material is dispersed in the aqueous dispersion in an amount of up to 45 weight percent, up to 30 weight percent, up to 25 weight percent, up to 20 weight percent, up to 15 weight percent, up to 12.5 weight percent, or up to 10 weight percent based on the weight of the aqueous dispersion.
In some embodiments, the aqueous dispersion is produced by the following method:
(a) mixing at least one hydrophobic polymeric material each independently having a neutralizable acid moiety, optionally with a pigment, in an aqueous carrier containing water, thereby forming a neutralizable mixture comprising particles of the hydrophobic polymeric material;
(B) adding a neutralizing agent to the neutralizable mixture, the adding being carried out with stirring at a temperature above at least one of the maximum softening temperature and/or the melting temperature of the at least one hydrophobic polymeric material. The neutralizing agent is added in an amount sufficient to neutralize at least 75% of the neutralizable acid moieties of the polymeric material to form a neutralized mixture comprising a portion of the hydrophilic polymeric material; and
(c) dispersing the neutralized mixture to form said aqueous dispersion comprising particles of at least one hydrophilic polymeric material.
In some embodiments, the aqueous dispersion is produced by the following method:
(a) mixing at least one hydrophobic polymeric material each independently having a neutralizable acid moiety in an aqueous carrier containing water to form a neutralizable mixture comprising particles of the hydrophobic polymeric material;
(b) adding a neutralizing agent to the neutralizable mixture, the adding being carried out with stirring at a temperature above at least one of the maximum softening temperature and/or the melting temperature of the at least one hydrophobic polymeric material. The neutralizing agent is added in an amount sufficient to neutralize at least 75% of the neutralizable acid moieties of the polymeric material to form a neutralized mixture comprising a portion of the hydrophilic polymeric material;
(c) adding at least one pigment to the neutralized mixture; and
(d) dispersing the colored neutralized mixture to form the aqueous dispersion, the aqueous dispersion comprising particles of at least one hydrophilic polymeric material, a portion of the hydrophilic polymeric material at least partially encapsulating the at least one pigment.
Although the amount of neutralizing agent can be determined experimentally by simple methods, it can also be estimated by equations since its concentration allows self-dispersibility of the polymer particles and (in the absence of pigments) formation of transparent micellar dispersions. For example, the amount of neutralizing agent to be added to a polymeric material having neutralizable acid moieties (B-weight (grams)) is:
B＝(W·A·N·E)/l000
where W is the weight of the polymeric material in grams,
a is the acidity of the polymeric material, expressed in mEq/gram of polymeric material,
n is the desired percent neutralization, expressed as a decimal fraction from 0 to 1, the latter representing 100% neutralization, an
E is the equivalent weight of the neutralizing agent used.
In some embodiments, the neutralizing agent used to prepare the aqueous dispersion is a volatile base. In this case, the resulting aqueous fractionThe dispersion comprises a volatile base. The volatile base is selected from ammonia (NH)3) Monoethanolamine, diethanolamine, triethanolamine and morpholine. When wash fastness is desired, it is preferred to avoid the use of alkali metal based bases as neutralizing agents, since the acid portion of the polymeric material may bind to the metal ions of the base, resulting in a decrease in the ionomer resistance to water. In some embodiments, the hydrophilic polymeric material having neutralized acid moieties has a solubility of at least 2%, at least 5%, at least 10%, or at least 15% by weight, or wherein the solubility is in the range of 2 to 30%, 5 to 30%, 10 to 30%, or 15 to 30% by weight at
In some embodiments, the particles of the aqueous dispersion and hydrophilic polymeric material further comprise pigment particles dispersed therein, the pigment optionally selected from those previously detailed, and further optionally meeting structural characteristics associated therewith (e.g., particle size).
In some embodiments, the pigment is present in the aqueous dispersion in an amount of at least 0.1 weight%, at least 0.5 weight%, at least 1 weight%, at least 2 weight%, or at least 5 weight%, based on the weight of the hydrophilic polymeric material. In some embodiments, the pigment is present in the aqueous dispersion in an amount of up to 50 weight percent, up to 40 weight percent, up to 30 weight percent, up to 20 weight percent, up to 15 weight percent, or up to 10 weight percent based on the weight of the hydrophilic polymeric material. In some embodiments, the pigment is present in the aqueous dispersion in an amount in the range of 0.1 to 50 weight percent, 1 to 30 weight percent, 2 to 20 weight percent, or 5 to 15 weight percent based on the weight of the hydrophilic polymeric material.
In some embodiments, the pigment is present in the aqueous dispersion in an amount of at least 0.05 wt%, at least 0.5 wt%, at least 1 wt%, by weight of the aqueous dispersion. In some embodiments, the pigment is dispersed in the aqueous dispersion in an amount of up to 15 weight percent, up to 10 weight percent, up to 7.5 weight percent, up to 5 weight percent, or up to 2.5 weight percent, based on the weight of the aqueous dispersion. In some embodiments, the pigment is present in the aqueous dispersion in an amount in the range of 0.05 to 15 wt%, 0.5 to 10 wt%, 1 to 7.5 wt%, 1.5 to 5 wt%, or 1.5 to 2.5 wt% by weight of the aqueous dispersion.
In some embodiments, the method of treating the external surface of a mammalian hair fiber having an aminosilicone coating with an aqueous dispersion of an at least partially neutralized polymeric material further comprises volatilizing a volatile base associated with the overlying polymeric layer (optionally pigmented) to acidify, mostly or predominantly acidify, or fully acidify the neutralized acid moieties.
After applying the aqueous dispersion, the method further comprises converting a portion, a majority, or all of the hydrophilic polymeric material in the overlying pigmented polymeric layer to its conjugate acid. In some embodiments, the conversion comprises, consists essentially of, or consists of acidifying the neutralized acid moiety to form a conjugate acid.
Once the hydrophilic polymeric material is sufficiently converted to its conjugate acid, a hydrophobic polymeric material is obtained. Thus, a polymer layer in which the polymer material has been sufficiently converted from a form having acid moieties to a conjugated acid form (hydrophobic) by a base (hydrophilic) may form sufficient adhesion to the underlying aminosilicone coating. In this case, the outer polymer coating is a hydrophobic coating.
In some embodiments, the polymeric material having neutralized acid moieties comprises, consists essentially of, or consists of one or more neutralized copolymers selected from the group consisting of: neutralized olefin-acrylic acid copolymers, neutralized olefin-methacrylic acid copolymers, and neutralized acrylamide/acrylate copolymers.
In some embodiments, the neutralized olefin-acrylic acid copolymer comprises, consists essentially of, or consists of a neutralized ethylene-acrylic acid (EAA) copolymer. In some embodiments, the neutralized olefin-methacrylic acid copolymer comprises, consists essentially of, or consists of a neutralized ethylene methacrylic acid (EMAA) copolymer. In some embodiments, the polymeric material having neutralized acid moieties comprises, consists essentially of, or consists of a neutralized acrylamide/acrylate (AAA) copolymer.
Suitable hydrophilic polymeric materials are self-dispersible in water in the pH range of 7.5 to 11 in the absence of dispersants and all other additives in water.
In some embodiments, the aqueous dispersion of neutralized hydrophilic polymeric material further comprises a surfactant and/or a thickener. In some embodiments, the surfactant is a super wetting agent capable of altering the surface tension of the aqueous dispersion, thereby facilitating wetting thereof with the aminosilicone coating.
In some embodiments, the surfactant or super wetting agent is selected and added in sufficient quantity in the aqueous dispersion such that the aqueous dispersion exhibits a surface tension at 25 ℃ of at most 30, at most 28, at most 26, or at most 24 millinewtons per meter (mN/m), and optionally at least 12, at least 14, or at least 16 millinewtons (mN/m). In some embodiments, the aqueous dispersion has a surface tension in the range of 12 to 30, 15 to 30, 18 to 28, 18 to 26, 18 to 24, 19 to 24, or 20 to 24 mN/m.
Suitable hydrophobic polymeric materials having neutralizable acid moieties, such as Acrylic Acid (AA) or methacrylic acid (MAA), that can be used to prepare aqueous dispersions according to the present disclosure are commercially available, including as non-limiting examples some EAA, EMAA, and AAA polymeric materials available under the following trade names from the following companies: dow chemical, trade name: primacorTM(ii) a Dupont, trade name:
Suitably, the hydrophobic polymeric material having neutralizable acid moieties is thermoplastic. The thermoplastic polymer facilitates, for example, partial encapsulation of the pigment particles during compounding processes, such as hot melt compounding.
In some embodiments, after the aqueous dispersion is applied over the aminosilicone coating, the overlying polymer layer is treated to produce an overlying (e.g., pigmented) polymer coating that adheres to the outer surface of the pre-coated mammalian hair fibers. Post-application treatment includes washing and/or carding the plurality of fibers to remove excess material therefrom, and optionally, subsequently drying and/or carding the plurality of fibers.
The treatment of the coated hair fibres (including washing and/or drying and/or combing, and more typically the entire coating process) is typically carried out at a temperature of at most 45 ℃,40 ℃, 35 ℃, 30 ℃ or 25 ℃. In some embodiments, such steps are performed at a temperature of at least 5 ℃,10 ℃, 12 ℃,15 ℃, 17 ℃, or 20 ℃, and optionally, within 7 ℃,5 ℃, or 3 ℃ of room or ambient temperature.
In some embodiments, the washing of the plurality of fibers is performed within at most 20 minutes, at most 10 minutes, at most 5 minutes, at most 3 minutes, at most 2 minutes, at most 1 minute, or at most 30 seconds after completion of the applying the aqueous dispersion.
In some embodiments, the drying of the hair fibers and the coating thereon is active drying. In some embodiments, the total length of time for applying the aqueous dispersion, rinsing and/or actively drying the hair fibers is in the range of 2 to 90 minutes, 2 to 75 minutes, 2 to 60 minutes, 2 to 45 minutes, 2 to 30 minutes, 2 to 20 minutes, 2 to 10 minutes, or 2 to 5 minutes.
In some embodiments, the overlying pigmented polymeric coating can achieve wash, permanent, or permanent coloration within 24 to 72 hours, within 24 to 48 hours, within 24 to 36 hours, or within 24 to 30 hours immediately after the total length of time (e.g., after washing or drying), while maintaining the plurality of fibers at room or ambient temperature within 7 ℃,5 ℃, 3 ℃, or 1 ℃.
It is believed that this elasticity of the overlying polymer coating is provided by the resistance of the underlying aminosilicone coating and its strength of adhesion to the underlying hair fibers. It should be noted that since curing of the aminosilicone coating may be carried out on the hair fibres, the overlying polymer coating may advantageously penetrate to diffuse humidity once such coating is encapsulated by the polymer layer, and since condensation curing may benefit from ambient humidity. When mammalian hair is living, the polymer layer preferably forms a "breathing" coating.
In some embodiments, the thickness of the overlying polymeric coating is such that the combined thickness, the combined average thickness, or the combined multiple fiber average thickness of the aminosilicone coating and the overlying pigmented polymeric coating is at least 100nm, at least 150nm, at least 200nm, at least 300nm, at least 500nm, at least 800nm, at least 1,200nm, or at least 2,000nm when combined with the thickness of the underlying aminosilicone coating. In some embodiments, the total thickness, the total average thickness, or the total plurality of fibers average thickness of the two coatings is at most 5,000nm, at most 3,500nm, at most 2,500nm, at most 2,000nm, at most 1,700nm, or at most 1,400 nm. In some embodiments, the total thickness, the total average thickness, or the total multi-fiber average thickness of the two coatings is in a range of 100nm to 5,000nm, 200nm to 3,500nm, 200nm to 2,500nm, 200nm to 1,000nm, 200nm to 700nm, 200nm to 500nm, 200nm to 450nm, or 200nm to 400 nm.
In some embodiments, the ratio of at least one of the total thickness, the total average thickness, and the total plurality of fiber average thicknesses of two coatings combined together to the thickness, average thickness, or plurality of fiber average thicknesses of the underlying aminosilicone layer is from 1.2:1 to 100: 1; 1:4 to 100: 1; 1:7 to 100: 1; 2:1 to 100: 1; 3:1 to 100: 1; 4:1 to 100: 1; 5:1 to 100: 1; 7:1 to 100: 1; 10:1 to 100: 1; 2:1 to 30: 1; 2:1 to 20: 1; 3:1 to 30: 1; 3:1 to 20: 1; 5:1 to 30: l; 5:1 to 20: 1; 7:1 to 30: 1; 7:1 to 20: 1; 10:1 to 50: 1; 10:1 to 30: 1; or in the range of 10:1 to 20: 1.
According to some embodiments, the composition according to the present teachings (or a kit enabling its preparation and use) further comprises at least one additive selected from the group consisting of dispersants, pH adjusters, preservatives, bactericides, fungicides, viscosity modifiers, thickeners, chelating agents, vitamins and perfumes. Depending on the mode of application, additional agents may be required, for example, a propellant may be added if the composition is to be applied in the form of a propellant spray.
According to some embodiments, the composition is in a form selected from the group consisting of a paste, a gel, a lotion, and a cream.
According to some embodiments, the mammalian hair is human hair or animal hair selected from body hair, facial hair (including, for example, beard, cheek hair, eyelashes and eyebrows), or hair. In further embodiments, the hair is attached to the body or scalp of a human or animal subject. Human hair may be of any ethnic nature (e.g., european, asian, african, etc.) and of any type, whether natural or man-made, such as straight, wavy, curly or kinked. The human hair that is not attached to the subject may be wigs, extensions of eyelashes, and the like. In some embodiments, the mammalian hair fibers are dry, unwetted, or pre-dyed. In some embodiments, the mammalian hair fibers are not pre-degreased, not pre-shampooed, and not pre-bleached.
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