Shampoo compositions comprising a chelant

Information

  • Patent Grant
  • 11246816
  • Patent Number
    11,246,816
  • Date Filed
    Thursday, June 22, 2017
    6 years ago
  • Date Issued
    Tuesday, February 15, 2022
    2 years ago
Abstract
Described herein is a shampoo composition and methods of using the same, the shampoo composition including a Class I and/or Class II chelant, a detersive surfactant, and a carrier.
Description
FIELD OF THE INVENTION

Described herein are shampoo compositions comprising a detersive surfactant, a Class I and/or Class II chelant, and a carrier, wherein the shampoo composition inhibits both deposition/penetration of copper salts and other transition metal salts in the hair and removes such salts from hair fiber. A method of cleansing hair with such shampoo compositions is also described herein.


BACKGROUND OF THE INVENTION

Many water sources that are used by consumers for personal care contain elevated levels of calcium and magnesium salts, as well as undesirable levels of redox metals (e.g., copper and/or iron) salts. As such, using chelants to sequester trace redox metals often proves to be ineffective because most chelants also competitively bind calcium and/or magnesium.


It has been found that even trace quantities of copper can deposit on the hair surface and in between the cuticle layers of hair. This deposition of copper on hair is especially problematic because transition metal ions, such as copper and iron, can facilitate reduction-oxidation (redox) reactions during hair coloring treatments and during UV exposure. These reactions generate reactive oxygen species (ROS), which in turn can cause damage to the hair. In addition, they can interfere with the oxidative color formation chemistry and lead to reduced color uptake for hair colorant users.


Accordingly, there is a need for improved shampoo compositions that can inhibit copper depositing on hair, as well as facilitate the removal of copper already deposited thereon.


SUMMARY OF THE INVENTION

A shampoo composition comprising:

    • (a) from about 0.005% to about 10% of one or more chelants, by weight of the shampoo composition, wherein the one or more chelants comprise a Class I chelant and/or a Class II chelant, wherein the Class I chelants are represented by molecular structure I:




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      • wherein

      • M is hydrogen or a metal ion;

      • R1, R2, R3, and R4 are independently selected from the group consisting of hydrogen, —COOM, hydroxyl, —NH2, methyl, ethyl, propyl, butyl, pentyl, phenyl, and combinations thereof;
        • and wherein the Class I chelant comprises:
        • (1) log of the formation constant log KML of its complex with copper is greater than 3;
        • (2) log P value is from about 0 to about 5; and
        • (3) molecular weight is from about 123 to about 350;
          • and wherein the Class II chelants are represented by molecular structure II:









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      • wherein

      • M is hydrogen or a metal ion;

      • R5, R6, R7, R5, R9, and R10 are independently selected from the group consisting of hydrogen, —COOM, hydroxyl, —NH2, methyl, ethyl, propyl, butyl, pentyl, phenyl, and combinations thereof;

      • and wherein the Class II chelant comprises:
        • (1) log of the formation constant log KML of its complex with copper is greater than 3;
        • (2) log P value is from about 0 to about 5; and
        • (3) molecular weight is from about 173 to about 400;



    • (b) from about 2% to about 50% of one or more detersive surfactants, by weight of the shampoo composition; and

    • (c) from about 75% to about 98% of an aqueous carrier, by weight of the shampoo composition;





wherein the shampoo composition has a pH of about 3 to about 8.







DETAILED DESCRIPTION OF THE INVENTION

While the specification concludes with claims particularly pointing out and distinctly claiming the invention, it is believed that the shampoo composition described herein will be better understood from the following description.


As used herein, the term “fluid” includes liquids and gels.


As used herein, the term “log x” refers to the common (or decadic) logarithm of x.


As used herein, the articles including “a” and “an” when used in a claim, are understood to mean one or more of what is claimed or described.


All percentages are by weight of the total composition, unless stated otherwise. All ratios are weight ratios, unless specifically stated otherwise. All ranges are inclusive and combinable. The number of significant digits conveys neither a limitation on the indicated amounts nor on the accuracy of the measurements. The term “molecular weight” or “M.Wt.” as used herein refers to the weight average molecular weight unless otherwise stated. “QS” means sufficient quantity for 100%.


As used herein, “mixtures” is meant to include a simple combination of materials and any compounds that may result from their combination.


All numerical amounts are understood to be modified by the word “about” unless otherwise specifically indicated. Unless otherwise indicated, all measurements are understood to be made at 25° C. and at ambient conditions, where “ambient conditions” means conditions under about one atmosphere of pressure and at about 50% relative humidity. All such weights percents (wt %) as they pertain to listed ingredients are based on the active level and do not include carriers or by-products that may be included in commercially available materials, unless otherwise specified.


Unless otherwise noted, all component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.


Herein, “comprising” means that other steps and other ingredients which do not affect the end result can be added. This term encompasses the terms “consisting of” and “consisting essentially of”. The compositions, methods, uses, kits, and processes of the shampoo composition described herein can comprise, consist of, and consist essentially of the elements and limitations of the invention described herein, as well as any of the additional or optional ingredients, components, steps, or limitations described herein. As used herein, the terms “include,” “includes,” and “including,” are meant to be non-limiting and are understood to mean “comprise,” “comprises,” and “comprising,” respectively.


The term “substantially free from” or “substantially free of” as used herein means less than about 1%, or less than about 0.8%, or less than about 0.5%, or less than about 0.3%, or about 0%, by total weight of the composition.


“Hair,” as used herein, means mammalian hair including scalp hair, facial hair and body hair, particularly on hair on the human head and scalp.


“Cosmetically acceptable,” as used herein, means that the compositions, formulations or components described are suitable for use in contact with human keratinous tissue without undue toxicity, incompatibility, instability, allergic response, and the like. All compositions described herein which have the purpose of being directly applied to keratinous tissue are limited to those being cosmetically acceptable.


“Derivatives,” as used herein, includes but is not limited to, amide, ether, ester, amino, carboxyl, acetyl, acid, and/or alcohol derivatives of a given compound.


“Polymer,” as used herein, means a chemical formed from the polymerisation of two or more monomers, which may be the same or different. The term “polymer” as used herein shall include all materials made by the polymerisation of monomers as well as natural polymers. Polymers made from only one type of monomer are called homopolymers. A polymer comprises at least two monomers. Polymers made from two or more different types of monomers are called copolymers. The distribution of the different monomers can be calculated statistically or block-wise—both possibilities are suitable for the shampoo composition. Except if stated otherwise, the term “polymer” used herein includes any type of polymer including homopolymers and copolymers.


The term “charge density” as used herein, means the ratio of the number of positive charges on a monomeric unit of which a polymer is comprised to the M.Wt. of said monomeric unit. The charge density multiplied by the polymer M.Wt. determines the number of positively charged sites on a given polymer chain. For cationic guars, charge density is measured using standard elemental analysis of percentage nitrogen known to one skilled in the art. This value of percentage nitrogen, corrected for total protein analysis, can then be used to calculate the number or equivalence of positive charges per gram of polymer. For the cationic copolymers, the charge density is a function of the monomers used in the synthesis. Standard NMR techniques know to one skilled in the art would be used to confirm that ratio of cationic and non-ionic monomers in the polymer. This would then be used to calculate the number or equivalence of positive charges per gram of polymer. Once these values are know, the charge density is reported in milliequivalence (meq) per gram of cationic polymer.


The term log P is the n-octanol/water partition coefficients of the material.


All percentages, parts and ratios are based upon the total weight of the compositions of the present invention, unless otherwise specified. All such weights as they pertain to listed ingredients are based on the active level and, therefore, do not include carriers or by-products that may be included in commercially available materials.


Unless otherwise noted, all component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.


It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.


Shampoo Composition

Described herein is a shampoo composition comprising (a) from about 0.005% to about 10% of one or more chelants, wherein the one or more chelants comprise a Class I and/or Class II chelant; (b) from about 2% to about 50% of one or more detersive surfactants, by weight of the shampoo composition; (c) from about 75% to about 98% of an aqueous carrier, by weight of the shampoo composition, wherein the shampoo composition has a pH of about 3 to about 8, and wherein the shampoo inhibits copper deposition on hair and facilitates the removal of copper deposited on hair. The shampoo composition also delivers consumer desired shampooing in addition to inhibiting the deposition of copper (i.e. from the water used to rinse) on the hair.


A. Chelants


The shampoo composition comprises from about 0.005% to about 10%, alternatively from about 0.01% to about 5%, alternatively from about 0.05% to about 3%, alternatively from about 0.1% to about 1.5%, and alternatively from about 0.1% to about 0.5% of one or more chelants by weight of the shampoo composition, wherein the one or more chelants comprise a Class I chelant and/or a Class II chelant, wherein the Class I chelants are represented by molecular structure I:




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    • wherein

    • M is hydrogen or a metal ion;

    • R1, R2, R3, and R4 are independently selected from the group consisting of hydrogen, —COOM, hydroxyl, —NH2, methyl, ethyl, propyl, butyl, pentyl, phenyl, and combinations thereof;

    • and wherein the Class I chelant comprises:
      • (2) log of the formation constant log KML of its complex with copper is greater than 3;
      • (2) log P value is from about 0 to about 5; and
      • (3) molecular weight is from about 123 to about 350;
        • and wherein the Class II chelants are represented by molecular structure II:







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      • wherein

      • M is hydrogen or a metal ion;

      • R5, R6, R7, R8, R9, and R10 are independently selected from the group consisting of hydrogen, —COOM, hydroxyl, —NH2, methyl, ethyl, propyl, butyl, pentyl, phenyl, and combinations thereof;

      • and wherein the Class II chelant comprises:
        • (2) log of the formation constant log KML of its complex with copper is greater than 3;
        • (2) log P value is from about 0 to about 5; and
        • (3) molecular weight is from about 173 to about 400.


          Stability Constants of Exemplary Chelants







The relative affinity of a chelant at a specified pH for Cu+2 can be assessed by its Stability Constant. The Stability Constant of a metal chelant interaction is defined as:







K
ML

=


[
ML
]



[
M
]



[
L
]








where:


[ML] is the concentration of metal ligand complex at equilibrium;


[M] is the concentration of free metal ion;


[L] is the concentration of free ligand in a fully deprotonated form; and


KML is the stability constant for the metal chelant complex.


The stability constants of chelant-metal ion complexes are well documented in the literature for commonly used chelants (see, for example, Arthur Martell & Robert M Smith, Critically Selected Stability Constants of Metal Complexes Database, Version 3.0 and above, incorporated herein by reference). When not documented the constants can be measured using various analytical methods (see “Metal Complexes in Aqueous Solutions”, Martel and Hancock, edition Modem Inorganic Chemistry, p. 226-228, incorporated herein by reference).


It has been found that effective chelants need to have a high affinity for copper in order to preferentially bind copper found in hair. However, it has been found that also important to efficacy is the ability for the chelant to penetrate inside the hair fibers rapidly during the shampoo lathering process (which typically lasts between 30 seconds and 1 minute). The copper to be removed is inside the hair and the chelant needs to penetrate inside hair and form a strong copper-chelant complex. This copper-chelant complex needs to be water soluble and thus easily removed during the rinsing process. To be able to do this, two additional parameters have been shown to be important for chelant efficacy. These are log P, the octanol/water partitioning coefficient, and the molecular weight of the chelant. Both are related to the ability of the chelant to penetrate into hair and also form a water soluble copper-chelant complex


Non-limiting examples of Class I chelants are picolinic acid, fusaric acid, quinolinic acid, dipicolinic acid, 6-methylpyridine-2-carboxylic acid, chelidamic acid, and 4-aminopyridine-2,6-dicarboxylic acid.




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A non-limiting example of a Class II chelant is quinaldic acid.




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Table 1 provides relevant properties and performance of representative Class I and Class II chelants. Details on determination of copper removing performance is described in the Examples section.









TABLE 1







Properties of representative Class I and Class II chelants












Copper Removing






Performance from
Log


Chelants
Shampoo
KML Cu
Log P
MW














Picolinic Acid
50%
7.9
0.7
123


Fusaric Acid
50%

2.6
179


Quinolinic Acid
50%

0.4
167


Dipicolinic Acid
40%
9.1
0.8
167


6-Methyl Picolinic Acid
35%
7.1
1
137


(6-Methylpyridine-2-


carboxylic acid)


Chelidamic Acid
35%
12.2
0.6
183


Quinaldic Acid
35%
5.9
2.1
173


4-Aminopyridine-2,6-
No data collected
11.4
0
182


dicarboxylic acid









For the Class I chelants and/or the Class II chelants, the log of the formation constant log KML of its complex with copper can be higher than 3, alternatively higher than 4, alternatively higher than 5, alternatively higher than 5.5, and alternatively higher than 10. For the Class I chelants and/or the Class II chelants, the log of the formation constant log KML of its complex with copper can be from about 3 to about 23, alternatively from about 4 to about 15, alternatively from about 5 to about 13, alternatively from about 5.5 to about 13, and alternatively from about 10 to about 13.


The log P value of the Class I chelants and/or the Class II chelants can be from about 0 to about 5, alternatively from about 0.1 to about 4, alternatively from about 0.3 to about 3, and alternatively from about 0.4 to about 2.6.


The molecular weight of the Class I chelants can be from about 123 to about 350, alternatively from about 123 to about 300, and alternatively from about 123 to about 190.


The molecular weight of the Class II chelants can be from about 173 to about 400, alternatively from about 173 to about 350, and alternatively from about 173 to about 250.


The copper removing performance of the shampoo composition is determined by treating hair with clarifying shampoo containing the corresponding chelant for 20 cycles and comparing the copper content of the hair compared to the same treatment using shampoo without the chelant.


B. Detersive Surfactant


The shampoo composition comprises from about 2% to about 50%, alternatively from about 5% to about 25%, alternatively from about 7% to about 22%, alternatively from about 9% to about 18%, and alternatively from about 11% to about 15% of one or more detersive surfactants by weight of the shampoo composition. The concentration of the detersive surfactant component in the shampoo composition should be sufficient to provide the desired cleaning and lather performance.


The one or more detersive surfactants can be selected from the group consisting of anionic surfactants, amphoteric or zwitterionic surfactants, or mixtures thereof. The one or more detersive surfactants can also be selected from the group consisting of anionic surfactants, cationic surfactants, non-ionic surfactants, amphoteric surfactants, and mixtures thereof. Various examples and descriptions of detersive surfactants are set forth in U.S. Pat. No. 6,649,155; U.S. Patent Application Publication No. 2008/0317698; and U.S. Patent Application Publication No. 2008/0206355, which are incorporated herein by reference in their entirety.


Anionic surfactants suitable for use in the compositions are the alkyl and alkyl ether sulfates. Other suitable anionic surfactants are the water-soluble salts of organic, sulfuric acid reaction products. Still other suitable anionic surfactants are the reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide. Other similar anionic surfactants are described in U.S. Pat. Nos. 2,486,921; 2,486,922; and 2,396,278, which are incorporated herein by reference in their entirety.


Exemplary anionic surfactants for use in the shampoo composition include ammonium lauryl sulfate, ammonium laureth sulfate, triethylamine lauryl sulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate, triethanolamine laureth sulfate, monoethanolamine lauryl sulfate, monoethanolamine laureth sulfate, diethanolamine lauryl sulfate, diethanolamine laureth sulfate, lauric monoglyceride sodium sulfate, sodium lauryl sulfate, sodium laureth sulfate, potassium lauryl sulfate, potassium laureth sulfate, sodium lauryl sarcosinate, sodium lauroyl sarcosinate, lauryl sarcosine, cocoyl sarcosine, ammonium cocoyl sulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate, sodium lauroyl sulfate, potassium cocoyl sulfate, potassium lauryl sulfate, triethanolamine lauryl sulfate, triethanolamine lauryl sulfate, monoethanolamine cocoyl sulfate, monoethanolamine lauryl sulfate, sodium tridecyl benzene sulfonate, sodium dodecyl benzene sulfonate, sodium cocoyl isethionate and combinations thereof. In a further embodiment, the anionic surfactant is sodium lauryl sulfate or sodium laureth sulfate.


Suitable amphoteric or zwitterionic surfactants for use in the shampoo composition include those which are known for use in shampoo or other personal care cleansing. Concentrations of such amphoteric surfactants range from about 0.5 wt % to about 20 wt %, and from about 1 wt % to about 10 wt %. Non limiting examples of suitable zwitterionic or amphoteric surfactants are described in U.S. Pat. Nos. 5,104,646 and 5,106,609, which are incorporated herein by reference in their entirety.


Amphoteric detersive surfactants suitable for use in the shampoo composition include those surfactants broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic group such as carboxy, sulfonate, sulfate, phosphate, or phosphonate. Exemplary amphoteric detersive surfactants for use in the present shampoo composition include cocoamphoacetate, cocoamphodiacetate, lauroamphoacetate, lauroamphodiacetate, and mixtures thereof.


Zwitterionic detersive surfactants suitable for use in the shampoo composition include those surfactants broadly described as derivatives of aliphatic quaternaryammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight or branched chain, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic group such as carboxy, sulfonate, sulfate, phosphate or phosphonate. In another embodiment, zwitterionics such as betaines are selected.


Non limiting examples of other anionic, zwitterionic, amphoteric or optional additional surfactants suitable for use in the shampoo composition are described in McCutcheon's, Emulsifiers and Detergents, 1989 Annual, published by M. C. Publishing Co., and U.S. Pat. Nos. 3,929,678, 2,658,072; 2,438,091; 2,528,378, which are incorporated herein by reference in their entirety.


The shampoo composition may also comprise a cationic conditioning polymer, an aqueous carrier, and other additional ingredients described herein.


C. Cationic Conditioning Polymers


The shampoo composition described herein may comprise one or more cationic conditioning polymers. This polymer may be selected from the group consisting of (a) a cationic guar polymer, (b) a cationic non-guar polymer, (c) a cationic tapioca polymer, (d) a cationic copolymer of acrylamide monomers and cationic monomers, (e) a synthetic, non-crosslinked, cationic polymer, which forms lyotropic liquid crystals upon combination with the detersive surfactant, and (f) mixtures thereof.


D. Carrier


The shampoo composition further comprises from about 75% to about 98%, alternatively from about 80% to about 98% of a cosmetically acceptable carrier, by weight of the shampoo composition. The carrier can be an aqueous carrier. The amount and chemistry of the carrier is selected according to the compatibility with other components and other desired characteristic of the product. In an embodiment, the carrier is selected from the group consisting of: water and water solutions of lower alkyl alcohols. Lower alkyl alcohols useful herein are monohydric alcohols having 1 to 6 carbons, such as ethanol and/or isopropanol. In an embodiment, the cosmetically acceptable carrier is a cosmetically acceptable aqueous carrier and is present at a level of from about 20% to about 95%, or from about 60% to about 85%.


The pH of the shampoo composition can be from about pH 3 to about pH 8, alternatively from about pH 4 to about pH 7, and alternatively from about pH 5 to about pH 6.


E. Benefit Agent


The shampoo composition may further comprise one or more benefit agents. Exemplary benefit agents include, but are not limited to, silicone emulsions, anti-dandruff actives, perfume microcapsules, gel networks, colorants, particles, and other insoluble skin or hair conditioning agents such as skin silicones, natural oils such as sun flower oil or castor oil.


(1). Silicone Emulsion


The silicone emulsions suitable for use herein include emulsions of insoluble polysiloxanes prepared in accordance with the descriptions provided in U.S. Pat. No. 4,476,282 and U.S. Patent Application Publication No. 2007/0276087. Accordingly, insoluble polysiloxanes referred to herein for the purpose of the invention include polysiloxanes such as alpha, omega hydroxy-terminated polysiloxanes or alpha, omega alkoxy-terminated polysiloxanes having a molecular weight within the range from about 50,000 to about 500,000 g/mol. As used herein, “insoluble polysiloxane” means that the water solubility of the polysiloxane is less than 0.05 wt %. In another embodiment, the water solubility of the polysiloxane is less than 0.02 wt %, or less than 0.01 wt %, or less than 0.001 wt %. According to an embodiment, the insoluble polysiloxane is present in the shampoo composition in an amount within the range from about 0.1 wt % to about 3 wt %, based on the total weight of the composition. For example, the insoluble polysiloxane can be present in an amount within the range from about 0.2 wt % to about 2.5 wt %, or from about 0.4 wt % to about 2.0 wt %, or from about 0.5 wt % to about 1.5 wt %, based on the total weight of the composition.


According to one aspect of the silicone emulsion, the insoluble polysiloxane used herein include alpha, omega hydroxy- or alkoxy-terminated polysiloxanes having a general formula I:

R1—[O—SiR2]n—OR1

wherein ‘n’ is an integer, R is a substituted or unsubstituted C1 to C10 alkyl or aryl, and R1 is a hydrogen or a substituted or unsubstituted C1 to C10 alkyl or aryl. Non-limiting examples of R and R1 may be independently selected from alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tertpentyl, hexyl such as n-hexyl, heptyl such as n-heptyl, octyl such as n-octyl and isooctyl such as 2,2,4-trimethyl-pentyl, nonyl such as n-nonyl, decyl such as n-decyl, dodecyl such as n-dodecyl, octadecyl such as n-octadecyl; or aryl groups such as phenyl, naphthyl, anthryl and phenanthryl. In an embodiment, the insoluble polysiloxane has a general formula H—[O—SiR2]n—OH.


According to another aspect of the silicone emulsion, the insoluble polysiloxane has an average molecular weight within the range from about 50,000 to about 500,000 g/mol. For example, the insoluble polysiloxane may have an average molecular weight within the range from about 60,000 to about 400,000; from about 75,000 to about 300,000; from about 100,000 to about 200,000; or the average molecular weight may be about 150,000 g/mol.


According to another aspect of the silicon emulsion, total content of a cyclic polysiloxane having a general formula:




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wherein R is as defined above, and wherein m is 4 or 5, is present in the silicone emulsion in an amount less than about 2.5 wt % based on the total weight of all polysiloxanes. For example, dimethiconol may include significant quantities of cyclic polysiloxanes, such as octamethylcyclotetrasiloxane (D4) and decamethylcyclotetrasiloxane (D5). In an embodiment, the amount of D4 is less than about 2.0%, or less than about 1.5%, or less than about 1.0%, or less than about 0.5%, based on the total weight of all polysiloxanes. In an embodiment, the amount of D5 is less than about 0.5%, or less than about 0.4%, or less than about 0.3%, or less than about 0.2%, based on the total weight of all polysiloxanes.


According to yet another aspect of the silicone emulsion, the emulsion has a viscosity up to about 500,000 cPs. For example, the viscosity may be within the range from about 75,000 to about 300,000, from about 100,000 to about 200,000, or about 150,000 cPs.


According to yet another aspect of the silicone emulsion, the insoluble polysiloxane has an average particle size within the range from about 30 nm to about 10 micron. The average particle size may be within the range from about 40 nm to about 5 micron, from about 50 nm to about 1 micron, from about 75 nm to about 500 nm, or about 100 nm, for example.


The average molecular weight of the insoluble polysiloxane, the viscosity of the silicone emulsion, and the size of the particle comprising the insoluble polysiloxane are determined by methods commonly used by those skilled in the art, such as the methods disclosed in Smith, A. L. The Analytical Chemistry of Silicones, John Wiley & Sons, Inc.: New York, 1991. For example, the viscosity of the silicone emulsion can be measured at 30° C. with a Brookfield viscosimeter with spindle 6 at 2.5 rpm.


According to another aspect of the silicone emulsion, the emulsion further includes an anionic surfactant that participates in providing high internal phase viscosity emulsions having particle sizes in the range from about 30 nm to about 10 micron. The anionic surfactant is selected from organic sulfonic acids. Most common sulfonic acids used in the present process are alkylaryl sulfonic acid; alkylaryl polyoxyethylene sulphonic acid; alkyl sulfonic acid; and alkyl polyoxyethylene sulfonic acid. General formulas of the sulfonic acids are as shown below:

R2C6H4SO3H  (II)
R2C6H4O(C2H4O)mSO3H  (III)
R2SO3H  (IV)
R2O(C2H4O)mSO3H  (IV)

Where R2, which may differ, is a monovalent hydrocarbon radical having at least 6 carbon atoms. Non-limiting examples of R2 include hexyl, octyl, decyl, dodecyl, cetyl, stearyl, myristyl, and oleyl. ‘m’ is an integer from 1 to 25. Exemplary anionic surfactants include but are not limited to octylbenzene sulfonic acid; dodecylbenzene sulfonic acid; cetylbenzene sulfonic acid; alpha-octyl sulfonic acid; alpha-dodecyl sulfonic acid; alpha-cetyl sulfonic acid; polyoxyethylene octylbenzene sulfonic acid; polyoxyethylene dodecylbenzene sulfonic acid; polyoxyethylene cetylbenzene sulfonic acid; polyoxyethylene octyl sulfonic acid; polyoxyethylene dodecyl sulfonic acid; and polyoxyethylene cetyl sulfonic acid. Generally, 1 to 15% anionic surfactant is used in the emulsion process. For example, 3-10% anionic surfactant can be used to obtain an optimum result.


The silicone emulsion may further include an additional emulsifier together with the anionic surfactant, which along with the controlled temperature of emulsification and polymerization, facilitates making the emulsion in a simple and faster way. Non-ionic emulsifiers having a hydrophilic lipophilic balance (HLB) value of 10 to 19 are suitable and include polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenyl ethers and polyoxyalkylene sorbitan esters. Some useful emulsifiers having an HLB value of 10 to 19 include, but are not limited to, polyethylene glycol octyl ether; polyethylene glycol lauryl ether; polyethylene glycol tridecyl ether; polyethylene glycol cetyl ether; polyethylene glycol stearyl ether; polyethylene glycol nonylphenyl ether; polyethylene glycol dodecylphenyl ether; polyethylene glycol cetylphenyl ether; polyethylene glycol stearylphenyl ether; polyethylene glycol sorbitan monostearate; and polyethylene glycol sorbitan monooleate.


In accordance with another embodiment, the composition may further comprise an anti-dandruff active, which may be an anti-dandruff active particulate.


F. Other Components


The shampoo composition can also additionally comprise any suitable optional ingredients as desired. Such optional ingredients should be physically and chemically compatible with the components of the composition, and should not otherwise unduly impair product stability, aesthetics, or performance. The CTFA Cosmetic Ingredient Handbook, Tenth Edition (published by the Cosmetic, Toiletry, and Fragrance Association, Inc., Washington, D.C.) (2004) (hereinafter “CTFA”), describes a wide variety of nonlimiting materials that can be added to the composition herein.


In accordance with another embodiment of the invention, a method of making a shampoo composition comprising a detersive surfactant, a cationic conditioning polymer, a chelant, and a carrier is provided. The method includes (i) combining the detersive surfactant and the cationic conditioning polymer in suitable carrier, and (ii) combining a chelant and a carrier composition that includes a product of step (i) to form the shampoo composition.


In an embodiment, the shampoo composition has a viscosity of 4,000 cP to 20,000 cP, or from about 6,000 cP to about 12,000 cP, or from about 8,000 cP to about 11,000 cP, measured at 26.6° C. with a Brookfield R/S Plus Rheometer at 2 s−1. cP means centipoises.


Also described herein is a method of inhibiting copper deposition on hair and facilitating the removal of copper deposited on hair comprising applying to the hair a shampoo composition described herein and rinsing the shampoo composition from the hair.


Inhibition of copper deposition on hair and facilitation of the removal of copper deposited on hair may also be achieved by applying a leave-on treatment to the hair after rinsing the conditioner from the hair. The leave-on treatment may deliver consumer desired conditioning in addition to inhibiting the deposition of copper (i.e. from the water used to rinse) on the hair. The leave-on treatment described herein may comprise from about 0.025% to about 0.50%, alternatively from about 0.05% to about 0.25% of one or more chelants described herein, by weight of the leave-on treatment. The leave-on treatment may also comprise one or more rheology modifiers and an aqueous carrier.


The shampoo composition can be prepared by conventional formulation and mixing techniques. It will be appreciated that other modifications of the shampoo composition within the skill of those in the hair care formulation art can be undertaken without departing from the spirit and scope of this invention. All parts, percentages, and ratios herein are by weight unless otherwise specified. Some components may come from suppliers as dilute solutions. The amount stated reflects the weight percent of the active material, unless otherwise specified.


Test Methods
Shampoo Treatment Protocol

All testing are performed on colored hair switches (see Method of Measurement of Copper on Hair below) weighing approximately 4.0 grams and having a length of approximately 6 inches. The hair switches are commercially available from IHIP (International Hair Importers). Three hair switches per shampoo composition are used. An amount of 0.20 g of shampoo is spread via a syringe onto separate hair switch. That is, the dosage is 0.10 g of shampoo per g of hair. Each application consists of adding shampoo to the hair, milking for 30 seconds followed by rinsing for 30 seconds. Shampoo is then reapplied (0.1 g/g), milked for 30 seconds and rinsed for 30 seconds. Excess water is squeezed from the hair switches and left to air dry or treated with a rinse-off conditioner and/or a leave-on treatment composition. This protocol is repeated for a number of times/cycles (as indicated in the tables below, which describe the details of hair treatments).


Method of Measurement of Copper on Hair

The following test method is used to assess the ability of the compositions and regimens to remove copper from the hair and to inhibit copper deposition onto the hair.


Hair switches are colored once with an oxidative hair colorant. An extra blonde shade is used for the testing. The hair switches are washed for 10 or 20 repeat wash cycles in tap water containing 7 grains per gallon water hardness (Ca/Mg) and 0.06 μg/g copper ions. Each wash cycle consists of two applications of 0.1 g/g a shampoo to the hair switches. Each application consists of adding shampoo to the hair, milking for 30 secs followed by rinsing for 30 secs. Shampoo is then reapplied 0.1 g/g, milked for 30 secs, rinsed for 30 secs and then dried in a heat box (60° C.) until dry.


Samples of 100 mg of hair are digested overnight with 2 ml of high purity concentrated nitric acid. The digestive mixture also contains 150 μL of 100 μg/g Yttrium internal standard (Inorganic Ventures, Christianburg, Va., USA). Following digestion, samples are heated to 70-80° C. for one hour, cooled to room temperature and diluted to 15 mL with deionized water. Copper content of the hair switches is determined by inductively coupled plasma atomic spectroscopy (ICP-OES)). For each leg, 3 different samples are analyzed.


EXAMPLES & DATA

The following are non-limiting examples of the shampoo composition described herein. The examples are given solely for the purpose of illustration and are not to be construed as limitations of the shampoo composition, as many variations thereof are possible without departing from the spirit and scope of the shampoo composition, which would be recognized by one of ordinary skill in the art.


The shampoo composition described herein is generally prepared by conventional methods. Such methods typically involve mixing of the ingredients in one or more steps to a relatively uniform state, with or without heating, cooling, application of vacuum, and the like. The compositions are prepared such as to optimize stability (physical stability, chemical stability, photostability) and/or delivery of the active materials. The shampoo composition may be in a single phase or a single product, or the shampoo composition may be in a separate phases or separate products. If two products are used, the products may be used together, at the same time, or sequentially. Sequential use may occur in a short period of time, such as immediately after the use of one product, or it may occur over a period of hours or days.


In order to minimize the variability of the resulting copper content on hair that is related to (a) lot-to-lot viariability due to hair switches and (b) day-to-day variability of the water used during shampoo and conditioner treatments, a single lot of hair switches is used for each experimental series and a separate control experiment/treatment is run for each experimental series (see below).


Experimental Series I

Investigation of treatments using shampoos containing naturally-derived cationic conditioning agent (modified cassia polymer).
















Ex. 1





Control
Ex. 2
Ex. 3


Components
Wt %
Wt %
Wt %


















Sodium Laureth-3 Sulfate1
10.00
10.00
10.00


Cocoamide MEA2
2.77
2.77
2.77


Sodium xylenesulfonate
2.00
2.00
2.00


Cassia
0.80
0.80
0.80


hydroxypropyltrimonium


chloride3


Disodium EDTA dehydrate
0.25
0.25
0.25


Citric Acid (Anhydrous)
0.55
0.55
0.55


Sodium benzoate
0.50
0.50
0.50


Methylchloroisothiazolinone/
0.001
0.001
0.001


Methylisothiazolinone4


Sodium chloride
4.00
4.00
4.00


Picolinic acid
0.00
0.10
0.50


Perfume
0.40
0.40
0.40


Distilled Water
Q.S. to 100
Q.S. to 100
Q.S. to 100






1Sodium laureth-3-sulfate available from BASF as Standapol ES-3 (28 wt. % active).




2Cocamide MEA available from BASF as Comperlan CMEA (85 wt. % active).




3Sensomer CT-400 avalibale from Lubrizol Advanced Materials.




4Kathon CG available from Dow (1.5 wt % active).








Results of Experimental Series I















Composition of











Ex. 1





Control
Ex. 2
Ex. 3














Summary Description of
Control
Shampoo with
Shampoo with


Composition
Shampoo with
naturally-derived
naturally-



naturally-
cationic
derived



derived
conditioning
cationic



cationic
agent and a
conditioning



conditioning
chelant
agent and a



agent

chelant


Concentration of Chelant in
0.00%
0.10%
0.50%


Shampoo


Chelant used

Picolinic acid
Picolinic acid


Chelant Class

Class I
Class I


Shampoo cycles
20
20
20


Average final copper
59
31
29


concentration in hair (ppm)


Standard deviation
1.8
2.9
1.6


Relative content of Copper
100
53
49


content on hair after treatment


(versus control shampoo


treatment)









Picolinic acid contributes to significant reduction of copper content on hair after 20 shampoo cycle treatments compared to treatment with shampoo composition that does not contain the chelant.


Experimental Series II

Investigation of treatments with clarifying shampoos containing simple surfactants and picolinic acid in two different pH values.

















Ex. 4
Ex. 5





Control
Control
Ex. 6
Ex. 7


Components
Wt %
Wt %
Wt %
Wt %



















Sodium Laureth-1 Sulfate1
10.50
10.50
10.50
10.50


Sodium Lauryl Sulfate2
1.50
1.50
1.50
1.50


Cocamidopropyl betaine
1.00
1.00
1.00
1.00


Sodium benzoate
0.25
0.25
0.25
0.25


Citric Acid
0.70
1.00
0.70
1.00


Methylchloroisothiazolinone/
0.0005
0.0005
0.0005
0.0005


Methylisothiazolinone3


Sodium chloride
1.00
1.00
1.00
1.00


Tetrasodium EDTA dihydrate
0.16
0.16
0.16
0.16


Picolinic acid
0.00
0.00
0.10
0.10


Deionized water
Q.S. to 100
Q.S. to 100
Q.S. to 100
Q.S. to 100


pH adjusted to
6.0
4.25
6.0
4.25






1Sodium laureth-3-sulfate available from BASF as Standapol ES-3 (28 wt. % active).




2Sodium Lauryl Sulfate available from BASF as Standapol WAQ-LC (29 wt. % active).




3Kathon CG available from Dow (1.5 wt % active).








Results of Experimental Series II















Composition of












Ex. 4
Ex. 5
Ex. 6
Ex. 7















Summary Description of
Control
Control
Clarifying
Clarifying


Composition
Clarifying
Clarifying
shampoo
shampoo



shampoo
shampoo
with simple
with simple



with simple
with simple
surfactant
surfactant



surfactant
surfactant
and a chelant
and a chelant


Concentration of Chelant in
0.0%
0.0%
0.10%
0.10%


Shampoo


Chelant used


Picolinic acid
Picolinic acid


Chelant Class


Class I
Class I


Shampoo pH
6.0
4.25
6.0
4.25


Shampoo cycles
10
10
10
10


Average final copper
123
80
69
60


concentration in hair (ppm)


Standard deviation
6.0
3.9
7.5
2.1


Relative content of Copper
100
65
69
60


content on hair after

v. Ex. 4
v. Ex. 4
v. Ex. 4


treatment (versus control


shampoo treatment)









Lower shampoo pH (4.25 versus 6.0) and the presence of picolinic acid contribute to a more effective removal of copper from hair after 10 shampoo cycles.


Experimental Series III

Investigation of treatments with clarifying shampoos containing simple surfactants (pH=6) and various Class I and Class II chelants.






















Ex. 8










Control
Ex. 9
Ex. 10
Ex. 11
Ex. 12
Ex. 13
Ex. 14
Ex. 15
























Components
Wt %
Wt %
Wt %
Wt %
Wt %
Wt %
Wt %
Wt %


Sodium Laureth-1 Sulfate1
10.50
10.50
10.50
10.50
10.50
10.50
10.50
10.50


Sodium Lauryl Sulfate2
1.50
1.50
1.50
1.50
1.50
1.50
1.50
1.50


Cocamidopropyl betaine
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00


Sodium benzoate
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25


Citric Acid
0.70
0.70
0.70
0.70
0.70
0.70
0.70
0.70


Methylchloroisothiazolinone/
0.0005
0.0005
0.0005
0.0005
0.0005
0.0005
0.0005
0.0005


Methylisothiazolinone3


Sodium chloride
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00


Tetrasodium EDTA
0.16
0.16
0.16
0.16
0.16
0.16
0.16
0.16


dihydrate


Picolinic acid
0.00
0.10
0.00
0.00
0.00
0.00
0.00
0.00


Fusaric acid
0.00
0.00
0.10
0.00
0.00
0.00
0.00
0.00


Quinolinic acid
0.00
0.00
0.00
0.10
0.00
0.00
0.00
0.00


Dipicolinic acid
0.00
0.00
0.00
0.00
0.10
0.00
0.00
0.00


6-Methylpicolinic acid
0.00
0.00
0.00
0.00
0.00
0.10
0.00
0.00


Chelidamic acid
0.00
0.00
0.00
0.00
0.00
0.00
0.10
0.00


Quinaldic acid
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.10


Deionized water
Q.S.
Q.S.
Q.S.
Q.S.
Q.S.
Q.S.
Q.S.
Q.S.


pH adjusted to
6.0
6.0
6.0
6.0
6.0
6.0
6.0
6.0






1Sodium laureth-3-sulfate available from BASF as Standapol ES-3 (28 wt. % active).




2Sodium Lauryl Sulfate available from BASF as Standapol WAQ-LC (29 wt. % active).




3Kathon CG available from Dow (1.5 wt % active).








Results of Experimental Series III

















Composition of












Ex. 8






Control
Ex. 9
Ex. 10
Ex. 11





Summary Description of
Control
Clarifying
Clarifying
Clarifying


Composition
Clarifying
shampoo
shampoo
shampoo



shampoo
with simple
with simple
with simple



with simple
surfactant
surfactant
surfactant



surfactant
and a
and a chelant
and a chelant




chelant


Concentration of Chelant in
0.0%
0.10%
0.10%
0.10%


Shampoo


Chelant used

Picolinic
Fusaric acid
Quinolinic




acid

acid


Chelant Class

Class I
Class I
Class I


Shampoo pH
6.0
6.0
6.0
4.5


Shampoo cycles
10
10
10
10


Average final copper
79
40
39
41


concentration in hair (ppm)


Standard deviation
7
2.9
0.6
2.2


Relative content of Copper
100
51
49
52


content on hair after


treatment (versus control


shampoo treatment)












Composition of












Ex. 12
Ex. 13
Ex. 14
Ex. 15





Summary Description of
Clarifying
Clarifying
Clarifying
Clarifying


Composition
shampoo
shampoo with
shampoo
shampoo



with simple
simple surfactant
with simple
with simple



surfactant
and a chelant
surfactant
surfactant



and a chelant

and a
and a





chelant
chelant


Concentration of
0.10%
0.10%
0.10%
0.10%


Chelant in Shampoo


Chelant used
Dipicolinic
6-Methylpicolinic
Chelidamic
Quinaldic



caid
aid
acid
acid


Chelant Class
Class I
Class I
Class I
Class II


Shampoo pH
6.0
6.0
6.0
6.0


Shampoo cycles
10
10
10
10


Average final copper
46
51
52
52


concentration in hair


(ppm)


Standard deviation
4.2
5.9
2.2
4


Relative content of
58
65
66
66


Copper content on hair


after treatment (versus


control shampoo


treatment)









All chelants from Class I and Class II evaluated in a 10 cycle cleaning treatment using a clarifying shampoo containing simple surfactants shows reduction of copper hair content compared to the control shampoo treatment. Fusaric acid, picolinic acid, quinolinic acid show more effective treatments.


The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as “40 mm” is intended to mean “about 40 mm.”


Every document cited herein, including any cross referenced or related patent or application, is hereby incorporated herein by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other reference or references, teaches, suggests or discloses any such invention. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.


While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims
  • 1. A shampoo composition comprising: (a) from about 0.1% to about 1.5%, by weight of the shampoo composition, of an effective chelant comprising picolinic acid;(b) from about 2% to about 50% of one or more detersive surfactants, by weight of the shampoo composition; and(c) from about 75% to about 98% of an aqueous carrier, by weight of the shampoo composition;wherein the shampoo composition has a pH of about 3 to about 8.
  • 2. The shampoo composition of claim 1, wherein the one or more detersive surfactants is selected from anionic surfactants, cationic surfactants, non-ionic surfactants, amphoteric surfactants, or mixtures thereof.
  • 3. The shampoo composition of claim 1, wherein the shampoo composition comprises from about 5% to about 25% of the one or more detersive surfactants by weight of the shampoo composition.
  • 4. The shampoo composition of claim 1, wherein the shampoo composition comprises from about 7% to about 22% of the one or more detersive surfactants by weight of the shampoo composition.
  • 5. The shampoo composition of claim 1, wherein the shampoo composition comprises from about 9% to about 18% of the one or more detersive surfactants by weight of the shampoo composition.
  • 6. The shampoo composition of claim 1, wherein the log of the formation constant log KML of the complex with copper of the picolinic acid is greater than 4.
  • 7. The shampoo composition of claim 1, wherein the log of the formation constant log KML of the complex with copper of the picolinic acid is greater than 5.
  • 8. The shampoo composition of claim 1, wherein the log P value of the picolinic acid is about 0.7.
  • 9. The shampoo composition of claim 1, wherein the molecular weight of the picolinic acid is about 123.
  • 10. The shampoo composition of claim 1, further comprising a gel network, wherein the gel network comprises a fatty alcohol and a surfactant.
  • 11. The shampoo composition of claim 1, wherein the shampoo composition comprises from about 0.1% to about 0.5% of the picolinic acid.
  • 12. A method of inhibiting copper deposition on hair and facilitating the removal of copper deposited on hair comprising: a. applying to the hair the shampoo composition of claim 1; andb. rinsing the shampoo composition from the hair.
US Referenced Citations (100)
Number Name Date Kind
3940482 Grand Feb 1976 A
4089945 Brinkman et al. May 1978 A
4185106 Dittmar et al. Jan 1980 A
4321156 Bushman Mar 1982 A
4412943 Hirota et al. Nov 1983 A
4749507 Varco Jun 1988 A
4822604 Knoll et al. Apr 1989 A
4855130 Konrad et al. Aug 1989 A
5306489 Goldberg et al. Apr 1994 A
5559092 Gibson et al. Sep 1996 A
5635167 Said Jun 1997 A
5804172 Ault Sep 1998 A
5847003 Ptchelintsev et al. Dec 1998 A
6069169 Ptchelintsev et al. May 2000 A
6071962 Ptchelintsev et al. Jun 2000 A
6287547 Oota et al. Sep 2001 B1
6348189 Tanabe et al. Feb 2002 B1
6358502 Tanabe et al. Mar 2002 B1
6365143 Lundmark et al. Apr 2002 B1
6380263 Pruche et al. Apr 2002 B1
6432147 Dias et al. Aug 2002 B1
6432394 Pyles et al. Aug 2002 B2
6509011 Ellis et al. Jan 2003 B1
6544500 O'Toole et al. Apr 2003 B1
6551361 Cornwell et al. Apr 2003 B1
6602493 Akhter et al. Aug 2003 B2
6624126 Kasuga et al. Sep 2003 B1
6743434 Landmark et al. Jun 2004 B1
6858202 Niemiec et al. Feb 2005 B2
6864314 Yeung et al. Mar 2005 B1
6927196 Snyder et al. Aug 2005 B2
7045493 Wang et al. May 2006 B2
7169743 Wang et al. Jan 2007 B2
7186274 Vic et al. Mar 2007 B2
7186275 Boswell Mar 2007 B2
7300647 O'Toole et al. Nov 2007 B1
7335700 Yeung et al. Feb 2008 B2
7547454 Gupta Jun 2009 B2
7700078 Huglin et al. Apr 2010 B2
7709430 Mizushima May 2010 B2
7745382 Sloan Jun 2010 B2
7915212 Yeung et al. Mar 2011 B2
8022020 Sloan Sep 2011 B2
8039424 Sloan Oct 2011 B2
8404257 Huglin et al. Mar 2013 B1
8449868 Jennings et al. May 2013 B2
8637489 Van Nguyen et al. Jan 2014 B2
8942481 Suarez Cambre et al. Jan 2015 B2
9044413 Yeung et al. Jun 2015 B2
9080135 Hough et al. Jul 2015 B2
9271908 Allef et al. Mar 2016 B2
9358195 Lupia et al. Jun 2016 B2
9586063 Marsh et al. Mar 2017 B2
9642788 Marsh et al. May 2017 B2
10539872 Tadokoro Jan 2020 B2
20030095938 Casero May 2003 A1
20030125224 Seitz Jul 2003 A1
20030176303 Niemiec et al. Sep 2003 A1
20030211953 Glenn Nov 2003 A1
20030215522 Johnson Nov 2003 A1
20040058855 Schwartz et al. Mar 2004 A1
20040123402 Marsh et al. Jul 2004 A1
20040261198 Kainz et al. Dec 2004 A1
20040266656 Sakurai Dec 2004 A1
20050095215 Popp May 2005 A1
20050095261 Popp May 2005 A1
20050239723 Amin Oct 2005 A1
20050256313 Norenberg et al. Nov 2005 A1
20060009371 Wang et al. Jan 2006 A1
20060063695 Wang et al. Mar 2006 A1
20060130246 Molenda et al. Jun 2006 A1
20060287219 Dykstra Dec 2006 A1
20080005715 Shimizu et al. Jan 2008 A1
20080057015 Oblong Mar 2008 A1
20080145328 Schwartz Jun 2008 A1
20090071493 Nguyen Mar 2009 A1
20090074700 Nguyen et al. Mar 2009 A1
20090092561 Lupia et al. Apr 2009 A1
20100069338 Ward et al. Mar 2010 A1
20100195039 Park Aug 2010 A1
20110015120 Bortolin Jan 2011 A1
20120034181 Hoffmann et al. Feb 2012 A1
20120034182 Hoffmann et al. Feb 2012 A1
20130122070 Barnett May 2013 A1
20130174863 Marsh et al. Jul 2013 A1
20130333715 Hutton, III et al. Dec 2013 A1
20140079660 Doi Mar 2014 A1
20140213499 Chen et al. Jul 2014 A1
20140349902 Allef et al. Nov 2014 A1
20150011449 Snyder Jan 2015 A1
20150030644 Oh et al. Jan 2015 A1
20150093420 Snyder et al. Apr 2015 A1
20150140052 Gizaw May 2015 A1
20150182431 Chaudhuri Jul 2015 A1
20160175210 Marsh et al. Jun 2016 A1
20180000705 Marsh Jan 2018 A1
20180000706 Marsh Jan 2018 A1
20180000714 Marsh Jan 2018 A1
20180000715 Marsh Jan 2018 A1
20190336426 Marsh Nov 2019 A1
Foreign Referenced Citations (44)
Number Date Country
1147262 May 1983 CA
19536420 Apr 1996 DE
10259199 Jun 2004 DE
102011079664 Apr 2012 DE
1046390 Oct 2000 EP
1714634 Oct 2006 EP
2067467 Jun 2009 EP
2853529 Oct 2004 FR
2853530 Oct 2004 FR
2853531 Oct 2004 FR
2288812 Jan 1995 GB
2315770 Feb 1998 GB
S57109711 Jul 1982 JP
S63150213 Jun 1988 JP
05262623 Oct 1993 JP
06041579 Feb 1994 JP
07258698 Oct 1995 JP
09183996 Jul 1997 JP
09291024 Nov 1997 JP
H11139941 May 1999 JP
11180836 Jul 1999 JP
11269487 Oct 1999 JP
2004059540 Feb 2004 JP
2006160708 Jun 2006 JP
2008169183 Jul 2008 JP
2011046652 Mar 2011 JP
1020090077562 Jul 2009 KR
WO9116878 Nov 1991 WO
WO9311737 Jun 1993 WO
WO9804237 Feb 1998 WO
WO9824400 Jun 1998 WO
WO0051555 Sep 2000 WO
WO0051556 Sep 2000 WO
WO200119327 Mar 2001 WO
WO-0220486 Mar 2002 WO
WO02065982 Aug 2002 WO
WO02102302 Dec 2002 WO
WO2007079793 Jul 2007 WO
WO2008136000 Nov 2008 WO
WO2008153050 Dec 2008 WO
WO2010106342 Sep 2010 WO
WO201220226 Feb 2012 WO
WO2012021472 Feb 2012 WO
WO2014182766 Nov 2014 WO
Non-Patent Literature Citations (29)
Entry
US 7,709,429 B2, 03/2010, Sloan (withdrawn)
U.S. Appl. No. 15/630,411, filed Jun. 22, 2017, Marsh et al.
U.S. Appl. No. 15/630,426, filed Jun. 22, 2017, Marsh et al.
U.S. Appl. No. 15/630,431, filed Jun. 22, 2017, Marsh et al.
U.S. Appl. No. 15/630,437, filed Jun. 22, 2017, Marsh et al.
All final and non-final office actions for U.S. Appl. No. 16/515,821.
All final and non-final office actions for U.S. Appl. No. 13/737,035.
All final and non-final office actions for U.S. Appl. No. 13/920,171.
All final and non-final office actions for U.S. Appl. No. 15/630,411.
All final and non-final office actions for U.S. Appl. No. 15/630,426.
All final and non-final office actions for U.S. Appl. No. 15/630,431.
All final and non-final office actions for U.S. Appl. No. 15/630,437.
Gary W. Evans, “The Role of Picolinic acid in Metal Metabolism”, Life Chemistry Reports, Jan. 1, 1982, pp. 57-67.
PCT International Search Report and Written Opinion for PCT/US2013/020735 dated Aug. 5, 2013.
PCT International Search Report and Written Opinion for PCT/US2017/038897 dated Sep. 18, 2017.
PCT International Search Report and Written Opinion for PCT/US2017/038899 dated Aug. 21, 2017.
PCT International Search Report and Written Opinion for PCT/US2017/038900 dated Aug. 21, 2017.
PCT International Search Report and Written Opinion for PCT/US2017/038903 dated Sep. 25, 2017.
PCT International Search Report and Written Opinion for PCT/US2017/038904 dated Sep. 18, 2017.
Vitality Unlimited: “What's A Picolinate?—Picolinic acid is the body's prime natural chelator”, Dec. 30, 1989.
Zurowska Bogum Ed—Lippert Bernhard et al., “Structural and Magnetic characterization of Cu-picolinate and Cu-Quinaldinate nad their mixed complexes with water or halides”, Inorganica Chimica Acta, vol. 418, May 2, 2014, pp. 136-152.
U.S. Appl. No. 16/515,821, filed Jul. 23, 2019, Marsh et al.
U.S. Appl. No. 16/931,880, filed Jul. 20, 2020, Marsh et al.
U.S. Appl. No. 16/985,902, filed Aug. 5, 2020, Marsh et al.
Alberto Culver, Canada, Shampoo, Mintel GNPD, Mar. 2008.
All final and non-final office actions for U.S. Appl. No. 16/931,880.
All final and non-final office actions for U.S. Appl. No. 16/985,902.
Procter & Gamble, UK, 0% Grease Shampoo, Mintel, Feb. 2016.
Charles N Reilley et al: “Chelan Approach to Analysis (I) Survey of Theory and Application”, Journal of Chemical Education, Nov. 1, 1959 (Nov. 1, 1959), XP0557 40258,Retrieved from the Internet:URL:https://pubs.acs.org/doi/pdf/10.1021 /ed036p555?rand=jisnuiqf [retrieved on Oct. 15, 2020], pp. 555-564.
Related Publications (1)
Number Date Country
20180000713 A1 Jan 2018 US
Provisional Applications (1)
Number Date Country
62356953 Jun 2016 US