Patent Grant
11229589
Personal care and cosmetic products appeal to consumers not only due to beauty and hygiene concerns, but also as a means of social integration and well-being. However, amongst all attributes of such products, consumers rely primarily on sensorial aspects to decide if they will purchase the same product again. Most personal care and cosmetic carriers are a composition of both water and oil phases stabilized according to the principles of emulsion technology, but full oil-based, alcohol or other solvent based, or aqueous solution-based formulations are also alternatives.
When water or any other volatile materials are present in a personal care product that is applied to, for example, skin, they evaporate after application due to regular body temperature. The non-volatile components, such as emollient oils, are left behind. Emollient oils condition the skin, hair or nails. By conditioning, it is meant refatting, lubricating, softening and smoothing, and/or reducing the appearance of fine lines and wrinkles.
Although many emollient oils are effective in conditioning skin, many may leave an unpleasant after-feel, an unctuous feeling, or a shininess that is not desired. What is often desired is effective conditioning without the aforementioned negative attributes. What is highly desired by consumers is effective conditioning in a platform that results in an after-feel described as “light.”
One aspect that strongly affects the achievement of “lightness” is, in addition to the property of the oils themselves, the thickness of the residual oil layer that remains on the treated surface. The property of “spreadability” refers to the ability of a liquid substance to spread over the surface of a certain substrate, that is, the rate at which the liquid moves from the application area to the surrounding area, and the distance from the application area. In the case of, for example, skin applications, the spreadability of a material affects its residual thickness, which in turn relates to the user's perception of “lightness”. A higher spreading material leads to a larger spreading area, and thus a thinner film remains.
Spreadability is also related to viscosity, to the affinity of the liquid for the substrate (adhesiveness) and the affinity of the liquid for itself (cohesiveness.) For this reason, a low viscosity liquid may spread more slowly than a higher viscosity liquid. As an example, water, a highly polar and very low viscosity liquid, does not spread at all on the non-polar surface material Teflon® (polytetrafluoroethylene). Water has high affinity for itself, and no affinity for Teflon®.
Fatty ester oils (“esters”) are used as emollients and conditioning agents, and are included in compositions meant to be used on keratinized surfaces, such as the skin, hair and nails. The ester linkage in ester materials is polar. Keratinized surfaces such as skin, hair and nails are also polar. Because of this, esters are adhesive to these substrates.
Esters adhere through polar-polar interactions and for that reason provide conditioning benefits, especially on the skin. This polar-polar interaction also makes the ester molecules adhere to themselves which makes them cohesive, and lowers their spreadability.
Conventional personal care products relied upon petrochemically derived esters delivered to these skin or “silicone fluids”/hair/nails in volatile carriers or solvents such as silicone oils or fluids. Volatile silicone oils, such as the cyclomethicones and lower molecular weight dimethicones, are essentially non-polar, so they are poorly adhesive and poorly cohesive. They possess a low contact angle to the hair and skin, which relates to faster spreadability, and are volatile—evaporating from surfaces at room temperature. Because of their volatility, silicone oils do not function as emollients or conditioning agents because they do not remain on the substrate. They are, however, useful for delivering non-volatile emollients, actives and other components such as higher viscosity esters to the substrate in applications such as antiperspirants. When blended with other ingredients such as emollients and polymers, silicone oils increase the overall spreadability on the material, resulting in a thinner residual layer remaining on the skin surface giving a desired, lighter skin feel. However, the silicone oils are also derived from petrochemicals.
The trend to move away from use of petrochemical-derived ingredients in personal and home care remains strong. Products derived from renewable resources such as vegetable/plant matter can be presented to consumers as “natural” in contrast to pertrochemically derived materials. In addition, many manufacturers prefer to avoid ingredients derived from “palm oil”, e.g., from plants of the genera Elaeis or Attalea, such as the African oil palm Elaeis oleifera, Elaeis guineessis and/or the maripa palm Attalea maripa in view of concerns related to deforestation, microclimate change, and indigenous specie's habitat disruption.
To date, some 100% vegetable-derived low viscosity esters have been developed and commercialized such as LexFeel Natural (heptyl undecylenate, INOLEX, Inc., USA), SustOleo DCS (diisooctyl succinate, INOLEX, Inc. USA) and SustOleo MCT (triheptanoin, INOLEX Inc., USA.) Furthermore, each of these products is not derived from palm oil.
Hydrocarbon fluids are also known for use as carrier fluids and solvents. Many are volatile, and like volatile silicones, they are non-polar and also give rise to low contact angle on the substrate which relates to faster spreadability. For example, the Parafol (Sasol, Germany) series of linear hydrocarbons are derived from both coconut and palm sources. Another example is Neossance Hemisqualane (Amyris, USA) which is hydrogenated farnesene, a branched hydrocarbon substance containing 15 carbon atoms overall.
The parent material, farnesene is derived from the fermentation of sugar cane, for example, as is described in WO2017059136 A1, the contents of which is incorporated herein by reference.
Use of ester oils blended with hydrocarbons have been disclosed. For example, WO2004103308 A2 describes mixtures of esters derived from neopentyl glycol with isododecane to replicate the feel of cycloinethicone fluids; however, these mixtures are derived from materials of petrochemical origin, and therefore cannot be described as natural.
WO2010115973A1 discloses mixtures of linear hydrocarbons derived from coconut with non-volatile oils that purportedly mimic the feel of silicones. Branching in the alkane structure provides a lighter feeling because they are not able to pack together as tightly as linear alkanes. There is a need in the industry for efficient methods to improve the spreadability of a non-volatile liquid emollient esters, and thus improve the feel. Surprisingly, while studying emollient spreadability on the skin and on skin-like substrates, the present inventors have found a method to improve esters spreadability, which results in improved sensory characteristics.
Described herein is an invention that includes a spreadable conditioning composition comprising a blend of: a branched hydrocarbon and an ester having a kinematic viscosity of less than or equal to about 100 centistokes. The composition may be natural, for example, if each of the branched hydrocarbon and the ester are independently vegetable-derived. In addition, the composition may lack ingredients that are derived from a palm oil. In an embodiment, the composition is a blend of hydrogenated farnesene and an esters selected from glyceryl triheptanoate, dicapryl succinate, heptyl undecylenate, and mixtures thereof. The composition exhibits an average spreading velocity of about 4 to about 8.
Also disclosed are formulations for use in products of personal care, home/institutional care, industry, pharmaceutical and medical and veterinary care.
The invention includes methods of preparing a surface conditioning formulation comprising mixing the composition described above with an additional ingredient, such as, for example, a surfactant, a colorant, a detersive agent, a mechanical sunscreen, a fragrance, a chealtor, an antioxidant, a UV absorbing compound, a particulate and a solvent or of preparing a natural composition having an average spreading velocity of about 4 to about 8 comprising blending a natural branched hydrocarbon with an natural ester having a kinematic viscosity of less than or equal to about 100 centistokes.
Methods of use of the composition include, for example, methods of increasing the spreadability of a conditioning agent that include combining the conditioning agent with a branched hydrocarbon, wherein the conditioning agent is an ester having a kinematic viscosity of less than or equal to about 100 centistokes; methods of delivering a material to a surface by applying a formulation of the invention to the surface whereon the formulation contains the composition of the invention and an additional ingredient, such as, for example, a UV absorbing agent, a biologic, a patinator, an antimicrobial agent, an antioxidant, a mica, glitter, a pigment, an anti-rust agents, an anti-tarnish agent, a whitener, and a self-tanner.
At least one Figure that is a color photograph is included herein. Copies of this patent or patent application publication with color drawings will be provided by the Office upon request and payment of the necessary fee.
The foregoing summary as well as the following detailed description of embodiments of the invention, may be better understood when read in conjunction with the appended drawings. For the purpose of illustrating the invention there is shown in the drawings embodiments which may be preferred. It should be understood, however, that the invention is not limited to the precise arrangements and instrumentalities shown. In the drawings:
The invention as described herein include a conditioning or emollient composition providing multifaceted advantages, in addition to its conditioning properties. For example, when applied to the skin or other keratinized surfaces, it has a high average spread velocity which results in a composition that conditions the surface while providing to the user a “light”, not greasy skinfeel. It can be prepared to be 100% natural, as all its components may be vegetable derived. However, use of palm oil derived ingredients can also be avoided. Within the scope of the invention are, without limitation, the composition itself, methods of using and/or making the composition, methods of improving the average spread velocity of a emollient ester, end products, such as personal care, pharmaceutical, or industrial, institutional and/or home care products or formulations that contain the composition, and method of conditioning surface, such as a keratinized surfaces, the surface of a textile or fiber and the like, by applying the compositions of the invention.
As used herein, “conditioning” means accomplishing any one or more of refatting, lubricating, smoothing, softening, patinating, and/or, with respect to living skin, reducing the appearance of fine lines and wrinkles. A “conditioning agent”, therefore, is a material that is chemically capable of carrying out any one or more of fatting, lubricating, smoothing, softening, patinating, and/or, with respect to living skin, reducing the appearance of fine lines and wrinkles.
If desired, the conditioning composition of the invention can be prepared to be 100% natural, that is, to have an absence of any ingredients that are derived from petrochemicals. In an embodiment, all components of the composition are obtained from botanical and plant (i.e., “vegetable”) sources. Such sources may include, without limitation, plants of the genera Pruna, plants of the family Arecaceae, coconut, palm, almond, castor, corn (maize), cottonseed, flax seed, hempseed, nut, olive, peanut, safflower, sesame, soybean, sunflower, jojoba, and combinations thereof.
In the practice of the invention, each of the ester(s), branched hydrocarbons, and/or any additional components may be vegetable-derived (i.e., “natural”). If all components are vegetable-derived, one may refer to the entire composition or formulation as “natural”.
The invention includes an ester or mixture of esters which may serve as the emollient or conditioning agent. Any ester(s) may be used. However, it may be preferred that the selected ester has a kinematic viscosity of less than or equal to about 100 centistokes, alternatively, less than or equal to about 75 centistokes, less than or equal to about 50 centistokes, or less than or equal to about 25 centistokes, when viscosity is measured by the protocol set forth in ASTM method D445, American Society for Testing and Materials, Conshohocken, N.Y. (see, Appendix A).
In an embodiment, the ester selected has about 1 to about 15 ester linkages, or about 2, about 3, about 4, about 5, about 6, or about 7 ester linkages. The linkages may be on the main chain of the ester molecule or on the substituents; however, it may be preferred that at least one to 4 of the linkages is on the main chain of the ester molecule.
Esters of any size/molecular weight may be used; however, in an embodiment, the ester has about 15 to 30 total carbons.
In an embodiment, the ester is selected from glyceryl triesters of medium chain carboxylic acids, diesters of medium chain diacids with medium chain linear or branched alcohols, monoesters of medium chain carboxylic acids with medium chain alcohols and mixtures thereof. (In all instances, “medium chain” is a hydrocarbon chain of about 6 to about 1 carbon atom(s)). It may be preferred that the ester is, for example, one or more of glyceryl triheptanoate, dicapryl succinate, heptyl undecylenate, and mixtures thereof. The chemical structures of these exemplary esters are shown in
The invention includes a hydrocarbon, preferably a branched hydrocarbon. With reference to IUPAC naming conventions, in an embodiment, the branched hydrocarbon includes a main hydrocarbon chain which bears at least one substituent chain (i.e., “branch”). The branched hydrocarbon may contain any number of carbon atoms in total (i.e., main chain plus the substituent chain(s) or branches) and/or in the main chain alone, if no branching is present.
In an embodiment, it may be preferred that the branched hydrocarbon contains about 10 to about 70, about 20 to about 50 or about 30 to about 40 carbon atoms in total. In a version of the inventive composition, the branched hydrocarbon contains about 9, about 10, about 11, about 12, about 13, about 14, and about 15, about 16, about 17, about 18, or about 19 carbon atoms in total.
With respect to the main hydrocarbon chain, in some embodiments, it may be desirable for the main hydrocarbon chain to have 5 to 50 or has 10 to 30 carbon atoms.
In an embodiment, it may be preferred that the substituent chain(s) are independently methyl groups (—CH2); alternatively, the substituent chains independently may have any number of carbon atoms, or be ethyl, propyl, butyl, pentyl hexyl, and/or heptyl. All of the substituent chain(s) on a given main hydrocarbon chain may be the same or different.
As noted above, the hydrocarbon is branched in that it has a main hydrocarbon chain that bears at least one substituent chain or “branch”. In an embodiment, the branched hydrocarbon has at least 3 branches, or about 2 to about 10, about 4 to about 5, branches that are on or extend from the main hydrocarbon chain.
In any embodiment that may be preferred, the branched hydrocarbon has a total carbon atom content represented by “X”, and a main hydrocarbon chain having a carbon atom content represented by “Y”. “X” is an integer of 13 to 50 and “Y” is 10 to 30 carbon atoms; alternatively, “X” is 15 carbon atoms and “Y” is 12 carbon atoms. In such instances, the carbon atoms not in the main hydrocarbon chain (that is, the difference between X and Y (e.g., X minus Y) serve to form one or more substituent chains from the main hydrocarbon chain.
In an embodiment, the branched hydrocarbon is hydrogenated farnesene, the structure of which is shown in
Regardless of specific structure, it may be preferred that the selected branched hydrocarbon(s) has a kinematic viscosity of less than or equal to about 100 centistokes, alternatively, less than or equal to about 80 centistokes, less than or equal to about 60 centistokes, or less than or equal to about 30 centistokes, when viscosity is measured by the protocol set forth in ASTM method D445, American Society for Testing and Materials, Conshohocken, N.Y. (see, Appendix A).
The composition is prepared by mixing the fluids in a suitable vessel to homogeneity. The amount of each of the ester and branched hydrocarbon components will vary depending on several factors, such as specific components selected, inclusion of other ingredients, end product to be formulated, end properties desired, etc. In general, it may be preferred that the branched hydrocarbon and the ester are present in a relative weight ratio (wt % hydrocarbon:wt % ester) that is one of: about 2:about 3, about 1:about 2.5, about 1:about 1, or about 2.5:about 1.
The composition may be prepared in advance, for example, as a concentrate or an admixture, an applied to the surface as-is. Or, it may subsequently be incorporated into a second prepared formulation to provide an end product. Attentively, the individual components may be added to a prepared formulation to form an end product. End products might be, for example, personal care products, home/institutional care products, industrial products, and/or pharmaceutical or veterinary products.
In embodiments where no other ingredients are present, it may be preferred that the branched hydrocarbon is present in the composition in an amount of about 30% to about 80% by weight of the total composition, about 40% to about 70% by weight of the total composition, or about 50% to about 60% by weight of the total composition.
Correspondingly therefore, it may be preferred that the ester is present in the composition in an amount of about 20% to about 70% by weight of the total composition, about 30% to about 50% by weight of the total composition, or 35% to about 45% by weight of the total composition.
Other ingredients may be included in the composition of the invention either to aid in the ease of manufacture, shipping and/or storage, or to provide the end user/consumer with added benefits or experiences. Examples are preservatives, colorants, fragrances, particulates, lipids, proteins, sensates and chelators. Moreover, by virtue of the composition's high average spread velocity, it provides an adherent thin film that is suitable for delivery of various additional agents to the surface to which it is applied. Without limitation, such agents may include mechanical sunscreens, UV light absorbers, pharmaceutical agents including biologics, patinators, antimicrobial agents, antioxidants, mica, glitter, pigments, anti-rust agents, anti-tarnish agents, a whitener, an optical brightener, a bluing agent, and/or self-tanners.
The composition of the invention may be incorporated into personal care, pharmaceutical, home/institutional care and industrial products for application to various surfaces, such as for example, hard surfaces, metals, wood, stone, tanned hides, furs and hairs, textiles, natural and synthetic fibers, and keratinized surfaces, such as hair, skin, nails/claws and hooves. It may contain substantially only the hydrocarbon and the ester, or other ingredients may be included.
Such products may also include other ingredients as is routine for the relevant product category, such as, for example, surfactants, fragrance, colorants, stabilizers, builders, ammonia, detersive agents, particulates, additional moisturizers or conditioners, glycerin, solvents, water, humectants, smectite and/or other clays, limonene, etc., as well as the additives listed above.
The composition of the invention can be used in method of increasing the spreadability of a conditioning agent, where the conditioning agent is a an ester having a kinematic viscosity of less than or equal to about 100 centistokes and/or is one or more of glyceryl triesters of medium chain carboxylic acids, diesters of medium chain diacids with medium chain linear or branched alcohols, monoesters of medium chain carboxylic acids with medium chain alcohols and mixtures thereof.
All permutations of the elements described above, including the presence or absence of an elements, are contemplated in the embodiments of the compositions, formulations, and/or the methods of the invention.
Ten compositions were prepared contain the ingredients shown below in Table 1.
All of the components are liquids at room temperature. The samples were each prepared by adding to a suitable vessel and agitating to homogeneity.
Each of the samples was evaluated for the following properties using the analytical methodologies shown in Table 2.
The contents of each ASTM are incorporated herein by reference.
The results of the evaluation are shown in
The spread velocity of each of the sample compositions 1-10 was evaluated using the following general procedure. An artificial skin substrate was used to determine average spreading velocity. Spreading is the rate at which the spreading area increases. Spreading always is fastest the moment the liquid touches the substrate, and then slows asymptotically to zero with time.
To determine these values, a 3×3 inch square piece of VITRO-SKIN® (IMS, Inc., Portland, Me., USA) membrane was previously hydrated in a humidity chamber set at room temperature (23° C.) and 60% humidity, for 16 hours. A micropipette was filled with test material and placed exactly 1-inch above the artificial membrane using a ring stand. The experimental set-up is shown in
A drop of sample composition (50 μL) was delivered to a central location onto the 3×3 inch square of VITRO-SKIN®. Spreading proceeds outward from the contact point and creates a circular spot. Since the wetted circular area of the VITRO-SKIN® can be seen, the diameter can be measured. This spreading diameter was measured after 1, 3 and 5 minutes of contact. The spreading area is determined taking the diameter of the spot in centimeters, halving to get the radius, squaring the radius, then multiplying by π. The resulting data will give an area at the 1, 3, and 5 minute time point. By subtracting the area at each time point from the area at the previous time point, the incremental additional area covered can be calculated. Thus the average spreading velocity can be determined by dividing the area covered by the time interval for each interval, then dividing by the total number of time intervals. Thus the equation for determining average spreading velocity for three time intervals per the experiments is as follows:
Wherein:
D1=diameter of circle after 1 minute
D2=diameter of circle after 3 minutes
D3=diameter of circle after 5 minutes
SAt1=area of circle after 1 minute
SAt2—area of circle after 3 minutes
SAt3=area of circle after 5 minutes
Therefore, the average spreading velocity=
[(SA1−0)cm2/1 min.+(SA2−SA1)cm2/2 min+(SA3−SA2)cm2/2]/3
For each sample number, the average spread velocity was determined. The results are shown in
Sensory analysis of personal care and cosmetic products relies on panelists' perception to assess and compare attributes of each product during all steps of human use. In this example, panelists focused on describing their perception after picking up, rubbing out and feeling the product on the skin after application (“after-feel”).
During the pick up step, panelists evaluated “stickiness”, which is the intensity of finger adherence to the skin, and was tested using the tips of index and thumb fingers.
In the rub out step, panelists assessed “spreadability”, which is the ease of distributing the product over the skin, and was tested by rubbing the product on the forearm with the opposite hand.
Finally, in after-feel step, panelists were instructed to consider slipperiness, residue and gloss. “Slipperiness” is the ease with which one can move two fingers over the forearm skin after the product was rubbed out. “Residue” is the perception of the amount of product left on the skin after the product was rubbed out, as perceived on the fingertips. “Gloss” is the amount or degree of light reflected off the skin, as seen under the same light settings.
Prior to testing of the sample compositions, all panelists were previously trained on the meaning of each technical terminology and on how to judge each aspect of this sensory analysis (pick up, rub out and after-feel). Before evaluating test-formulations, the panel was calibrated by trying standard reference samples for low and high levels of each one of the five parameters (stickiness, spreadability, slipperiness, residue and gloss).
Even though panelists perceived different intensities for each reference, they all agreed on which samples represented the lower and the higher level of each parameter. Procedures used in this sensory panel were based on the recommendations of the American Society for Testing and Materials (ASTM E1958, the contents of which are incorporated here by reference.)
Whitening of the skin or clothing is undesired in anti-perspirant sticks that contain solid antiperspirant actives such as aluminum salts. Common aluminum salts used in antiperspirant applications are Aluminum Chlorohydrate (ACH), Activated Aluminum Chlorohydrate (AACH), Conventional Aluminum Zirconium Actives (ZAG Actives), and Activated Aluminum Zirconium Actives (AZAG). A typical antiperspirant stick may comprise a waxy substance, a film-former, a fragrance, and a volatile carrier fluid. The example below shows how the composition of the invention can reduce whitening.
Exemplary anti-perspirant sticks were prepared according to the following composition. Cyclomethicone, a common silicone material was the comparative prior-art fluid.
Brassica Glycerides
1INOLEX, Incorporated;
2Clearco Products Co., Inc.;
3Summit Reheis;
4Carruba
The formulation was made by blending the ingredients of Phase A in a beaker. In a separate beaker, the components of Phase B were blended together using a Speed Mixer. Phase B is was then added to Phase A, and stirred with a magnetic stirrer, then heated to 80° C. and held for 10 to 30 minutes. The mixture was allowed to cool to 70°, and Phase C was then added. The mixture was allowed to cool to 65° and poured into canisters, then allowed to cool to room temperature. What resulted in each case was a solid stick.
To illustrate the reduction in whitening, the sticks were rubbed on to black paper. Photos were taken at time zero (initially), after about one half hour, and after one hour.
The photos of
Desirable attributes in color cosmetics such as eyeshadow pots include ease of pick-up, improved color pay-off, the feeling of richness, and a moisturizing feeling in the after-feel. By color pay-off it is meant the amount depth and vibrance of the color observed given the application of equal amounts of product. That is to say, if the same amount of product A is applied to the skin as product B, if product B shows a higher depth of color, it is considered to be better. Also, a more pleasant, silky and smooth after-feel is a desired attribute.
The formulations below were prepared as examples of prior art and inventive eye shadows for comparison. Cyclomethicone, a common silicone material was the comparative prior-art fluid. Formula EA includes the inventive composition, while EB does not.
1INOLEX, Incorporated;
2Clearco Products Co., Inc.
To prepare the formulations, the components of Phase A were combined in a beaker using a high speed mixer at a stirring rate of 3500 rpm. The components of Phase B were then added, and the mixture was heated to 80° C. and stirred using a magnetic stirrer. When the mixture became smooth and homogeneous, the mixture was allowed to cool and then was poured off into containers, and allowed to cool to room temperature.
To illustrate color pay-off, equal amounts of each formulation were rubbed on to black paper.
To illustrate the improved sensory properties that can be obtained using the inventive fluid relative to the very popular prior art fluid, cyclopentasiloxane, the following cationic lotions were prepared.
Brassica Aclohol1
1INOLEX Inc.;
2Clearco Products Co., Inc.;
3Ajinomoto
4Carruba., Inc.
The formulations were prepared by combing the components of phase A in a beaker and heating with propeller agitation to about 80° C. until homogeneous. In a separate beaker, the components of phase B were combined and heated with propeller agitation to about 80° C. Phase B was then added to phase A, and was homogenized at 4000 RPM for about 3 minutes.
Homogenization was then ceased, and agitation was replaced with propeller mixing and the mixture was allowed to cool to about 50° C. at which time an emulsion was formed. The emulsion was poured off to canisters and allowed to cool to room temperature. The resulting viscosity for CA was 58,500. centipoise, and 39,000 centipoise for CB. The resulting pH for CA was 4.16, and 4.06 for CB.
The sensory properties of the emulsion were panel evaluated as described previously. The results are shown in the diagram of
It will be appreciated by those skilled in the art that changes could be made to the embodiments described above without departing from the broad inventive concept thereof. It is understood, therefore, that this invention is not limited to the particular embodiments disclosed, but it is intended to cover modifications within the spirit and scope of the present invention as defined by the appended claims.
This application claims the benefit under 35 U.S.C. § 119(e) of U.S. Provisional Patent Application No. 62/637,129, filed on Mar. 1, 2018, entitled “Natural Hydrocarbon/Ester Compositions With Improved Sensory Properties, Formulations and Related Methods” the entire disclosure of which is incorporated herein by reference.
| Number | Name | Date | Kind |
|---|---|---|---|
| 20130059021 | Grossman | Mar 2013 | A1 |
| 20130085119 | Boskamp | Apr 2013 | A1 |
| 20140356303 | Rocco | Dec 2014 | A1 |
| 20160120778 | Greco | May 2016 | A1 |
| 20180289601 | Eppler | Oct 2018 | A1 |
| Number | Date | Country |
|---|---|---|
| 2017059136 | Apr 2017 | WO |
| Entry |
|---|
| Database GNPD [Online], MINTEL; Sep. 8, 2016 (Sep. 8, 2016), anonymous: “Bio Active Conditiner”, XP055584830, retrieved from www.gnpd.com; Database accession No. 4253655. |
| Database GNPD [Online], MINTEL; Nov. 24, 2017 (Nov. 24, 2017), anonymous: “Co Wash No Poo Cleansing Conditioner”, XP055584832, retrieved from www.gnpd.com; Database accession No. 5260239. |
| Database GNPD [Online], MINTEL; Feb. 7, 2018 (Feb. 7, 2018), anonymous: “The Renaissance Circle”, XP055584834, retrieved from www.gnpd.com; Database accession No. 5446145. |
| Office Action dated Jul. 27, 2020 for European Application No. 19159814.3-1112 from EPO. |
| Number | Date | Country | |
|---|---|---|---|
| 20190269587 A1 | Sep 2019 | US |
| Number | Date | Country | |
|---|---|---|---|
| 62637129 | Mar 2018 | US |
