Personal care compositions and methods comprising trans-1-chloro-3,3,3-trifluoropropene and trans-1,3,3,3-tetrafluoropropene

Abstract

The personal care composition in the form of a stable oil-in-water emulsion comprises: (i) a continuous aqueous phase comprising water; (ii) a discontinuous phase comprising foam-forming components, trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)) and trans-1-3,3,3-tetrafluoropropene (1234ze(E)), wherein 1233zd(E) and 1234ze(E) collectively constitute from about 40% to about 60% by weight of the personal care composition and are present in a weight ratio of from about 8:1 to about 8:1 of trans-1233zd:trans-1234ze; (iii) an emulsifier having an HLB value of from about 7 to about 18, which may be present in the continuous phase and / or the discontinuous phase; and (iv) one or more active ingredients, which may be present in the continuous phase and / or the discontinuous phase. A method for treating human skin, hair, and / or mucous membranes comprises providing the personal care composition.

Description

Technical Field

[0001] (Cross - Reference to Related Applications) This application claims the benefit of priority to U.S. Provisional Patent Application No. 62 / 827,714, filed Apr. 2, 2019, which is incorporated herein by reference in its entirety.

[0002] This application claims the benefit of priority to PCT Application No. PCT / CN2020 / 080355, filed Mar. 20, 2020, which is incorporated herein by reference in its entirety.

[0003] (Field of the Invention) The present invention relates to methods and devices for providing personal care, including, but not limited to, personal care compositions, and compositions, articles, and methods that provide a novel foamed form and / or provide a foaming effect.

Summary of the Invention

Problems to be Solved by the Invention

[0004] Personal care compositions such as skin lotions and cleansers and shaving creams (including foams and gels) generally contain several ingredients in addition to the active ingredient. Such additional ingredients may include, for example, thickeners, suspending agents, surfactants, and foaming agents, which are included to affect the properties of the composition when the composition is dispensed onto the skin and / or when applied to the skin.

[0005] One particular type of formulation is a gel that self-foams when dispensed and / or when applied onto or within the area of skin or scalp being treated. For example, one of the more common forms of personal care products used today is a post-foaming shaving gel. In such post-foaming compositions, it is common to add soap, surfactants, active ingredients, and other ingredients having relatively volatile hydrocarbons to form a clear and stable gel or emulsion when maintained under pressure. When these materials are dispensed and mechanically agitated, the gel generally forms a foam due to the application of energy to the gel after dispensing.

[0006] Applicants have come to understand that the performance of conventional personal care formulations, including post-foaming and non-post-foaming formulations, is lacking and / or can be improved in several respects. By way of example, Applicants have found that in many conventional formulations, the volatile hydrocarbons that have heretofore been used to form a foam in post-foaming applications have resulted in the degradation of other desirable aspects of the formulation. For example, Applicants have come to understand that such conventional post-foaming formulations foam too soon after application, thereby tending to cancel out the ability of the formulation to spread onto the skin or hair of the user and / or penetrate the skin / hair to the extent that would be desirable for the user. Further, even within the relatively small range in which conventional post-foaming formulations could be spread onto the skin prior to foaming, such formulations did not enhance or improve the ability of the active ingredient to penetrate the pores of the skin, thereby giving neither the perception nor the reality of improved performance.

[0007] Furthermore, Applicants have come to recognize that in many conventional formulations, the appearance and / or initial feel on the skin / scalp are not as appealing to the user as might be achieved, and that the product substantially impairs user satisfaction when used for its intended purpose. For example, Applicants have recognized that if a foam or gel that is otherwise acceptable for its intended purpose appears to leak, sag, and / or otherwise be unappealing when dispensed, the success of the product may be unacceptable or at least less than desired.

[0008] Another aspect of conventional formulations is the ability to impart a cooling sensation to the user as a result of applying a personal care product to the skin and / or hair. Such sensations are provided in many conventional formulations by including certain ingredients known as sensates that act on transient receptor potential (TRP) channels contained in human tissue. See, for example, U.S. Patent Application Publication No. 2017 / 0000713. Applicants have come to recognize that the use of such sensate ingredients can have several drawbacks, including the relatively high cost of these ingredients and their derivatives. Another potential drawback is the need for the sensate to interact directly with the biological functions of the user, which can be undesirable in certain cases / applications, such as users who are particularly sensitive and / or allergic to direct biological interactions and who may experience lingering side effects as a result of ingredients that remain in contact with the user. Accordingly, Applicants have come to recognize the desirability of achieving such a cooling sensation using a simpler and lower-cost mechanism and without the other drawbacks of the sensates described above. Additionally, Applicants have come to recognize the desire of many users to experience a cooling sensation that appears essentially immediately upon application to the skin / hair / mucosa, and that these sensates are clearly limited in use to applications to the skin, body, and mucosa where an instantaneously refreshing cooling sensation is desired. In addition, Applicants have also come to understand the advantages of treatment compositions and methods where the cooling effect persists for an extended period of time and preferably, simultaneously, provides an essentially immediate cooling sensation upon application.

[0009] Applicants have also come to recognize that the use of certain materials for forming foams can have advantages in the manufacture of desirable and / or novel foam morphologies, as described below. However, Applicants have also come to recognize that in many such cases, the ability to maintain components in a stable form while in a container under pressure can pose a substantial challenge with unpredictable results. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] The patent or application file includes at least one drawing executed in color. A copy of this patent or patent application publication having the color drawing(s) is provided by the office upon request and payment of the necessary fees.

[0011]

Figure 1

[0012]

Figure 2

[0013]

Figure 3

DETAILED DESCRIPTION OF THE INVENTION

[0014] Summary The applicants have come to understand that one or more, preferably all, of the drawbacks and obstacles described above in connection with conventional formulations and methods can be reduced or substantially eliminated using the methods, articles, and personal care formulations according to the present invention. Additionally and / or alternatively, the applicants have developed highly desirable and / or novel formulations that were not previously known or available.

[0015] The present invention is a method for treating human skin, hair, and / or mucous membranes, comprising: (a) providing a personal care composition in the form of a gel, lotion, or cream, comprising: (i) one or more active ingredients; (ii) optionally but preferably one or more auxiliary gel, lotion, or cream - forming ingredients; and (iii) a foam - forming ingredient comprising trans - 1 - chloro - 3,3,3 - trifluoropropene (1233zd(E)) and trans - 1,3,3,3 - tetrafluoropropene (1234ze(E)); (b) spreading the gel, lotion, or cream onto and / or into the skin, hair, and / or mucous membranes of the human being being treated; (c) foaming the gel, lotion, or cream by evaporating 1233zd(E) and 1234ze(E) from the gel, lotion, or cream during delivery and / or while in contact with the skin, hair, and / or mucous membranes. A method comprising the steps of is provided. For convenience, the method according to the present invention is referred to herein as Method 1.

[0016] The present invention also relates to a method of treating human skin, hair, and / or mucous membranes, (a) providing a personal care composition in the form of a stable water-in-oil emulsion in a pressurized container, the emulsion comprising (i) a continuous aqueous phase containing water, (ii) a discontinuous phase containing a foam-forming component, trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)) and trans-1,3,3,3-tetrafluoropropene (1234ze(E)), wherein 1233zd(E) and 1234ze(E) together comprise from about 40% to about 60% by weight of the personal care composition and are present in a weight ratio of trans 1233zd:trans 1234ze of from about 8:1 to about 1:1, (iii) an emulsifier having an HLB value of from about 7 to about 18 and which may be present in the continuous phase and / or the discontinuous phase, (iv) one or more active ingredients which may be present in the continuous phase and / or the discontinuous phase, (v) optionally, one or more auxiliary gel, lotion, or cream-forming components which may be present in the continuous phase and / or the discontinuous phase; (b) distributing the personal care composition onto and / or into the skin, hair, and / or mucous membranes of the human being being treated by releasing at least a portion of the personal care composition from the container to ambient pressure conditions to form a foam. A method comprising the steps of is provided. For convenience, the method according to the present invention is referred to herein as Method 2.

[0017] As used herein, the term "ambient pressure conditions" means atmospheric pressure or approximately atmospheric pressure.

[0018] The present invention also provides a method for treating human skin, hair, and / or mucous membranes, comprising: (a) providing a personal care composition in the form of a stable water-in-oil emulsion in a container under pressure, wherein the emulsion comprises: (i) a continuous aqueous phase containing water; (ii) a discontinuous phase containing trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)) and trans-1,3,3,3-tetrafluoropropene (1234ze(E)), wherein 1233zd(E) and 1234ze(E) together constitute from about 40% to about 60% by weight of the personal care composition and are present in a weight ratio of trans 1233zd:trans 1234ze of from about 1:8 to less than 1:1; (iii) a solid emulsifier having an HLB value of from about 7 to about 18 and which may be present in the continuous phase and / or the discontinuous phase; (iv) preferably, a stability aid component of from about 9% to less than about 14% by weight which may be present in the continuous phase and / or the discontinuous phase and which is selected from the group consisting of ester oils, silicones, aliphatic alcohols, waxes, and combinations of two or more thereof; (v) one or more active ingredients which may be present in the continuous phase and / or the discontinuous phase; (vi) optionally, one or more auxiliary gel, lotion, or cream-forming components which may be present in the continuous phase and / or the discontinuous phase; and (b) distributing the personal care composition onto and / or into the skin, hair, and / or mucous membranes of a human being being treated by discharging at least a portion of the personal care composition from the container to ambient pressure conditions to form a foam. For convenience, the method according to the present invention is referred to herein as Method 3. As used herein, the term "stability assisting component" refers to a component other than an emulsifier that is described herein and that the applicants have found can assist in achieving a stable oil-in-water emulsion for the formulations of the present invention.

[0019] The present invention also provides a method of treating human skin, hair, and / or mucous membranes, comprising: (a) providing a personal care composition in the form of a stable oil-in-water emulsion in a container under pressure, wherein the emulsion comprises: (i) a continuous aqueous phase comprising water; (ii) a discontinuous phase comprising a foaming component, trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)) and trans-1,3,3,3-tetrafluoropropene (1234ze(E)), wherein 1233zd(E) and 1234ze(E) together constitute at least about 60% by weight of the personal care composition and are present in a weight ratio of trans 1233zd:trans 1234ze of from about 1:8 to less than about 1:1; (iii) an emulsifier having an HLB value of from about 7 to about 18 and that may be present in the continuous phase and / or the discontinuous phase; (iv) one or more active ingredients that may be present in the continuous phase and / or the discontinuous phase; (v) optionally, one or more auxiliary gel, lotion, or cream-forming components that may be present in the continuous phase and / or the discontinuous phase; and (b) discharging at least a portion of the personal care composition from the container to ambient pressure conditions to form a foam on the user and distributing the personal care composition onto and / or into the human skin, hair, and / or mucous membranes being treated by providing a cooling sensation to the user. For convenience, the method according to the present invention is referred to herein as Method 4.

[0020] The present invention also provides a method of treating human skin, hair, and / or mucous membranes, comprising: (a) providing a personal care composition in the form of a stable oil-in-water emulsion in a container under pressure, wherein the emulsion comprises: (i) A continuous aqueous phase containing water, (ii) A discontinuous phase containing a foam-forming component, trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)) and trans-1,3,3,3-tetrafluoropropene (1234ze(E)), wherein 1233zd(E) and 1234ze(E) together constitute at least about 40% by weight of the personal care composition and are present in a weight ratio of trans 1233zd:trans 1234ze of from about 1:8 to less than about 8:1, (iii) A solid long-chain linear emulsifier, which may be present in the continuous phase and / or the discontinuous phase, effective to ensure that the oil-in-water emulsion is stable and provides an emulsifier HLB of from about 7 to about 18, v) One or more active ingredients, which may be present in the continuous phase and / or the discontinuous phase, (vi) Optionally, one or more auxiliary gel, lotion, or cream-forming components, which may be present in the continuous phase and / or the discontinuous phase, and a process comprising: (b) Releasing at least a portion of the personal care composition from the container to ambient pressure conditions to form a foam on the user in a form selected from a sherbet-like foam, an ice cream-like foam, a crackling foam, or a combination of two or more thereof, and distributing the personal care composition onto and / or into the skin, hair, and / or mucous membranes of the human being being treated. The method according to the present invention is, for convenience, referred to herein as Method 5.

[0021] The present invention also relates to a method of treating human skin, hair, and / or mucous membranes, (a) Providing a personal care composition in the form of a stable oil-in-water emulsion in a container under pressure, the emulsion comprising: (i) A continuous aqueous phase containing water, (ii) a discontinuous phase comprising a foam-forming component, trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)) and trans-1,3,3,3-tetrafluoropropene (1234ze(E)), wherein 1233zd(E) and 1234ze(E) together constitute at least about 40% by weight of the personal care composition and are present in a weight ratio of trans 1233zd:trans 1234ze of from about 1:8 to less than about 8:1, (iii) an emulsifier, present in an effective amount in the continuous phase and / or the discontinuous phase, to ensure that the oil-in-water emulsion is stable, v) one or more active ingredients, which may be present in the continuous phase and / or the discontinuous phase, (vi) optionally, one or more auxiliary gel, lotion, or cream-forming components, which may be present in the continuous phase and / or the discontinuous phase, and a process comprising: (b) releasing at least a portion of the personal care composition from a container to ambient pressure conditions to form a foam on the user in a form selected from a sherbet-like foam, an ice cream-like foam, a crackling foam, or a combination of two or more thereof, and distributing the personal care composition onto and / or into the skin, hair, and / or mucous membranes of the human being being treated. For convenience, the method according to the present invention is referred to herein as Method 6.

[0022] As used herein, the term "sherbet-like foam" means a foam that is translucent and has a textured surface.

[0023] As used herein, the term "ice cream-like foam" means a foam having a highly textured non-smooth surface that includes a number of relatively sharp but soft points / discontinuities.

[0024] The present invention also provides a method for treating human skin, hair, and / or mucous membranes, which comprises methods 1 to 6, wherein the step of forming the foam comprises evaporating trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)) during delivery and / or while in contact with the skin, hair, and / or mucous membranes to form a foam in a form selected from a sherbet-like foam, an ice cream-like foam, a crackling foam, and combinations of two or more thereof. The present invention also provides a personal care composition in a container under pressure for forming a personal care foam at ambient pressure, wherein the foam is in a form selected from a sherbet-like foam, an ice cream-like foam, a crackling foam, or combinations of two or more thereof, and the composition comprises (a) a continuous aqueous phase comprising water, (b) one or more personal care active ingredients, (c) a combination of trans 1233zd and trans-1234ze in a weight ratio of 1:8 to 8:1, and about 40 wt% to about 60 wt% of trans 1233zd and trans-1234ze, (d) one or more nonionic emulsifiers having a combined HLB value greater than 4, to form a substantially homogeneous oil-in-water emulsion, wherein at least trans HFCO1233zd and trans HFO-1234ze form one or more dispersed phases in the continuous aqueous phase. For convenience, the method according to the present invention is referred to herein as personal care composition 1. The present invention also provides a personal care composition in a container under pressure for forming a personal care foam at ambient pressure, wherein the foam is in a form selected from a sherbet-like foam, an ice cream-like foam, a crackling foam, or combinations of two or more thereof, and the composition comprises (a) a continuous aqueous phase comprising water, which constitutes at least about 40 wt% of the personal care composition, (b) one or more personal care active ingredients, (c) Trans-1,1,1,2,3,3,3-heptafluoropropane (1233zd): a combination of trans-1,1,1,2,3,3,3-heptafluoropropane and trans-1,3,3,3-tetrafluoropropene (1234ze) in a weight ratio of 1:8 to 8:1, and about 40% to about 60% by weight of the combination of trans-1233zd and trans-1234ze based on the total weight of the personal care composition, (d) A substantially homogeneous oil-in-water emulsion comprising one or more liquid emulsifiers having an HLB value greater than 4 and one or more water-based thickeners, wherein at least trans-HFCO1233zd and trans-HFO-1234ze form one or more dispersed phases in the continuous aqueous phase, the personal care composition. For convenience, the method according to the present invention is referred to herein as the personal care composition 2. The present invention also provides a stable oil-in-water emulsion, (i) A continuous aqueous phase containing water, (ii) A discontinuous phase comprising a foam-forming component, trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)) and trans-1,3,3,3-tetrafluoropropene (1234ze(E)), wherein 1233zd(E) and 1234ze(E) together constitute about 40% to about 60% by weight of the personal care composition and are present in a weight ratio of trans-1233zd:trans-1234ze of about 8:1 to about 1:1, (iii) An emulsifier having an HLB value of about 7 to about 18 and which may be present in the continuous and / or discontinuous phases, (iv) One or more active ingredients which may be present in the continuous and / or discontinuous phases, (v) Optionally, one or more auxiliary gel, lotion, or cream-forming components which may be present in the continuous and / or discontinuous phases. For convenience, the method according to the present invention is referred to herein as the personal care composition 3. The present invention also provides a personal care composition in the form of a stable oil-in-water emulsion, the emulsion comprising (i) A continuous aqueous phase containing water, (ii) a discontinuous phase comprising trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)) and trans-1,3,3,3-tetrafluoropropene (1234ze(E)), wherein 1233zd(E) and 1234ze(E) together constitute from about 40% to about 60% by weight of the personal care composition and are present in a weight ratio of trans 1233zd:trans 1234ze of from about 1:8 to less than 1:1, (iii) a solid emulsifier having an HLB value of from about 7 to about 18 and which may be present in the continuous phase and / or the discontinuous phase, (iv) a stability assisting component of from about 9% to less than about 14% by weight, which may be present in the continuous phase and / or the discontinuous phase and is preferably selected from the group consisting of ester oils, silicones, aliphatic alcohols, waxes, and combinations of two or more thereof, (v) one or more active ingredients which may be present in the continuous phase and / or the discontinuous phase, (vi) optionally, one or more auxiliary gel, lotion, or cream forming components which may be present in the continuous phase and / or the discontinuous phase. Also included is a personal care composition. For convenience, the method according to the present invention is referred to herein as personal care composition 4. The present invention also relates to a personal care composition in the form of a stable oil-in-water emulsion, the emulsion comprising (i) a continuous aqueous phase comprising water, (ii) a discontinuous phase comprising a foam forming component, trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)) and trans-1,3,3,3-tetrafluoropropene (1234ze(E)), wherein 1233zd(E) and 1234ze(E) together constitute at least about 60% by weight of the personal care composition and are present in a weight ratio of trans 1233zd:trans 1234ze of from about 1:8 to less than about 1:1, (iii) an emulsifier having an HLB value of from about 7 to about 18 and which may be present in the continuous phase and / or the discontinuous phase, v) one or more active ingredients which may be present in the continuous phase and / or the discontinuous phase, (vi) Optionally, one or more auxiliary gel, lotion, or cream-forming components that may be present in the continuous and / or discontinuous phases, and a personal care composition is also included. For convenience, the method according to the present invention is referred to herein as personal care composition 5.

[0025] The present invention also relates to a personal care composition in the form of a stable oil-in-water emulsion, wherein the emulsion comprises (i) A continuous aqueous phase containing water, and (ii) A discontinuous phase containing a foam-forming component, trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)) and trans-1,3,3,3-tetrafluoropropene (1234ze(E)), wherein 1233zd(E) and 1234ze(E) together constitute at least about 40% by weight of the personal care composition and are present in a weight ratio of trans 1233zd:trans 1234ze of from about 1:8 to less than about 8:1, and (iii) An emulsifier present in an effective amount in the continuous and / or discontinuous phases to ensure the stability of the oil-in-water emulsion, and v) One or more active ingredients that may be present in the continuous and / or discontinuous phases, and (vi) Optionally, one or more auxiliary gel, lotion, or cream-forming components that may be present in the continuous and / or discontinuous phases, and a personal care composition is also included. For convenience, the method according to the present invention is referred to herein as personal care composition 6.

[0026] It will be understood by those skilled in the art that the components used to form the gel, lotion, or cream may be considered to have an active function in the sense of providing a desired effect on the skin, hair, or mucosa. By way of example, a skin conditioner may be in the form of a cream and is itself considered an active ingredient of the formulation. Thus, the term "auxiliary gel, lotion, or cream-forming component" is used herein mainly to identify components included in the formulation for purposes other than improving the skin or hair, such as affecting the viscosity, feel, texture, delivery characteristics, etc. of the formulation.

[0027] As used herein, the terms "foaming a gel, lotion, or cream" and similar terms mean that at least a substantial proportion of the gel, lotion, cream, etc. is foamed. Thus, the term includes in its meaning the stage where a portion of the gel, lotion, or cream remains unfoamed, but in a preferred embodiment of the present invention, substantially all (e.g., 90% or more) of the gel, lotion, cream, etc. is foamed.

[0028] The present invention also includes a method of treating human skin, hair, and / or mucous membranes, each of Methods 1 - 6, wherein the step of forming the foam comprises evaporating trans-1-chloro-3,3,3-trifluoropropene, and spreading the gel, lotion, cream, and / or foam on and / or into the skin, hair, and / or mucous membranes of the human being being treated.

[0029] The present invention also includes a method of treating human skin, hair, and / or mucous membranes, each of Methods 1 - 6, wherein the foam-forming component consists essentially of or consists of 1233zd(E) and 1234ze(E), and a personal care composition, each of Personal Care Compositions 1 - 6.

[0030] The present invention also includes a method of treating human skin, hair, and / or mucous membranes, each of Methods 1, 2, and 4 - 6, wherein 1233zd(E) and 1234ze(E) are present in a weight ratio of trans 1233zd:trans 1234ze of about 4:1 to about 1:1, and a personal care composition, each of Personal Care Compositions 1 - 3 and 6.

[0031] The present invention also includes a method of treating human skin, hair, and / or mucous membranes, each of Methods 1, 2, and 4 - 6, wherein 1233zd(E) and 1234ze(E) are present in a weight ratio of trans 1233zd:trans 1234ze of about 2:1 to about 1:1, and a personal care composition, each of Personal Care Compositions 1 - 3 and 6.

[0032] The present invention also includes a method for treating human skin, hair, and / or mucous membranes, each of methods 1, 2, and 4 - 6, wherein 1233zd(E) and 1234ze(E) are present in a weight ratio of trans-1233zd:trans-1234ze of about 4:1 to about 1:1, and the foam is in the form of a sherbet-like foam, and also includes a personal care composition including each of personal care compositions 1 - 3 and 6.

[0033] The present invention also includes a method for treating human skin, hair, and / or mucous membranes, each of methods 1, 2, and 4 - 6, wherein 1233zd(E) and 1234ze(E) are present in a weight ratio of trans-1233zd:trans-1234ze of about 4:1 to about 2:1, and the foam is in the form of a sherbet-like foam, and also includes a personal care composition including each of personal care compositions 1 - 3 and 6.

[0034] The present invention also includes a method for treating human skin, hair, and / or mucous membranes, each of methods 1 and 3 - 6, wherein 1233zd(E) and 1234ze(E) are present in a weight ratio of trans-1233zd:trans-1234ze of about 1:4 to less than 1:1, and also includes a personal care composition including each of personal care compositions 1, 2, and 4 - 6.

[0035] The present invention also includes a method for treating human skin, hair, and / or mucous membranes, each of methods 1 and 3 - 6, wherein 1233zd(E) and 1234ze(E) are present in a weight ratio of trans-1233zd:trans-1234ze of about 2:1 to less than 1:1, and also includes a personal care composition including each of personal care compositions 1, 2, and 4 - 6.

[0036] The present invention also relates to a method for treating human skin, hair, and / or mucous membranes, which comprises each of methods 1 and 3 to 6, wherein 1233zd(E) and 1234ze(E) are present in a weight ratio of trans-1233zd:trans-1234ze of about 1:4 to less than 1:1, and the foam is in the form of an ice cream-like foam, and also to a personal care composition comprising each of personal care compositions 1, 2, and 4 to 6.

[0037] The present invention also relates to a method for treating human skin, hair, and / or mucous membranes, which comprises each of methods 1 and 3 to 6, wherein 1233zd(E) and 1234ze(E) are present in a weight ratio of trans-1233zd:trans-1234ze of about 1:4 to about 1:2, and the foam is in the form of an ice cream-like foam, and also to a personal care composition comprising each of personal care compositions 1, 2, and 4 to 6.

[0038] The present invention includes a method for treating human skin, hair, and / or mucous membranes, the method comprising applying a personal care composition of the present invention comprising each of personal care formulations 1 to 6 to human skin, hair, and / or mucous membranes.

[0039] The present invention includes a method for treating human skin, hair, and / or mucous membranes, the method comprising spreading a personal care composition of the present invention comprising each of personal care formulations 1 to 6 on human skin, hair, and / or mucous membranes.

[0040] The present invention includes a method for treating human skin, hair, and / or mucous membranes, the method comprising delivering a personal care composition of the present invention comprising each of personal care formulations 1 to 6 to human skin, hair, and / or mucous membranes, and then foaming the delivered personal care composition.

[0041] The present invention relates to a method for treating human skin, hair, and / or mucous membranes, comprising the steps of delivering a personal care composition of the present invention containing each of personal care agents 1 to 6 to human skin, hair, and / or mucous membranes, and then foaming the delivered personal care composition by evaporation of a morphogenic component.

[0042] The present invention includes the step of providing a personal care composition comprising (a) one or more active ingredients and trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)), wherein the one or more active ingredients are carried by and / or with 1233zd(E), and includes each of methods 1 to 6 for treating human skin, hair, and / or mucous membranes.

[0043] As used herein, the term "evaporating trans-1-chloro-3,3,3-trifluoropropene (1233zd(E))" and similar terms mean that at least a substantial proportion of 1233zd evaporates. Thus, the term includes stages where a portion of 1233zd remains unevaporated, but in preferred embodiments of the invention, substantially all (e.g., 90% or more) of 1233zd is evaporated. Also, the requirement that one or more active ingredients remain on and / or in the skin, hair, and / or mucous membranes of the human being being treated is understood to be intended for both "remaining" compositions and methods and "rinsing off" compositions and methods. Thus, the invention includes methods where the active ingredient is intended to remain on the skin, hair, and / or mucous membranes used without the active intent or effort of the user to remove the product. In such "remaining" uses, it is preferred that substantially all of 1233zd evaporates over a substantial period (e.g., 5 minutes or more) after application. On the other hand, in "rinsing off" uses, an active action (e.g., by rinsing with water) is assumed to remove creams, lotions, gels, foams, etc. after application, and in such embodiments, it is assumed that a portion, possibly a substantial portion, of 1233zd is removed from the user before evaporation. Thus, both "remaining" and "rinsing off" uses are within the scope of the invention.

[0044] One of ordinary skill in the art will understand that the present invention includes articles that include an openable closed container for dispensing a personal care composition of the present invention, each of personal care compositions 1-6. Accordingly, the present invention includes containers that are openable but not easily reclosed (such as in the case of a sachet that can be torn or slit to provide an opening for dispensing a personal care formulation), and reclosable containers (such as in the case of a can having a nozzle with a valve that can be opened to allow dispensing of a personal care formulation and then reclosed to maintain the remainder of the formulation within the can for use at a later time). In either case, but primarily in the case of reclosable containers, it is contemplated that the foaming component of the present invention may also provide a force useful for discharging the personal care formulation from the container. As an example, in a preferred embodiment where the foaming component includes both 1233zd and 1234ze, the 1234ze component of the personal care composition generally exits the container with the formulation and functions not only to provide a foaming action but also to at least assist in discharging the personal care formulation from the container. In such embodiments, the formulation preferably includes both 1233zd(E) and 1234ze(E) as components that mix with and / or disperse in and / or emulsify the formulation, and in such cases, the 1234ze(E) component contributes to the foaming of the formulation and the provision of an ejection force as it exits the container. For the purposes of the description of the present invention, 1234ze and 1233zd in such embodiments, as well as other components that behave in the same or a similar manner, are within the scope of terms such as "foaming component" because they substantially contribute to the foaming of the personal care composition. Detailed Description

[0045] The preferred methods, articles, and compositions of the present invention provide one or more, preferably several, unexpected performance characteristics as compared to conventional personal care methods and personal care compositions. These performance advantages include the following. - Improvement and enhancement of the senses for the user, including appearance, feel, and sound, - Improvement in the stability of the emulsion forming the foam - Improvement in the penetration of the active ingredient into the skin, hair, and / or mucous membranes of the user - A feeling of cold on the skin / mucous membranes that is felt essentially immediately upon application or at least recognized - Enhancement and long-term persistence of the feeling of cold provided to the user, preferably without using a sensory agent. As used herein, the terms "personal care composition", "personal care formulation", etc. mean compositions, formulations, etc. that are applied topically to a person.

[0046] The personal care compositions and formulations of the present invention can be in the form of, for example, lotions, creams, gels, etc., and in each of such forms, the composition is preferably a post-foaming composition or formulation. Thus, while post-foaming formulations are preferred for many applications, it will be understood that lotions, creams, gels, etc. that are not post-foamed, including certain embodiments that provide a feeling of cold to the user, are also within the broad scope of the present invention. The compositions and formulations of the present invention are generally not post-foaming compositions, but can be in the form of sprays or aerosolized powders, mists, etc. that provide the advantageous feeling of cold of the present invention.

[0047] As used herein, the term "post-foaming" refers to gels, creams, lotions, etc. that are not essentially in the form of a foam when applied, but that produce a foamed product as a result of the application of heat (which may be in the form of body temperature) or other energy (such as kinetic energy associated with rubbing or spreading the formulation on the skin and / or hair). For convenience, but not necessarily by limitation, the compositions, formulations, and methods related to the post-foaming action are described below separately from non-post-foaming compositions, formulations, and methods. Active ingredient

[0048] The active ingredients used in the compositions and methods of the present invention can have a wide variety of purposes and functions, and all such ingredients are within the scope of the present invention. Generally, such ingredients are expected to provide, or at least provide, some benefit to the user, preferably to the user's skin, hair, and / or mucous membranes. Thus, active ingredients can include cosmetics (i.e., agents that cosmetically treat the skin, hair, or mucous membranes by topical application, provide nutrition to, and / or condition them), pharmaceuticals (i.e., agents that can preferably promote or assist in the recovery from injury or disease to the skin, hair, or mucous membranes), and pharmaceutically active drugs (i.e., drugs suitable for delivery by topical application, preferably containing drugs effective in treating the skin, hair, and mucous membranes). It will be understood by those skilled in the art that an active ingredient can have two or more modes of operation and / or effects, and can thus be appropriately included in two or more product categories for the purposes of the present invention.

[0049] Examples of active ingredients include coloring, decoloring, and appearance-changing agents (e.g., pigments, pigment deposition inhibitors, skin whitening agents, reflectants, etc.); hair treatment agents (e.g., shaping agents, anti-tangling agents, wet combing agents, anti-hair loss agents, hair growth promoters, hair growth inhibitors, hair dyes, hair conditioners, hair softeners; hair moisturizers, anti-dandruff agents, etc.); film-forming polymers; humectants; amino acids and their derivatives; antimicrobial agents; allergy inhibitors; anti-acne agents (such as salicylic acid, benzoyl peroxide, sulfur, adapalene, and glycolic acid, etc.); anti-aging and anti-wrinkle agents (such as dimethylaminoethanol, "DMAE", retinol, vitamin C, hydroxy acids, peptides, tea extracts, grape seed extracts, and niacinamide, etc.), preservatives; analgesics; antitussives; antipruritics; local anesthetics; antihistamines; anti-infection agents; inflammation inhibitors; deodorants and antiperspirants (such as aluminum chlorohydrate and aluminum-zirconium tetrachlorohydrate); pharmaceutical agents; skin softeners and skin moisturizers; skin farming agents; antifungal agents; shaving preparations, lotions, creams, and gels; fragrances; makeup preparations; cosmetics (e.g., skin cleansers, skin conditioners, makeup, etc.), as well as sunscreens and sunblocks (such as benzophenone, borneol, butyl paba, cinamidopropyltrimethylammonium chloride, distyrylbiphenyl disulfonic acid disodium salt, paba, potassium methoxycinnamate, butyl methoxydibenzoylmethane, octyl methoxycinnamate, oxybenzone, octocrylene, octyl salicylate, phenylbenzimidazole sulfonic acid, ethyl hydroxypropylaminobenzoate, menthyl anthranilate, aminobenzoic acid, cinoxate, methoxycinnamic acid diethanolamine, glyceryl aminobenzoate, titanium dioxide, zinc oxide, oxybenzone, padimate 0, and red petrolatum, etc.);Insect repellents, skin protectants (e.g., oatmeal, beta-glucan, Artemisia princeps Pamp., soybeans and their derivatives, sodium bicarbonate, colloidal oatmeal, surfactant-based colloidal oatmeal cleanser, Artemisia argyi, Glechoma hederacea L., Dryopteris erythrosora, etc.), vitamins (vitamin B complex, e.g., thiamine, nicotinic acid, biotin, pantothenic acid, choline, riboflavin, vitamin B6, vitamin B12, pyridoxine, inositol, carnitine; vitamins A, C, D, E, K, and their derivatives, e.g., vitamin A palmitate and provitamins, e.g., (i.e., panthenol (provitamin B5) and panthenol triacetate), but are not limited thereto.;

[0050] The amount of the active ingredient used in conjunction with the present invention can vary widely depending on the particular use, and all such amounts can be determined by one skilled in the art in view of the teachings contained herein and are within the broad scope of the present invention. For example, the amount of the active ingredient can vary depending on the ability of the component to penetrate into, onto, or into the pores of the skin, hair, or mucous membranes, taking into account the improvement provided by the present invention. Other factors that can affect the relative amount of the active ingredient include the particular active ingredient involved, the particular benefit desired, the sensitivity of the user to the active ingredient, the health status of the user, age, and the condition of the skin, hair, and / or mucous membranes. In summary, the beneficial agent is preferably used in a "safe and effective amount", which is high enough to provide the desired skin, hair, or mucous membrane benefit or to modify the particular condition to be treated and to avoid undesirable and severe side effects. In a preferred embodiment, the active ingredient is present in a personal care composition or personal care formulation system in an amount of about 0.01 weight percent to about 50 weight percent, or about 0.01 weight percent to about 20 weight percent, or about 0.01 weight percent to about 10 weight percent, or about 0.01 weight percent to about 5 weight percent, or about 0.01 weight percent to about 1.0 weight percent, based on the total weight of the composition / formulation. Auxiliary gel, lotion, or cream-forming component

[0051] The types of auxiliary components that can be used in the formulations of the present invention can vary widely depending on the specific form of the formulation (e.g., gel, cream, or lotion) and the specific attributes of the desired formulation, and any such components are included within the scope of the present invention.

[0052] In connection with gels, for example, in a preferred embodiment, the gel-forming component preferably comprises aqueous soap in a major proportion based on the total weight of the formulation. The soap in the aqueous soap component can be, for example, either a soap or a surfactant, which may also be commonly referred to as a wetting agent that is generally anionic or nonionic.

[0053] Soaps (water-soluble salts of higher fatty acids), which are preferably amines or basic salts and are suitable for the production of post-foaming gels, are generally known in the art, and all such soaps are within the scope of the present invention. Generally, such components can preferably be alkali, ammonium, or soluble amine salts of fatty acids such as stearic acid, palmitic acid, myristic acid, etc. As is known in the art, soaps may be prepared by the neutralization or saponification of animal fats such as tallow or vegetable fats. The selection of suitable soap components is considered to be within the scope of those skilled in the art from the teachings of this specification.

[0054] Anionic or nonionic surfactants that can be used instead of or together with soap should be reasonably soluble in water. Examples of such agents include lauryl sulfate of triethanolamine, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, water-soluble polyoxyethylene ethers of alkyl-substituted phenols, and water-soluble polyoxyethylene cetyl ethers. The selection of suitable wetting agents is considered to be within the scope of those skilled in the art from the teachings of this specification.

[0055] Preferably, in the method of the present invention including each of Methods 1 to 6 and the personal care composition of the present invention including each of Personal Care Compositions 1 to 6, the emulsifier comprises or consists essentially of a nonionic, solid, long-chain, straight-chain emulsifier having an HLB value of about 9 to about 16. An example of such an emulsifier is Tween 20.

[0056] One problem associated with the formation of gels for use in post-foaming applications is that in their non-foamed state, they are difficult to form gels that can spread easily on the skin or hair in a uniform fluid pattern. See, for example, U.S. Patent No. 5,334,325, which describes the use of certain alkoxylated alkyl phosphate ester surfactants, the contents of which are incorporated herein by reference.

[0057] Other auxiliary components that may be included in the gels, creams, and lotions of the present invention for use in post-foaming applications include polymers for gel thickening and lubrication, cosmetic esters for skin softening, humectants for moisturization, fragrances, dyes, and preservatives.

[0058] The amounts of the auxiliary components used with the present invention can vary widely depending on the particular application, and all such amounts can be determined by one of ordinary skill in the art in view of the teachings included herein and are within the broad scope of the present invention. In a preferred embodiment, the auxiliary components are present in the personal care composition or personal care formulation system in an amount of about 1 percent to about 60 percent, together, based on the total weight of the composition / formulation and based on the total weight of the components in the formulation.

[0059] As described above, the present invention also includes creams, lotions, gels, foams, mists, powders, sprays, etc. that do not exhibit a post-foaming effect. By way of example, the advantageous cooling effect as described herein can also be provided to creams, lotions, gels, foams, mists, powders, sprays, etc. that are not designed to exhibit a post-foaming effect. In any case, 1233zd of the present invention evaporates after creams, lotions, gels, foams, mists, powders, sprays, etc. are applied to the user's skin, hair, and / or mucous membranes, thereby providing the advantageous cooling effect as described herein. As a further example, the advantageous ability of the present formulation, by including 1233zd of the present invention in part, provides the advantageous ability of the active ingredient to penetrate into and / or be directly delivered into the pores of the user's skin / mucous membranes and / or the user's hair follicles even in embodiments where a post-foaming effect is not achieved or not desired.

[0060] Accordingly, non-post-foaming embodiments of the present invention can also utilize formulations and compositions in the form of creams, lotions, gels, foams, mists, powders, sprays, etc., where such formulations and compositions generally include (a) one or more active ingredients, preferably including a cleanser, (b) one or more auxiliary ingredients, which are optional but preferably useful for forming creams, lotions, gels, foams, mists, powders, sprays, etc., (c) a foaming agent comprising or consisting essentially of or consisting of 1233zd(E) and 1234ze(E), and (d) optional additional ingredients other than ingredients (a), (b), and (c) that can be included in the composition. The types and amounts of ingredients (a), (b), and (c) in such non-post-foaming applications can vary widely and include the types and amounts of such ingredients described herein in connection with post-foaming applications. In non-post-foaming embodiments, for convenience and not by way of limitation, ingredients (a), (b), and (d) may also be referred to herein as "formulation base" or "cleanser base" (when the active ingredient includes a cleanser), etc.

[0061] The personal care compositions of the present invention can be in the form of, and / or used in, a wide range of personal care products / applications, including shampoos (including baby shampoos, conditioning shampoos, moisturizing shampoos, etc.), skin and body cleansers (including shower gels, bath foams, facial cleansers, delicate zone cleansers, moisturizing body washes, antibacterial body washes, bath gels, hand soaps, facial scrubs, foot scrubs, etc.), hair care compositions (including hair dyes, hair conditioners, hair creams, and hair styling preparations), skin care compositions (including skin lotions, balms and creams, skin whitening agents, self-tanning lotions, sunscreens, carrier lotions, moisturizers, vitamin C creams, antibacterial lotions, facial masks, body masks, makeup foundations, sun care preparations, antiperspirants, etc.).

Example

[0062] Example 1 - Moisturizing Body Lotion for Forming Ice-Cream-Like Foam The moisturizing body lotion was prepared using a moisturizing base containing the following ingredients: water, cetearyl alcohol (as a stability aid), glycerin, cetyl alcohol (as a stability aid), behentrimonium chloride (as a cationic emulsifier), argania spinosa (argan) kernel oil, silk amino acids, dimethicone, cyclopentasiloxane (a stability aid, dimethiconol, glycol distearate (as a stability aid with an HLB of 1), glycol stearate (a stability aid with an HLB of 2.9), ceteareth-20 (as an emulsifier with an HLB of 15.2), isopropyl alcohol, citric acid, phenoxyethanol, ethylhexylglycerin, DMDM hydantoin, fragrance (perfume), Red 40 (CI 16035), Yellow 5 (CI 19140), Yellow 6 (CI 15985 water). This moisturizing base and various amounts of trans-1,2,3,3-tetrafluoropropene (trans-1233zd), trans-1,2,3,4-tetrafluoropropene (trans-1234zd) were used in several formulations in the relative amounts shown in Table 1 below. Here, all amounts are shown as percentages by weight.

[0063]

Table 1

[0064] As can be seen from Figure 1, Formulations A and B, each using a total amount of 40% or more of trans-1233zd and trans-1234ze and a zd / ze weight ratio of 1:4, formed a textured ice cream-like foam, which had a semi-transparent characteristic. In contrast, Formulations C and D produced foams with a relatively smooth continuous surface and a characteristic of being relatively little or not at all semi-transparent. In these cases, the zd / ze weight ratio was 1:4, but the total application amount was less than 40% (30% and 20% respectively). Example 1B - Moisturizing Body Lotion for Forming an Ice Cream-like Foam

[0065] Repeat Example 1A, except that the zd / ze weight ratio of Formulations A and B is adjusted to 1:1 (i.e., 25 wt% zd and 25 wt% ze for Formulation A, and 20 wt% zd and 20 wt% ze for Formulation B). Similar results are obtained. Example 1C - Moisturizing Body Lotion for Forming an Ice Cream-like Foam

[0066] Repeat Example 1A, except that the zd / ze weight ratio of Formulations A and B is adjusted to 1:2 (i.e., 16.67 wt% zd and 33.33 wt% ze for Formulation A, and 13.3 wt% zd and 26.7 wt% ze for Formulation B). Similar results are obtained. Example 2A - Moisturizing Body Lotion for Forming a Sherbet-like Foam

[0067] A moisturizing body lotion was prepared using a moisturizing base containing the following ingredients: water (aqua), cetearyl alcohol (as a stability aid), glycerin, cetyl alcohol (as a stability aid), behentrimonium chloride (as a cationic emulsifier), argania spinosa (argan) kernel oil, silk amino acids, dimethicone, cyclopentasiloxane (as a stability aid), dimethiconol, glycol distearate (as a stability aid with an HLB of 1), glycol stearate (as a stability aid with an HLB of 2.9), ceteareth-20 (as an emulsifier with an HLB of 15.2), isopropyl alcohol, citric acid, phenoxyethanol, ethylhexylglycerin, DMDM hydantoin, fragrance (perfume), Red 40 (CI 16035), Yellow 5 (CI 19140), Yellow 6 (CI 15985 water). Several formulations were prepared using this moisturizing base and various amounts of trans-1,2,3,3-tetrafluoropropene (trans-1233zd) and trans-1,2,3,4-tetrafluoropropene (trans-1234zd) in the relative amounts shown in Table 2 below. Here, all amounts are shown as percentages by weight.

[0068]

Table 2

[0069] As can be seen from Figure 2, Formulations A and B, which utilized a total amount of trans-1233zd and trans-1234ze of 40% or more each and a zd / ze weight ratio of 4:1, formed a sherbet-like foam having a translucent characteristic. In contrast, Formulations C and D produced foams having a relatively smooth, continuous, opaque surface. In these cases, the zd / ze weight ratio was 4:1, but the total applied amount was less than 40% (30% and 20% respectively). Example 2B - Moisturizing Body Lotion for Forming a Sherbet-Like Foam

[0070] Repeat Example 2A, except that the zd / ze weight ratio of Formulations A and B is adjusted to 1:1 (i.e., 25 wt% zd and 25 wt% ze for Formulation A, and 20 wt% zd and 20 wt% ze for Formulation B). Similar results are obtained. Example 2C - Moisturizing Body Lotion for Forming Sherbet-Like Foams

[0071] Repeat Example 2A, except that the zd / ze weight ratio of Formulations A and B is adjusted to 2:1 (i.e., 33.33 wt% zd and 16.67 wt% for Formulation A, and 26.7 wt% zd and 13.3 wt% ze for Formulation B). Similar results are obtained.

[0072] Thus, Examples 1 and 2 demonstrate that formulations in which trans-1233zd and trans-1234ze together constitute at least about 40 wt% of the personal care composition are preferred for forming ice cream and sherbet-type foams.

[0073] Also, a ratio of trans-1233zd:trans-1234ze of from about 4:1 to about 1:4 is preferably further crackling upon application and / or providing cooling upon application, and is clearly preferred for forming a sherbet-like structure. Comparative Example 1 - Personal Care Formulation with a Low HLB Emulsifier

[0074] As shown in Table C3 below, a personal care formulation containing 50 wt% trans-1233zd and trans-1234ze is formed.

Table 3

[0075] As can be seen from the above table, the HLB of the emulsifier used in the formulation was Brij 93, and thus a formulation having an emulsifier with an HLB value of about 4 was obtained. At room temperature, according to measurements based on whether phase separation was observed when shaken for 24 hours after formation, a stable emulsion was not formed. Unless otherwise described herein, the tests described herein were those used in the examples herein to determine the stability of the formulation, and the observation of phase separation indicates that the formulation is not stable and is not acceptable for forming a foam. Examples 3A, 3B, 3C, and 3D - Personal Care Formulations with High HLB Emulsifiers

[0076] As shown in Table 3 below, a series of personal care formulations (3A, 3B, 3C, and 3D) containing 50 wt% of trans 1233zd and trans 1234ze in a 1:4 weight ratio were formed. [Table 4]

[0077] As can be seen from the above table, a series of personal care formulations used a solid long-chain substantially linear nonionic surfactant (Tween 20) to increase the HLB value of the emulsifying package, and had emulsifier HLB values of 9.08, 12.26, 14.16, and 16.7 for Examples 3A, 3B, 3C, and 3D, respectively. A stable emulsion was formed in each case, and a cold foam was formed from each formulation. These results are clarified in Figure 3 herein, and the photographs are of Comparative Example 1 and Examples 3A - 3D from left to right within the figure. However, an ice cream-like foam was not formed from any of the formulations. Comparative Examples 2A, 2B, 2C, 2D, and 2E - Unstable Personal Care Formulations

[0078] A series of personal care formulations containing 50 wt% of trans-1233zd and trans-1234ze, generally described in Comparative Example 1 and Examples 3A to 3D, were formed, but as described in Table 4 below, no long-chain substantially linear nonionic surfactant was used to increase the HLB. [Table 5]

[0079] None of the formulations described in Table 4 formed a stable emulsion. Examples 4A and 4B - Personal Care Formulations with High HLB Liquid Emulsifiers and Ester Oils

[0080] Two personal care formulations (4A and 4B), similar to Formulations C2C and C2D but with the addition of ester oil, were formed as described in Table 4 below. [Table 6]

[0081] As can be seen from the above table, the addition of 2 wt% of ester oil (isopropyl myristate) assisted in the preparation of a stable personal care composition and made it possible. However, an ice cream-like foam was not formed from any of the formulations. Examples 5A, 5B, and 5C - Personal Care Formulations with High HLB Liquid Emulsifiers and Aliphatic Alcohols

[0082] Three personal care formulations (5A, 5B, and 5C), similar to Formulation C2C but using a liquid emulsifier with an HLB of 14 and adding 4%, 8%, and 12% of aliphatic alcohol, were formed. The formulations using 12% and 8% of aliphatic alcohol did not form a stable emulsion, but the formulation using 4% of aliphatic alcohol formed a stable personal care composition. However, an ice cream-like foam was not formed. Examples 6A, 6B, and 6C - Personal Care Formulations with High HLB Solid Emulsifiers, Aliphatic Alcohols, and Ester Oils

[0083] Three personal care formulations (6A, 6B, and 6C) were formed that were similar to Formulation C2C but used a liquid emulsifier with an HLB of 14 and 4% ester oil, and added 4%, 8%, and 12% aliphatic alcohol, respectively. All three formulations formed stable emulsions, but no ice cream-like foams were formed. Examples 7A, 7B, and 7C - Personal Care Formulations with High HLB Solid Emulsifiers, Aliphatic Alcohols, and Ester Oils

[0084] Three personal care formulations (7A, 7B, and 7C) were formed that were similar to Formulation C2C but used a solid emulsifier with an HLB of 14 and 4% ester oil, and added 4%, 8%, and 12% aliphatic alcohol, respectively. All three formulations formed stable emulsions, but no ice cream-like foams were formed. Example 8 - Personal Care Formulation with High HLB Solid Emulsifier, Aliphatic Alcohol, Ester Oil, and Silicone

[0085] A personal care formulation was formed that was similar to Formulation C2C but used a solid emulsifier (Steareth 21) with an HLB of 15.5, 4% ester oil, 8% aliphatic alcohol, no water-based thickener, and 2% silicone. The formulation formed a stable emulsion and produced an ice cream-like foam. Example 9A - Personal Care Formulation with High HLB Solid Emulsifier, Aliphatic Alcohol, Ester Oil, and Silicone

[0086] A personal care formulation was formed that was similar to Formulation C2C but used a solid emulsifier (Steareth 21) with an HLB of 15.5, 2% ester oil, 12% aliphatic alcohol, no water-based thickener, and 2% silicone. The formulation formed a stable emulsion, but no ice cream-like foam was produced. Example 9B - Personal Care Formulation with High HLB Solid Emulsifier, Aliphatic Alcohol, Ester Oil, Silicone, and Carnauba Wax

[0087] A personal care formulation similar to Formulation C2C was formed using a solid emulsifier (Steareth 21) with an HLB of 15.5, 2% ester oil, 4% aliphatic alcohol, no water - based thickener, 2% silicone, and 4% carnauba wax. The formulation formed a stable emulsion and produced an ice - cream - like foam.

[0088] Comparative Example 3 - Personal Care Formulation with Low HLB Emulsifier

[0089] As shown in Table C4 below, a personal care formulation containing 50 wt% of trans - 1233zd and trans - 1234ze was formed.

Table 7

[0090] As can be seen from the above table, the HLB of the emulsifier used in the formulation was Brij 93, and thus a formulation with an emulsifier having an HLB value of about 4 was obtained. A stable emulsion was not formed. Examples 10A, 10B, 10C, and 10D - Personal Care Formulations with High HLB Solid Emulsifiers

[0091] As shown in Table 5 below, a series of personal care formulations (10A, 10B, 10C, and 10D) containing 50 wt% of trans - 1233zd and trans - 1234ze in a 4:1 weight ratio were formed.

Table 8

[0092] As can be seen from the above table, a series of personal care formulations used a solid, long-chain, substantially linear non-ionic surfactant (Tween 20) to increase the HLB value of the emulsifying package, and had emulsifier HLB values of 9.08, 12.26, 14.16, and 16.7 for Examples 10A, 10B, 10C, and 10D, respectively. A stable emulsion was formed in each case, and a sherbet-like foam with a pleasant cracking sound was formed from each formulation. Comparative Examples 4A, 4B, 4C, 4D, and 4E - Unstable Personal Care Formulations

[0093] Generally, a series of personal care formulations containing 50 wt% of trans 1233zd and trans 1234ze as described in Comparative Example 3 and Examples 10A - 10D were formed, but as described in Table 4 below, a long-chain, substantially linear non-ionic surfactant was not used to increase the HLB.

Table 9

[0094] None of the formulations described in Table 4 formed a stable emulsion. Examples 11A and 11B - Personal Care Formulations with High HLB Liquid Emulsifiers and Ester Oils

[0095] Two personal care formulations (4A and 4B) similar to Formulations C2C and C2D but with the addition of ester oil were formed as described in Table 5 below.

Table 10

[0096] As can be seen from the above table, the addition of 2 wt% of ester oil (isopropyl myristate) assisted in the preparation of a stable personal care composition, enabling it, and furthermore, a sherbet-like foam with a pleasant cracking sound was formed. Examples 12A, 12B, and 12C - Personal Care Formulations with High HLB Liquid Emulsifiers and Aliphatic Alcohols

[0097] Three personal care formulations (12A, 12B, and 12C) were formed that were similar to Formulation C4C, but used a liquid emulsifier having an HLB of 14 and added 4%, 8%, and 12% aliphatic alcohol. The formulations using 12% and 8% aliphatic alcohol did not form a stable emulsion, but the formulation using 4% aliphatic alcohol formed a stable personal care composition, however, a sherbet-like foam was not formed. Examples 13A, 13B, and 13C - Personal Care Formulations with High HLB Solid Emulsifiers, Aliphatic Alcohols, and Ester Oils

[0098] Three personal care formulations (13A, 13B, and 13C) were formed that were similar to Formulation C4C, but used a liquid emulsifier having an HLB of 14 and 4% ester oil and added 4%, 8%, and 12% aliphatic alcohol, respectively. All three formulations formed a stable emulsion, but a sherbet-like foam was not formed. However, each of the foams exhibited a pleasant cracking sound. Examples 14A, 14B, and 14C - Personal Care Formulations with High HLB Solid Emulsifiers, Aliphatic Alcohols, and Ester Oils

[0099] Three personal care formulations (14A, 14B, and 14C) were formed that were similar to Formulation C4C, but used a solid emulsifier having an HLB of 14 and 4% ester oil and added 4%, 8%, and 12% aliphatic alcohol, respectively. All three formulations formed a stable emulsion, but each of the formulations having 8% and 12% aliphatic alcohol was too viscous to dispense. A sherbet-like foam was not formed from the formulation having 4% aliphatic alcohol, but the foam exhibited a pleasant cracking sound. Example 15 - Personal Care Formulation with High HLB Solid Emulsifier, Aliphatic Alcohol, Ester Oil, and Silicone

[0100] A personal care formulation was formed that is similar to Formulation C4C but uses a solid emulsifier (Steareth 21) with an HLB of 15.5, 4% ester oil, 8% fatty alcohol, no water-based thickener, and 2% silicone. The formulation formed a stable emulsion and a sherbet-like foam was produced. Example 16 - Personal Care Formulation with High HLB Solid Emulsifier, Fatty Alcohol, Ester Oil, and Silicone

[0101] A personal care formulation was formed that is similar to Formulation C4C but uses a solid emulsifier (Steareth 21) with an HLB of 15.5, 2% ester oil, 12% fatty alcohol, no water-based thickener, and 2% silicone. The formulation formed a stable emulsion and a sherbet-like foam was produced that exhibited a pleasant cracking sound. Example 17 - Personal Care Formulation with High HLB Solid Emulsifier, Fatty Alcohol, Ester Oil, and Silicone

[0102] A personal care formulation was formed that is similar to Formulation C4C but uses a solid emulsifier (Steareth 21) with an HLB of 15.5, 2% ester oil, 4% fatty alcohol, no water-based thickener, 2% silicone, and 4% carnauba wax. The formulation formed a stable emulsion and a sherbet-like foam was produced that exhibited a pleasant cracking sound. This specification includes the disclosure of the following invention. [1] A method for treating human skin, hair, and / or mucous membranes, comprising: (a) providing a personal care composition in the form of a stable water-in-oil emulsion in a container under pressure, said emulsion comprising: (i) a continuous aqueous phase containing water; (ii) a discontinuous phase containing a foam-forming component, trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)) and trans-1,3,3,3-tetrafluoropropene (1234ze(E)), wherein said 1233zd(E) and said 1234ze(E) together constitute from about 40% to about 60% by weight of the personal care composition and are present in a weight ratio of trans 1233zd:trans 1234ze of about 8:1 to about 8:1; (iii) an emulsifier having an HLB value of about 7 to about 18 and which may be present in said continuous phase and / or said discontinuous phase; (iv) one or more active ingredients which may be present in said continuous phase and / or said discontinuous phase; (v) optionally, one or more auxiliary gel, lotion, or cream-forming components which may be present in said continuous phase and / or said discontinuous phase; (b) discharging at least a portion of said personal care composition from said container to ambient pressure conditions to form a foam, thereby dispensing said personal care composition onto and / or into said human skin, hair, and / or mucous membranes being treated. [2] The method according to claim 1, wherein said 1233zd(E) and said 1234ze(E) together constitute from about 40% to about 60% by weight of the personal care composition and are present in a weight ratio of trans 1233zd:trans 1234ze of about 1:8 to less than 1:1. [3] The method according to claim 1, wherein said 1233zd(E) and said 1234ze(E) together constitute from about 40% to about 60% by weight of the personal care composition and are present in a weight ratio of trans 1233zd:trans 1234ze of about 8:1 to 1:1. [4] The method according to any one of claims 1 to 3, wherein said emulsifier comprises a solid emulsifier. [5] The method according to any one of claims 1 to 3, wherein said emulsifier is a linear long-chain solid emulsifier. [6] The method according to any one of claims 1 to 5, further comprising from about 9% to less than about 14% by weight of a stability assisting component. [7] The method according to 6, wherein the stability assisting component is selected from the group consisting of ester oil, silicone, aliphatic alcohol, wax, and combinations of two or more thereof. [8] The method according to 1, wherein the 1233zd(E) and the 1234ze(E) together constitute at least about 60% by weight of the personal care composition, and the trans 1233zd:trans 1234ze is present in a weight ratio of from about 1:8 to less than about 1:1. [9] The method according to 1, wherein the step of forming the foam on the user provides a cooling sensation and / or a cracking sound to the user.

[10] The method according to any one of 1 to 9, wherein the foam is formed on the user in a form selected from the group consisting of a sherbet-like foam, an ice cream-like foam, a cracking foam, or combinations of two or more thereof.

Claims

Claim 1 A non-therapeutic method for treating human skin, hair, and / or mucous membranes, comprising: (a) providing a personal care composition in the form of a stable water-in-oil emulsion in a pressurized container, said emulsion comprising: (i) a continuous aqueous phase containing water; (ii) a discontinuous phase containing a foaming component, trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)) and trans-1,3,3,3-tetrafluoropropene (1234ze(E)), wherein said 1233zd(E) and said 1234ze(E) together constitute 40% to 60% by weight of said personal care composition and are present in a weight ratio of trans 1233zd:trans 1234ze of 1:8 to 8:1; (iii) an emulsifier having an HLB value of 7 to 18 and capable of being present in said continuous aqueous phase and / or said discontinuous phase, wherein said emulsifier is a linear long-chain solid emulsifier; (iv) one or more active ingredients capable of being present in said continuous aqueous phase and / or said discontinuous phase; (v) optionally, one or more auxiliary gel, lotion, or cream-forming components capable of being present in said continuous aqueous phase and / or said discontinuous phase; (b) discharging at least a portion of said personal care composition from said container to ambient pressure conditions to form a foam, thereby dispensing said personal care composition onto and / or into said human skin, hair, and / or mucous membranes being treated. Claim 2 The non-therapeutic method according to claim 1, wherein said 1233zd(E) and said 1234ze(E) together constitute 40% to 60% by weight of said personal care composition and are present in a weight ratio of trans 1233zd:trans 1234ze of 1:8 to less than 1:

1. Claim 3 The non-therapeutic method according to claim 1, wherein said 1233zd(E) and said 1234ze(E) together constitute 40% to 60% by weight of said personal care composition and are present in a weight ratio of trans 1233zd:trans 1234ze of 8:1 to 1:

1. Claim 4 The non-therapeutic method according to any one of claims 1 to 3, further comprising a stability assisting component in an amount of less than 9% to 14% by weight. Claim 5 The non-therapeutic method according to claim 4, wherein said stability assisting component is selected from the group consisting of ester oils, silicones, aliphatic alcohols, waxes, and combinations of two or more thereof. Claim 6 Said 1233zd(E) and said 1234ze(E) together constitute at least 60% by weight of said personal care composition, and the non-therapeutic method according to claim 1, wherein trans 1233zd: trans 1234ze is present in a weight ratio of 1:8 to less than 1:

1.

7. The step of forming a foam on the user provides a cooling sensation and / or a cracking sound to the user, the non-therapeutic method according to claim 1.

8. The foam is formed on the user in a form selected from a sherbet-like foam, an ice cream-like foam, a cracking foam, or a combination of two or more of these, the non-therapeutic method according to any one of claims 1 to 7.

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