Hairspray formulations for HFO propellants

Abstract

The present disclosure provides a formulation comprising a fluoroolefin, an amine neutralizing agent, a fixative polymer, and a solvent. The formulation may be trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), and the amine neutralizing agent may be triethanolamine (TEA), triisopropanolamine (TIPA), or a mixture thereof. The formulation may be suitable for use as a personal care product, such as a hairspray.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims priority to U.S. Provisional Patent Application No. 63 / 290,132, filed December 16, 2021, which claims the benefit of U.S. Provisional Patent Application No. 18 / 080,312, filed December 13, 2022, both of which are incorporated by reference herein in their entireties.

[0002] FIELD OF THEINVENTION The present invention relates to cosmetic formulations, including in particular hair treatment formulations, and to methods of producing such formulations which are environmentally friendly and stable. [Background technology]

[0003] Hair treatment formulations, especially hairsprays, are now widely used and are usually formulations that contain one or more preformed polymeric materials (sometimes called resins) that are included to impart desired properties to hair. For example, polymers can be used to impart shine to hair, style hair, hold hairstyles, impart desired texture or feel to hair, improve hair color, condition hair, dry and set hair quickly, straighten or smooth hair, soften hair, strengthen hair, make unruly hair easier to manage, improve optical properties, provide hold to hair, control frizz, and / or repair damaged hair. Polymers can be fixative ingredients that provide "hold" to hair, i.e., help maintain hair in a desired style or shape. Such polymers are usually included in the formulation with one or more other ingredients, such as propellants.

[0004] The propellant in such hair treatment formulations allows the polymeric component to be applied to the hair in a finely dispersed spray, whereupon the polymeric component performs its intended function in relation to the hair. For example, hairsprays containing fixatives tend to add a degree of stiffness so that the hair retains a desired shape.

[0005] It has been common practice in the past to use propellants that have one or more harmful effects when released into the environment. For example, many of the propellants previously and currently used have high Global Warming Potential (GWP) and are volatile organic compounds (VOCs). It is well established that compounds with these properties can adversely affect the Earth's atmosphere and / or environment. As a result, there has been both commercial and governmental efforts to reduce the use of such materials in many applications, including as propellants.

[0006] Although several compounds and blends of compounds have been proposed for use as propellants in various applications, the selection of a propellant for use in a hair treatment formulation is particularly complex, since the substitution of a new propellant in a formulation to improve environmental performance may result in the degradation of one or more other properties of the hair treatment formulation.For example, it has been found that certain types of hair treatment polymers and formulations may degrade or degrade in performance when exposed to certain environmentally advantageous propellants.

[0007] Improvements to the above are desirable. Summary of the Invention

[0008] The present disclosure provides fluoroolefins of the formula:

[0009] [ka] In the formula, R 1 is hydrogen or fluorine, R 2 is hydrogen or fluorine, R 3is hydrogen or fluorine, a solvent, an amine neutralizing agent, and a fixative polymer. The fluoroolefin may have a global warming potential (GWP) measured in carbon dioxide (CO2) equivalents of 10 or less, e.g., 10 or less, 9 or less, 8 or less, 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, or 1 or less. Suitable fluoroolefins can include trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)).

[0010] The present disclosure further provides personal care products, such as hairsprays, comprising the formulations provided herein. The present disclosure also provides methods of making the formulations provided herein. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] 1.Definition The singular forms "a," "an," and "the" include the plural forms unless the context clearly dictates otherwise or unless otherwise clearly indicated by the referenced context.

[0012] The term "about" as used herein generally indicates a relative difference of 10 percent of the specified value. Numeric ranges used herein are meant to include any number or subset of numbers contained within the range, whether or not specifically disclosed. Moreover, these numerical ranges are intended to be understood as supporting claims directed to any number or subset of numbers within the range.

[0013] All percentages, parts, proportions and ratios used herein are by weight of the total formulation given, unless otherwise specified.

[0014] All references to singular features or limitations of the invention are intended to include the corresponding plural features or limitations, and vice versa, unless otherwise specified or clearly indicated otherwise by the referenced context.

[0015] As used herein, the terms "preferred" or "preferably" and variations refer to embodiments of the invention that provide certain benefits, under particular circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention.

[0016] As used herein, the term "homopolymer" is intended to include a polymer formed essentially from only a single monomer structure.

[0017] As used herein, the term "copolymer" is intended to include polymers formed from two or more monomer structures, and thus includes polymers formed from three monomer structures (known as terpolymers), etc.

[0018] 2. Hairspray formulations The formulations of the present disclosure may be suitable for use in personal care products such as hair sprays. These formulations may include one or more propellants, one or more fixative polymers, one or more solvents, and one or more amine neutralizers. The amine neutralizers may improve the performance of the fixative polymer. However, the amine neutralizers can react with the propellant, especially when the propellant contains an olefin. Thus, the selection of the appropriate combination of amine neutralizer and propellant may be difficult, as many combinations may be chemically unstable. The present disclosure provides a stable formulation in which the amine neutralizer does not significantly react with the olefin while maintaining the performance of the fixative polymer. Each component of the formulation is described in more detail below.

[0019] 3. Propellant Aerosol propellants often contain fluorocarbon-based compounds. The industry is constantly searching for new fluorocarbon-based mixtures that offer alternatives and are considered to be environmentally safer replacements for the CFCs, HCFCs, and HFCs used today. Of particular interest are mixtures containing hydrofluorocarbons, fluoroolefins, iodide-containing compounds, and other fluorinated compounds that have low ozone depletion potential and low global warming potential.

[0020] The present disclosure provides formulations that include propellants with lower Global Warming Potential (GWP) than those currently used in aerosolized formulations, such as 1,2-difluoroethane (HFC-152a). GWP was developed to allow for comparison of the global warming impact of various gases. Specifically, it is a measure of how much energy the emission of one ton of a gas absorbs over a given period of time, relative to the emission of one ton of carbon dioxide. The higher the GWP, the more a given gas will warm the earth over the same period of time, compared to CO2. The period used for GWP is 100 years. GWP provides a common measure that allows analysts to add up emission estimates of different gases. 1,2-difluoroethane (HFC-152a), for example, has a GWP of 138.

[0021] In comparison, the fluoroolefins included in the formulations of the present disclosure have a Global Warming Potential (GWP), measured in carbon dioxide equivalents, of 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, or 1 or less.

[0022] Formulations of the present disclosure may include a fluoroolefin of Formula I, as shown below:

[0023] [ka] In the formula, R 1 is hydrogen or fluorine, R 2 is hydrogen or fluorine, R 3is hydrogen or fluorine.

[0024] A particular fluoroolefin for use in the formulations of the present disclosure can include trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)).

[0025] The fluoroolefin may be present in the formulation in an amount of about 10% by weight or more, about 15% by weight or more, about 20% by weight or more, about 25% by weight or more, 30% by weight or more, about 35% by weight or more, about 40% by weight or more, about 45% by weight or less, about 50% by weight or less, about 55% by weight or less, about 60% by weight or less, about 65% by weight or less, about 70% by weight or less, about 75% by weight or less, about 80% by weight or less, about 85% by weight or less, about 90% by weight or less, or any value inclusive of these endpoints, based on the total weight of the formulation.

[0026] The formulations of the present disclosure may further include a co-propellant. Suitable co-propellants include 1,1-difluoroethane (HFC-152a), dimethyl ether, hydrocarbons such as propane, isobutane, and n-butane, and compressed gases such as nitrogen, air, and carbon dioxide.

[0027] 4. Fixative polymers The formulations of the present disclosure may vary widely according to the particular needs or target properties of the formulation. For example, the formulations may be used in personal care formulations, such as hair sprays, in which the fixative polymer may be present in an amount of about 4% to 8% by weight, or texturizing sprays, in which the fixative polymer may be present in an amount of about 1% to 2% by weight. Thus, the formulations of the present disclosure may include fixative polymers suitable for hair treatment.

[0028] The fixative polymer suitable for use in the formulation of the present disclosure may include copolymers. The copolymer may include two-component copolymers, such as, for example, acrylate-octyl acrylamide copolymer. The copolymer may include three-component copolymers, such as, for example, vinyl acetate-crotonate-vinyl neodecanoate copolymer. The copolymer may include four-component copolymers, such as, for example, octyl acrylamide-acrylate-butylaminoethyl-methacrylate copolymer.

[0029] Fixative polymers can be described by their acid value. The acid value of a polymer is defined as the mass in milligrams of potassium hydroxide (KOH) required to neutralize one gram of polymer, as described, for example, in ASTM D974. A fixative polymer suitable for the formulation of the present disclosure has an acid value of 2.05 meq / g.

[0030] The fixative polymer may be present in the formulation in an amount of 1% by weight or more, about 2% by weight or more, about 3% by weight or more, about 5% by weight or more, about 7% by weight or more, about 10% by weight or less, about 12% by weight or less, about 15% by weight or less, about 17% by weight or less, about 20% by weight or less, or any value encompassed by these endpoints, based on the total weight of the formulation.

[0031] 5. Amine Neutralizer As mentioned above, many hairspray formulations use amine neutralizers to impart performance attributes to the polymer on the hair. However, amines can easily react with olefins such as trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), a low GWP propellant used in the formulations of the present disclosure.

[0032] One widely used neutralizing agent is aminomethylpropanol (AMP), a primary amine that further imparts good performance characteristics to fixative polymers. However, as described further below, AMP has been found to react with the low GWP propellant trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)) in a similar manner to another widely used amine neutralizing agent, monoisopropanolamine (MIPA).

[0033] The reactivity of amines with olefins is more likely when primary amines are used due to the lack of steric hindrance at the nitrogen atom. In contrast, sterically hindered tertiary amines are expected to be less reactive with olefins. However, when tertiary amines are used in hairspray formulations, the performance of fixative polymers on hair is often unacceptable. Without being bound by theory, it is believed that tertiary amines may have a negative effect on the performance of fixative polymers.

[0034] Surprisingly, two tertiary amines, triethanolamine (TEA) and triisopropanolamine (TIPA), were found to perform well in terms of both stability towards trans-1,3,3,3-tetrafluoropropene and the ability to impart good performance to the fixative polymer.

[0035] The formulations of the present disclosure may include an amount of amine neutralizing agent, based on the total weight of the formulation, of about 0.1% by weight or more, about 0.2% by weight or more, about 0.5% by weight or more, about 1.0% by weight or more, about 1.2% by weight or less, about 1.5% by weight or less, about 2.0% by weight or less, or any value encompassed by these endpoints.

[0036] The stability of the mixture was tested by accelerated aging test. The formulation was stored in a sealed container at 50°C for 3 months. After the aging period of 3 months, the formulation was tested to determine the amount of fluoride present using an ion-selective electrode. If the amount of fluoride present was less than 300 ppm, the formulation was considered stable. For example, a stable formulation contained fluoride in an amount of 300 ppm or less, 250 ppm or less, 225 ppm or less, 200 ppm or less, 150 ppm or less, 100 ppm or less, 50 ppm or less, 10 ppm or less, or 5 ppm or less.

[0037] After the three month waiting period, the formulations were also observed to determine the presence or absence of precipitate. If no precipitate was present upon visual inspection, the formulation was considered stable.

[0038] 6. Solvent The formulations of the present disclosure may include one or more solvents. Suitable solvents can include water and low molecular weight alcohols, such as ethanol and isopropanol.

[0039] The solvent may be present in the formulation in an amount of about 10% by weight or more, about 15% by weight or more, about 20% by weight or more, about 25% by weight or more, about 30% by weight or more, about 35% by weight or more, about 40% by weight or more, about 45% by weight or more, about 50% by weight or less, about 55% by weight or less, about 60% by weight or less, about 65% by weight or less, about 70% by weight or less, about 75% by weight or less, about 80% by weight or less, about 85% by weight or less, about 90% by weight or less, or any value inclusive of these endpoints, based on the total weight of the formulation.

[0040] Suitable co-solvents for use in the formulations of the present disclosure can include, for example, water, ethanol, isopropanol, and mixtures thereof.

[0041] The co-solvent may be present in the formulation in an amount of 0% by weight or more, about 1% by weight or more, about 5% by weight or more, about 10% by weight or more, about 20% by weight or more, about 30% by weight or more, about 40% by weight or more, about 50% by weight or more, about 60% by weight or more, about 70% by weight or more, about 80% by weight or more, about 90% by weight or more, about 95% by weight or more, about 99% by weight or more, or any value inclusive of these endpoints, based on the total weight of the formulation.

[0042] 7. Additives The formulation of the present disclosure may further comprise additives.Additives may comprise one or more of each of lubricants, stabilizers, corrosion inhibitors, fragrances, starches, and performance modifiers.Suitable performance modifiers may include, for example, silicones.

[0043] 8. Manufacturing method The formulations of the present disclosure can be synthesized by first slowly adding the fixative polymer to the solvent with stirring at room temperature. Then, while continuing to stir the mixture, other ingredients such as the amine neutralizer and optional additives are added. Finally, the propellant is added to complete the formulation.

[0044] 9.How to use The formulations of the present disclosure may be suitable for use as personal care products. In one aspect, the personal care product may be a hair treatment product. When used in this way, the formulations may be applied to hair to impart desired properties such as stylability, volume, shine, hair manageability, style durability, softness, ease of styling, anti-frizz, hair fiber alignment, excellent wet conditioning, dry conditioning, wet combing, ease of use with styling tools, or hair protection from styling tools. In one aspect, the formulations of the present disclosure may be used as hair sprays. The effectiveness of these formulations may be determined by evaluating curl retention, stiffness, combability, feel, and washability.

[0045] The following non-limiting examples serve to illustrate the present disclosure. EXAMPLES

[0046] Example 1: Reactivity of amines towards 1,1-difluoroethane (HFC-152a) and trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)) Four different amine neutralizers (two primary and two tertiary) were formulated with octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer in an amount of 5% by weight, solvent in an amount of 50% by weight, and 45-x% by weight of 1234ze and x% by weight of amine neutralizer, where x=approximately 1. This formulation was then tested for stability alongside a formulation containing the current industry standard, 1,1-difluoroethane (HFC-152a), instead of trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)).

[0047] As shown in Table 1 below, stability and performance can vary significantly from propellant to propellant and from amine to amine.

[0048] [Table 1]

[0049] Example 2: Reactivity of amines towards trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)) Eight different neutralizers were tested for their stability against trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)) by detection of fluoride with an ion selective electrode and visual observation of precipitate formation, and for their performance on hair when the stability results were favorable. The results are shown in Table 2 below.

[0050] [Table 2]

[0051] In stability testing of tromethamine and Neutrol TE, it was found that no precipitate formed, but the fluoride levels were at levels above normal for precipitate formation in the inventors' experience, and therefore the stability is considered intermediate. Both of these examples are notable in that prior to testing tromethamine, a primary amine, all primary amines tested had clearly unacceptable stability, and conversely, prior to testing Neutrol TE, a tertiary amine, all tertiary amines had clearly acceptable stability, yet both of these examples have intermediate stability.

[0052] Aspects Aspect 1 is a fluoroolefin of the formula:

[0053] [ka] In the formula, R 1 is hydrogen or fluorine, R 2 is hydrogen or fluorine, R 3 is hydrogen or fluorine, a solvent, an amine neutralizing agent, and a fixative polymer.

[0054] Aspect 2 is a formulation according to aspect 1, wherein the fluoroolefin has a GWP of 5 or less, as measured in carbon dioxide (CO2) equivalents.

[0055] Aspect 3 is a formulation of either Aspect 1 or Aspect 2, wherein the fluoroolefin comprises trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)).

[0056] Aspect 4 is the formulation of any one of Aspects 1 to 3, wherein the solvent comprises ethanol.

[0057] Aspect 5 is a formulation according to any one of Aspects 1-4, wherein the amine neutralizing agent comprises an amine that is non-reactive towards HFO-1234ze(E) as determined by detection of fluoride with an ion selective electrode.

[0058] Aspect 6 is the formulation of any one of Aspects 1-5, wherein the amine neutralizing agent comprises a tertiary amine.

[0059] Aspect 7 is the formulation of any one of Aspects 1-6, wherein the amine neutralizing agent comprises triethanolamine (TEA), triisopropanolamine (TIPA), or a mixture thereof.

[0060] Aspect 8 is the formulation of any one of Aspects 1-7, further comprising at least one of one or more co-propellants and one or more co-solvents.

[0061] Aspect 9 is a formulation according to any one of Aspects 1 to 8, further comprising one or more additives selected from the group consisting of lubricants, stabilizers, corrosion inhibitors, flavors, starches, and performance modifiers.

[0062] Aspect 10 is the formulation of any one of Aspects 1-9, wherein the fixative polymer is selected from the group consisting of acrylates-octylacrylamide copolymer, vinyl acetate-crotonate-vinyl neodecanoate copolymer, and octylacrylamide-acrylate-butylaminoethyl-methacrylate copolymer.

[0063] Example 11 is a formulation according to any one of Examples 1 to 10, wherein the fluoroolefin is present in the formulation in an amount of 35% to 45% by weight, based on the total weight of the formulation.

[0064] Embodiment 12 is the formulation of any one of embodiments 1 to 11, wherein the solvent is present in an amount of 45% to 55% by weight, based on the total weight of the formulation.

[0065] Aspect 13 is a formulation according to any one of Aspects 1 to 12, wherein the amine neutralizing agent is present in the formulation in an amount of 0.2% to 1.5% by weight, based on the total weight of the formulation.

[0066] Example 14 is a formulation according to any one of Examples 1 to 13, wherein the fixative polymer is present in the formulation in an amount of 1% to 15% by weight, based on the total weight of the formulation.

[0067] Aspect 15 is a personal care formulation comprising a formulation according to any one of aspects 1-14.

[0068] Example 16 is a personal care formulation according to example 15, wherein the formulation is an aerosol.

[0069] Example 17 is a personal care formulation according to either example 15 or example 16, wherein the formulation is a hairspray.

[0070] Example 18 is a method comprising applying the formulation of example 17 to hair.

[0071] Aspect 19 is the formulation of any one of Aspects 1-16, wherein the formulation contains less than 300 ppm fluoride as measured by an ion selective electrode after storage of the formulation at 50° C. for 3 months in a sealed container.

[0072] Embodiment 20 comprises contacting a polymer with a solvent, adding an amine neutralizing agent, and adding a propellant.

[0073] Example 21 is a formulation according to any one of Examples 1 to 10, wherein the fluoroolefin is present in the formulation in an amount of 10% to 90% by weight, based on the total weight of the formulation.

[0074] Embodiment 22 is the formulation of any one of embodiments 1 to 11, wherein the solvent is present in an amount of 10% to 90% by weight, based on the total weight of the formulation.

Claims

1. Fluoroolefins of the formula: 【Chemistry 1】 In the formula, R １ is hydrogen or fluorine, R ２ is hydrogen or fluorine, R ３ is hydrogen or fluorine; and A solvent; An amine neutralizing agent; and a fixative polymer.

2. The fluoroolefin is carbon dioxide (CO ２ 13. The formulation of claim 1, having a GWP of 10 or less when measured at 100% (w / w) equivalents.

3. 2. The formulation of claim 1, wherein the fluoroolefin comprises trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)).

4. The formulation of claim 1 , wherein the solvent comprises ethanol.

5. 10. The formulation of claim 1, wherein the amine neutralizing agent comprises an amine that is non-reactive toward trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)) as determined by detection of fluoride with an ion selective electrode.

6. 10. The formulation of claim 1, wherein the amine neutralizing agent comprises a tertiary amine.

7. 10. The formulation of claim 1, wherein the amine neutralizing agent comprises triethanolamine (TEA), triisopropanolamine (TIPA), or a mixture thereof.

8. 10. The formulation of claim 1, further comprising at least one of one or more co-propellants and one or more co-solvents.

9. 10. The formulation of claim 1, further comprising one or more additives selected from the group consisting of lubricants, stabilizers, corrosion inhibitors, flavors, starches, and performance modifiers.

10. 2. The formulation of claim 1, wherein the fixative polymer is selected from the group consisting of acrylates-octylacrylamide copolymer, vinyl acetate-crotonate-vinyl neodecanoate copolymer, and octylacrylamide-acrylate-butylaminoethyl-methacrylate copolymer.

11. 10. The formulation of claim 1, wherein the fluoroolefin is present in the formulation in an amount of 10% to 90% by weight based on the total weight of the formulation.

12. 2. The formulation of claim 1, wherein the solvent is present in an amount of 10% to 90% by weight based on the total weight of the formulation.

13. 10. The formulation of claim 1, wherein the amine neutralizing agent is present in the formulation in an amount of 0.2% to 1.5% by weight based on the total weight of the formulation.

14. 10. The formulation of claim 1, wherein the fixative polymer is present in the formulation in an amount of 1% to 15% by weight based on the total weight of the formulation.

15. A personal care formulation comprising the formulation of claim 1.

16. 16. The personal care formulation of claim 15, wherein the formulation is an aerosol.

17. 16. The personal care formulation of claim 15, wherein the formulation is a hairspray.

18. 20. A method comprising applying the formulation of claim 17 to hair.

19. 10. The formulation of claim 1, wherein the formulation contains less than 300 ppm fluoride as measured by an ion selective electrode after storage of the formulation at 50°C for 3 months in a sealed container.

20. 13. A method for preparing the formulation of claim 1, comprising the steps of: contacting the polymer with the solvent; adding said amine neutralizing agent; adding said propellant.

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