Polyvinyl alcohol film-forming polymers for alcohol-based hair styling formulations and methods of use thereof

Abstract

The present disclosure relates to a hair styling formulation comprising: (a) a volatile solvent; and (b) at least one film-forming polymer comprising at least one of (i) a polyvinyl alcohol or (ii) a polyvinyl alcohol ester having other ester functions in addition to proprietary acetate esters, and (i) and (ii) being soluble in a volatile solvent, with the proviso that if the at least one film-forming polymer comprises a polyvinyl alcohol, if the at least one film-forming polymer comprises a polyvinyl alcohol, the at least one film-forming polymer is not soluble in the volatile solvent. The degree of hydrolysis of the polyvinyl alcohol is less than about 60%. Methods of styling hair using the hair styling formulations are also disclosed.

Description

[0001] Priority claim

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 355,177, filed on June 24, 2022, the entire contents of which are hereby incorporated by reference. Technical Field

[0003] The present disclosure relates to film-forming polymers for use in hair styling formulations (compounds) and methods of using the hair styling formulations. Background Art

[0004] The polymer used in the hair styling formulation is usually made of synthetic materials. In order to make the polymer suitable for such hair styling applications, they should be soluble in alcohol-based (alcohol-based, based on alcohol) systems and / or systems containing a small amount of volatile organic compounds (VOCs), and in the case of aerosol (aerosol) based hair care sprays, they should also be compatible with propellants. Conventional synthetic polymers are usually cheap and have acceptable performance. However, because they are non-biodegradable, conventional synthetic polymers are unsustainable. In addition, the cost and performance of regenerated synthetic polymers are not easy.

[0005] Therefore, there is a need for biodegradable film-forming polymers that provide the same or better performance at a cost comparable to non-biodegradable alternatives and that are soluble in alcohol-based systems, such as ethanol-based systems, and optionally compatible with propellants such as hydrocarbons or dimethyl ether.

[0006] Our US 11,135,148 describes hair fixatives made from renewable resources, including polyglucose polymers based on starch esters.

[0007] Sunscreen formulations based on biodegradable polyesters are the subject of our recent patent publications: US 2021 / 0259930; US 2021 / 0259945; and US 2021 / 0259946. Do we need this phrase? It refers to sunscreen formulations,

[0008] US 6,602,489 and WO 2006 / 018328 describe concentrated hair spray products comprising a film-forming polymer, which may be sold by Kuraray under the trade name Poval TM Polyvinyl alcohol for sale. Poval available TM The DH of the product is >99%. Kuraray usually provides these materials with a specific viscosity without indicating the molecular weight. For example, Poval TM LM-10HD is supplied with a viscosity of 4.5-5.7 MPa·s. Poval TMThe viscosity of LM-20 is 3.0-4.0 MPa·s. However, it is interesting that the Poval TM The number average molecular weight of LM-20 is about 20,000, but it is not known whether this is accurate. Polyvinyl alcohols may also be those available from Sekisui, for example under the trade name Selvol TM PVOH 523 / E 523 and Selvol TM PVOH 540 is available commercially with a DH of 88%.

[0009] US2015 / 0328130 describes a sunscreen composition comprising 0.1 to 10% of a nonlinear polymer selected from polyvinyl alcohol; and 40 to 80% of water. Exemplary compositions include various polyvinyl alcohols with a degree of hydrolysis of 86-99%; and at least 70% of water; but no ethanol.

[0010] AU 2017 / 204073 describes cosmetic compositions, in particular sun protection products, to which polyvinyl alcohol is added in order to facilitate the washing away of UV filters from textiles soiled with these compositions. According to the teaching, the addition of polyvinyl alcohol to the composition has a favorable effect on washability, reducing the staining of textiles caused by the composition. This effect is demonstrated by polyvinyl alcohol having a degree of hydrolysis of 86 to 89 mol %.

[0011] US 3,417,180 describes a hair spray formulation comprising polyvinyl acetate whose acetate groups are partially hydrolyzed to an extent of about 15% to 60%. Solubility in absolute ethanol is demonstrated to be up to 50% and solubility in halogenated hydrocarbon propellants (particularly trichlorofluoromethane and dichlorodifluoromethane) is demonstrated to be up to 48%. The use of hydrocarbon propellants and ethers is not taught or suggested, nor is the solubility of partially hydrolyzed polyvinyl acetate in such propellants demonstrated. Copolymers of partially hydrolyzed polyvinyl acetate with other monomers, including (meth)acrylic acid and crotonic acid, are theoretical (inferred), but not illustrated.

[0012] US 3,005,809 describes sheets or films of vinyl alcohol-crotonic acid copolymers.

[0013] The compatibility of film-forming polymers with alcohol-based (especially ethanol-based) hair styling formulations remains a significant issue for formulators, and there is a pressing need for film-forming polymers that are biodegradable but at the same time soluble and compatible in alcohol-based systems.

[0014] It is therefore an object of the present disclosure to provide film-forming polymers which are biodegradable, exhibit excellent compatibility with alcohol-based formulations, especially ethanol-based formulations, and can therefore be formulated into stable hair styling formulations providing biodegradability. Summary of the invention

[0015] In one embodiment, the present disclosure relates to a hair styling formulation comprising:

[0016] (a) volatile solvents; and

[0017] (b) at least one film-forming polymer comprising at least one of: (i) polyvinyl alcohol or (ii) a polyvinyl alcohol ester having ester functionalities in addition to the proprietary acetate, and (i) and (ii) are soluble in a volatile solvent; provided that if the at least one film-forming polymer comprises polyvinyl alcohol, the degree of hydrolysis of the polyvinyl alcohol is less than about 60%.

[0018] In a second embodiment, the present disclosure is directed to a method of styling hair comprising spraying the hair with the hair styling formulation described herein. DETAILED DESCRIPTION

[0019] Polyvinyl alcohol ("PVOH") has the following general structure:

[0020]

[0021] And are characterized by pendant OH and acetate (CH3-CO-) groups / functional groups.

[0022] There are many known methods for preparing PVOH. However, from an industrial perspective, the current mainstream production method is as follows: polyvinyl acetate is prepared by free radical polymerization using vinyl acetate as a raw material, and then the polyvinyl acetate is hydrolyzed / esterified. Methanol or ethanol is mainly used as a solvent in the polymerization process / hydrolysis process.

[0023] The basic properties of PVOH are usually determined by the degree of polymerization and the degree of hydrolysis.

[0024] The degree of polymerization of PVOH is usually expressed as the viscosity average degree of polymerization obtained from the viscosity in water. In addition, when the degree of hydrolysis is expressed by repeating units m and n, the degree of hydrolysis can be expressed as follows: Degree of hydrolysis (mol%) = m / (n+m) × 100. This is a value expressing the proportion of vinyl alcohol units in all repeating units in mol%.

[0025] We found that the degree of hydrolysis is an important parameter for the solubility of the base polyvinyl alcohol in volatile solvents. On the other hand, when the base polyvinyl alcohol is derivatized with hydrophobic functional groups, the degree of hydrolysis is less important.

[0026] In one embodiment, the film-forming polymer comprises underivatized polyvinyl alcohol (also referred to herein as "base polyvinyl alcohol").

[0027] In a preferred embodiment, the degree of hydrolysis of the base polyvinyl alcohol is 60% or less, in particular 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 100%, 101%, 102%, 103%, 104%, 105%, 106%, 107%, 108%, 109%, 110%, , 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59% and / or 60%; or a continuous sequence of percentages within this range, for example 1% to 60%, 1% to 59%, 2% to 59%, 2% to 58%, 3% to 58%, etc.

[0028] In another preferred embodiment, the degree of hydrolysis of the base polyvinyl alcohol is from 20% to 58%, in particular 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57% and / or 58%; or a continuous sequence of percentages within this range, for example 20% to 58%, 21% to 58%, 21% to 57%, 22% to 57%, 22% to 56%, etc.

[0029] In another preferred embodiment, the degree of hydrolysis of the base polyvinyl alcohol is from 35% to 58%, in particular 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57% and / or 58%; or a continuous sequence of percentages within this range, for example 35% to 58%, 36% to 58%, 36% to 57%, 37% to 57%, 37% to 56%, etc.

[0030] For ranges defined with the term "about", for example "less than about 60%" or "about 35% to about 58%", the range is expanded by up to 1%, preferably by up to 0.5%.

[0031] Once the base PVOH has been prepared, the base PVOH can be esterified by further reaction with a suitable functionalizing agent (e.g., an acid, anhydride, or lactone) according to methods known in the art. The esters can also be prepared by starting with vinyl acetate and other vinyl monomers in a specified ratio to form an intermediate copolymer with pendant acetate functional groups, and then selectively hydrolyzing the acetate groups to obtain the desired PVOH portion.

[0032] Thus, in another embodiment, the at least one film-forming polymer comprises a polyvinyl alcohol derivatized with additional ester functionalities different from the pendant OH and acetate groups characterizing the base polyvinyl alcohol.

[0033] As used herein, simply "polyvinyl alcohol" or "PVOH" or "base polyvinyl alcohol" or "base PVOH" without further modification refers to polyvinyl alcohol consisting only of pendant OH and acetate groups.

[0034] As used herein, "polyvinyl alcohol ester" or "PVOH ester" and the like refers to polyvinyl alcohol derivatized with additional ester functionality other than the pendant OH and acetate groups that characterize the base polyvinyl alcohol.

[0035] As noted above, one method of forming PVOH esters is to react the base PVOH with a suitable acid or a suitable acid derivative such as an anhydride or a lactone.

[0036] Suitable acids include linear, branched or cyclic, saturated or unsaturated, non-aromatic or aromatic mono- or polycarboxylic acids.

[0037] Exemplary acids that can be used for this purpose include, but are not limited to, propionic acid, butyric acid, valeric acid, isovaleric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, octadecanoic acid, neopentanoic acid, 2-ethylhexanoic acid, isononanoic acid, neononanoic acid, neodecanoic acid, Versatic Acid 9 (a highly branched nonanoic acid available from Hexion), Versatic Acid 10 (a highly branched decanoic acid available from Hexion), palmitic acid, benzoic acid, anthranilic acid, salicylic acid, phenylacetic acid, cinnamic acid, 4-chlorobenzoic acid, 1,4-dichlorobenzoic acid, 4-nitrobenzoic acid, 2,4-dinitrobenzoic acid, succinic acid, glutaric acid, adipic acid, octanedioic acid (suberic acid), acid), malonic acid, malic acid, octenylsuccinic acid, dodecenylsuccinic acid, azelaic acid, sebacic acid, pimelic acid, 2,2-dimethylsuccinic acid, 3,3-dimethylglutaric acid, 2,2-dimethylglutaric acid, maleic acid, fumaric acid, itaconic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, stearic acid, oleic acid, oxalic acid, malonic acid, pimelic acid, azelaic acid, sebacic acid, benzene Formic acid, phthalic acid, citric acid, tartaric acid, lactic acid, malic acid, methyl benzoic acid, isophthalic acid, phthalic acid, terephthalic acid, trimellitic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, tetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, hexahydrophthalic acid, tetrachlorophthalic acid, methylhexahydrophthalic acid, substituted derivatives thereof, and mixtures of one or more of the foregoing.

[0038] Anhydrides of the above acids, if present, such as succinic anhydride, dimethyl and diethyl malonate, octenylsuccinic anhydride, dodecenylsuccinic anhydride, phthalic anhydride, trimellitic anhydride, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, may also be used.

[0039] In addition, certain materials that react in a manner similar to the acids to form esters are also useful. Such materials include lactones such as caprolactone, propiolactone, methyl caprolactone, and butyrolactone.

[0040] As also described above, PVOH esters can be prepared by free radical polymerization of vinyl acetate and other vinyl monomers in a specified ratio to form an intermediate copolymer having pendant acetate functional groups, and then selectively hydrolyzing the acetate groups to obtain the desired PVOH portion. Polymerization methods known in the art such as, but not limited to, solution polymerization, bulk polymerization, precipitation polymerization, emulsion polymerization, and suspension polymerization can be used to polymerize vinyl acetate with other vinyl monomers. In a preferred embodiment, the polymerization is solution polymerization. In another preferred embodiment, the polymerization is suspension polymerization.

[0041] The disclosed hair styling formulations additionally comprise a volatile solvent. Examples of volatile solvents include one or more alcohols such as methanol, ethanol and isopropanol; volatile hydrocarbons such as isooctane, isododecane and isohexadecane; volatile aldehydes; volatile silicones; and volatile ketones such as acetone and methyl ethyl ketone. Hydrofluoroolefins may also be used as carrier solvents in the formulations.

[0042] In a preferred embodiment, the volatile solvent is an alcohol-based solvent system, wherein the alcohol-based solvent system comprises at least one C 1-6 Straight or branched chain alcohols.

[0043] In another preferred embodiment, the volatile solvent is a ketone.

[0044] In a particularly preferred embodiment, the volatile solvent is selected from ethanol, methanol, isopropanol, acetone, and mixtures thereof.

[0045] In another especially preferred embodiment, the hair styling formulation comprises ethanol.

[0046] In a more preferred embodiment, the ethanol-containing hair styling formulation is anhydrous. The terms "non-aqueous" and "anhydrous" are used interchangeably herein and refer to compositions containing less than about 10% by weight of water, especially less than about 5% by weight of water, or less than 1% by weight of water, or even 0% water.

[0047] In a most preferred embodiment, the hair styling formulation comprises ethanol but does not contain any other alcohol or water.

[0048] In an alternative embodiment, where water is present, such small amounts of water may be desirable, for example, as a processing aid or co-solvent. In certain exemplary embodiments, the water content of the composition will be no greater than about 9% water in order to prevent the active ingredient from phase separation or precipitation from solution. One of ordinary skill in the art will recognize that different active ingredients have different tolerances to water in solution and will adjust the water content accordingly.

[0049] In one embodiment, the polymer is completely soluble in ethanol or a mixture consisting mainly of ethanol and containing 0-20% by weight, preferably 5-10% by weight, of water.

[0050] In another embodiment, the polymer is completely soluble in ethanol.

[0051] In another embodiment, the polymer is completely soluble in anhydrous ethanol.

[0052] In another embodiment, after incorporating the polymer into anhydrous ethanol, the polymer is completely dissolved in the solvent immediately. As used in this disclosure, the phrase "immediately" means one hour or less, preferably half an hour or less, most preferably 15 minutes or less.

[0053] In another embodiment, the polymer remains completely soluble in anhydrous ethanol 24 hours after incorporation of the polymer into the solvent.

[0054] In a particularly preferred embodiment,

[0055] (a) upon incorporation of the polymer into anhydrous ethanol, the polymer immediately and completely dissolves in the solvent; and

[0056] (b) 24 hours after the polymer was incorporated into anhydrous ethanol, the polymer was completely dissolved in the solvent.

[0057] In an even more preferred embodiment, the polymer comprises polyvinyl alcohol or an ester thereof, wherein if the polymer comprises underivatized polyvinyl alcohol, the degree of hydrolysis of the polyvinyl alcohol is 35-58% and:

[0058] (a) upon incorporation of the polymer into anhydrous ethanol, the polymer immediately and completely dissolves in the solvent; and

[0059] (b) 24 hours after the polymer was incorporated into anhydrous ethanol, the polymer was completely dissolved in the solvent.

[0060] In a more preferred embodiment, the polymer comprises polyvinyl alcohol or an ester thereof, wherein if the polymer comprises underivatized polyvinyl alcohol, the degree of hydrolysis of the polyvinyl alcohol is 35-45% and:

[0061] (a) upon incorporation of the polymer into anhydrous ethanol, the polymer immediately and completely dissolves in the solvent; and

[0062] (b) 24 hours after the polymer was incorporated into anhydrous ethanol, the polymer was completely dissolved in the solvent.

[0063] In an even more preferred embodiment, the polymer comprises polyvinyl alcohol or an ester thereof, wherein if the polymer comprises underivatized polyvinyl alcohol, the degree of hydrolysis of the polyvinyl alcohol is 38-42% and:

[0064] (a) upon incorporation of the polymer into anhydrous ethanol, the polymer immediately and completely dissolves in the solvent; and

[0065] (b) 24 hours after the polymer was incorporated into anhydrous ethanol, the polymer was completely dissolved in the solvent.

[0066] In one embodiment, the hair styling formulation further comprises a propellant.

[0067] In certain embodiments of the present disclosure, the disclosed formulation can be stored in a pressure vessel by combining with a propellant, and the present disclosure also extends to a pressure vessel comprising the disclosed formulation. The formulation stored in this way can be used by opening the valve in the container to release the propellant and composition usually in the form of spray or mist. The propellant used in the composition can be any suitable gas or gas combination, which can be compressed or liquefied in a distribution spray can, expanded or volatilized into a vapor or gaseous form under exposure to ambient temperature and pressure conditions, so as to deliver the composition in an aerosol form. Suitable propellants include hydrocarbons with 1 to 5 carbon atoms, including but not limited to methane, ethane, propane, isopropyl ether, butane, isobutane, butylene, pentane, isopentane, neopentane and pentene, hydrofluorocarbons (HFC), including but not limited to 1,1-difluoroethane (HP 152a), chlorofluorocarbons (CFCs), hydrofluoroolefins (HFOs), nitrogen, ethers (including dimethyl ether) and any mixture thereof. Those of ordinary skill in the art recognize that in a closed container such as an aluminum can or a glass bottle, a propellant such as dimethyl ether condenses into a liquid state at ambient temperature. Therefore, the composition in the aerosol container is a liquid formulation that can contain dissolved propellant, undissolved liquid propellant, and gaseous propellant. All of these are under pressure due to the vapor pressure of the propellant. In the practice of this aspect of the present disclosure, the propellant can be present in an amount of up to about 90% by weight, preferably about 2% by weight to about 50% by weight, more preferably about 5% by weight to about 40% by weight, more preferably about 30% by weight, based on the total weight of the aerosol composition.

[0068] In another embodiment, the propellant is a hydrocarbon derived ether.

[0069] In another embodiment, the propellant is dimethyl ether (DME).

[0070] In a preferred embodiment, the polymer is fully compatible with DME.

[0071] In a particularly preferred embodiment,

[0072] (a) After the polymer is incorporated into anhydrous ethanol, the polymer immediately and completely dissolves in the solvent;

[0073] (b) the polymer is completely dissolved in anhydrous ethanol 24 hours after the polymer is incorporated into the solvent; and

[0074] (c) The polymer is completely compatible with DME.

[0075] In an even more preferred embodiment, the polymer comprises polyvinyl alcohol or an ester thereof, wherein if the polymer comprises underivatized polyvinyl alcohol, the degree of hydrolysis of the polyvinyl alcohol is 35-58% and:

[0076] (a) After the polymer is incorporated into anhydrous ethanol, the polymer immediately and completely dissolves in the solvent;

[0077] (b) the polymer is completely dissolved in anhydrous ethanol 24 hours after the polymer is incorporated into the solvent; and

[0078] (c) The polymer is completely compatible with DME.

[0079] In a more preferred embodiment, the polymer comprises polyvinyl alcohol or an ester thereof, wherein if the polymer comprises underivatized polyvinyl alcohol, the degree of hydrolysis of the polyvinyl alcohol is 35-45% and:

[0080] (a) After the polymer is incorporated into anhydrous ethanol, the polymer immediately and completely dissolves in the solvent;

[0081] (b) the polymer is completely dissolved in anhydrous ethanol 24 hours after the polymer is incorporated into the solvent; and

[0082] (c) The polymer is completely compatible with DME.

[0083] In an even more preferred embodiment, the polymer comprises polyvinyl alcohol or an ester thereof, wherein if the polymer comprises underivatized polyvinyl alcohol, the degree of hydrolysis of the polyvinyl alcohol is 38-42% and:

[0084] (a) After the polymer is incorporated into anhydrous ethanol, the polymer immediately and completely dissolves in the solvent;

[0085] (b) the polymer is completely dissolved in anhydrous ethanol 24 hours after the polymer is incorporated into the solvent; and

[0086] (c) The polymer is completely compatible with DME.

[0087] In another embodiment, the propellant is a hydrofluorocarbon.

[0088] In another embodiment, the propellant is 1,1-difluoroethane.

[0089] In a preferred embodiment, the polymer is completely compatible with 1,1-difluoroethane.

[0090] In a particularly preferred embodiment,

[0091] (a) After the polymer is incorporated into anhydrous ethanol, the polymer immediately and completely dissolves in the solvent;

[0092] (b) the polymer is completely dissolved in anhydrous ethanol 24 hours after the polymer is incorporated into the solvent; and

[0093] (c) The polymer is completely compatible with 1,1-difluoroethane.

[0094] In a more preferred embodiment, the polymer comprises polyvinyl alcohol or an ester thereof, wherein if the polymer comprises underivatized polyvinyl alcohol, the degree of hydrolysis of the polyvinyl alcohol is 35-58% and:

[0095] (a) After the polymer is incorporated into anhydrous ethanol, the polymer immediately and completely dissolves in the solvent;

[0096] (b) the polymer is completely dissolved in anhydrous ethanol 24 hours after the polymer is incorporated into the solvent; and

[0097] (c) The polymer is completely compatible with 1,1-difluoroethane.

[0098] In a more preferred embodiment, the polymer comprises polyvinyl alcohol or an ester thereof, wherein if the polymer comprises underivatized polyvinyl alcohol, the degree of hydrolysis of the polyvinyl alcohol is 35-45% and:

[0099] (a) After the polymer is incorporated into anhydrous ethanol, the polymer immediately and completely dissolves in the solvent;

[0100] (b) the polymer is completely dissolved in anhydrous ethanol 24 hours after the polymer is incorporated into the solvent; and

[0101] (c) The polymer is completely compatible with 1,1-difluoroethane.

[0102] In an even more preferred embodiment, the polymer comprises polyvinyl alcohol or an ester thereof, wherein if the polymer comprises underivatized polyvinyl alcohol, the degree of hydrolysis of the polyvinyl alcohol is 38-42% and:

[0103] (a) After the polymer is incorporated into anhydrous ethanol, the polymer immediately and completely dissolves in the solvent;

[0104] (b) the polymer is completely dissolved in anhydrous ethanol 24 hours after the polymer is incorporated into the solvent; and

[0105] (c) The polymer is completely compatible with 1,1-difluoroethane.

[0106] In one embodiment, the hair styling formulation disclosed herein is dispensed from a bag-on-valve device. Typically, a bag-on-valve device comprises a spray can equipped with an aerosol valve and comprising a welded bag. The product is placed in the bag, and the propellant is filled in the space between the bag and the can. When the spray button is pressed, the product is dispensed by simply squeezing the bag through the propellant.

[0107] Typically, the compositions according to the present disclosure are prepared as non-aqueous, volatile solvent based compositions. However, in some embodiments, the compositions comprise a single liquid phase that may further comprise dispersed particles (eg, UV active agent in particulate form).

[0108] We have discovered that, in certain circumstances, the base polyvinyl alcohol polymer described above containing primarily only pendant alcohol and acetate groups can be derivatized without loss of solubility in volatile solvents.

[0109] The solubility of derivatized polyvinyl alcohols in such volatile solvents can be evaluated using the test protocol outlined in the Examples below.

[0110] As mentioned above, the main production methods for producing polyvinyl alcohol include making polyvinyl acetate by free radical polymerization using vinyl acetate as a raw material and then hydrolyzing the polyvinyl acetate. Derivatives can then be prepared, for example, by (a) reacting polyvinyl alcohol with an acid, anhydride or lactone; or (b) directly (i) polymerizing a polymerizable monomer precursor (e.g., vinyl alkanoate) of a derivatized functional group with vinyl acetate, followed by (ii) hydrolysis to produce an alcohol functional group with any desired degree of hydrolysis.

[0111] In one embodiment, polyvinyl alcohol is derivatized with crotonic acid, for example by copolymerizing crotonic acid with vinyl acetate, followed by at least partial hydrolysis / transesterification of the product to obtain the desired polyvinyl alcohol derivative. In a preferred embodiment, the product is a partially hydrolyzed vinyl acetate-crotonic acid copolymer comprising pendant carboxylic acid groups and pendant hydroxyl groups condensed together to form an internal γ-lactone functionality.

[0112] In one embodiment, the polyvinyl alcohol polymer is derivatized with succinic acid, for example by reacting polyvinyl alcohol soluble in a volatile solvent with succinic anhydride.

[0113] In another embodiment, the polyvinyl alcohol polymer is derivatized with caprolactone, for example by reacting polyvinyl alcohol soluble in a volatile solvent with the caprolactone.

[0114] In another embodiment, the polyvinyl alcohol polymer is derivatized with pivalic acid, for example by copolymerizing vinyl pivalate with vinyl acetate, followed by hydrolysis / transesterification of the product to obtain the desired polyvinyl alcohol derivative.

[0115] In another embodiment, the polyvinyl alcohol polymer is derivatized with neononanoic acid, for example by copolymerizing vinyl neononanoate with vinyl acetate, followed by hydrolysis / transesterification of the product to obtain the desired polyvinyl alcohol derivative.

[0116] In another embodiment, the polyvinyl alcohol polymer is derivatized with Versatic Acid 9, for example by copolymerizing the vinyl ester of Versatic Acid 9 (eg, VeoVa 9 from Hexion) with vinyl acetate and then hydrolyzing / transesterifying the product to obtain the desired polyvinyl alcohol derivative.

[0117] In another embodiment, the polyvinyl alcohol polymer is derivatized with neodecanoic acid, for example by copolymerizing vinyl neodecanoate with vinyl acetate, followed by hydrolysis / transesterification of the product to obtain the desired polyvinyl alcohol derivative.

[0118] In another embodiment, the polyvinyl alcohol polymer is derivatized with Versatic Acid 10, for example by copolymerizing vinyl neodecanoate (eg, VeoVa 10 from Hexion) with vinyl acetate, followed by hydrolysis / transesterification of the product to obtain the desired polyvinyl alcohol derivative.

[0119] In another embodiment, the polyvinyl alcohol polymer is derivatized with 2-ethylhexanoic acid, for example by polymerizing vinyl 2-ethylhexanoate with vinyl acetate, followed by hydrolysis / transesterification of the product to obtain the desired polyvinyl alcohol derivative.

[0120] In another embodiment, the polyvinyl alcohol polymer is derivatized with lauric acid, for example by polymerizing vinyl laurate with vinyl acetate, followed by hydrolysis / transesterification of the product to obtain the desired polyvinyl alcohol derivative.

[0121] In another embodiment, the poly(vinyl alcohol) polymer is derivatized with carboxylic acids pendant to the polymer backbone to provide internal lactone (cyclic ester) moieties.

[0122] In a preferred embodiment, a carboxylic acid pendant to the polymer backbone is reacted with an alcohol pendant to the γ-carbon relative to the carbon pendant to the carboxylic acid to form an internal γ-lactone (five-membered ring).

[0123] In a preferred embodiment, the carboxylic acid pendant to the polymer backbone is an acrylic acid or crotonic acid residue obtained after copolymerization of acrylic acid or crotonic acid, respectively, with vinyl acetate and optionally one or more vinyl alkanoates and subsequent hydrolysis to produce alcohol functionality to any desired degree of hydrolysis.

[0124] In a more preferred embodiment, the carboxylic acid pendant to the polymer backbone is a crotonic acid residue obtained after copolymerization of crotonic acid with vinyl acetate and optionally one or more vinyl alkanoates and subsequent hydrolysis to produce alcohol functionality at any desired degree of hydrolysis.

[0125] In a most preferred embodiment, the carboxylic acid pendant to the polymer backbone is a crotonic acid residue obtained after copolymerization of crotonic acid with vinyl acetate and optionally one or more vinyl alkanoates and subsequent hydrolysis to produce alcohol functionality at any desired degree of hydrolysis, and the internal lactone formed is a γ-lactone.

[0126] In a particularly preferred embodiment, the polyvinyl alcohol is derivatized with 1 to 15 wt % of crotonic acid gamma-lactone, based on 100 wt % of the polyvinyl alcohol polymer.

[0127] In a more preferred embodiment, the polyvinyl alcohol is derivatized with 2-13% by weight of crotonic acid gamma-lactone based on 100% by weight of the polyvinyl alcohol polymer.

[0128] In an even more preferred embodiment, the polyvinyl alcohol is derivatized with 6-12 wt% of crotonic acid gamma-lactone, based on 100 wt% of the polyvinyl alcohol polymer.

[0129] In a most preferred embodiment, the polyvinyl alcohol is derivatized with 6-12% by weight of crotonic acid gamma-lactone, based on 100% by weight of the polyvinyl alcohol polymer, and the degree of hydrolysis thereof is 35-50%.

[0130] It should be noted that the carboxylic acid pendant to the polymer is an acrylic acid or crotonic acid residue obtained after copolymerization of acrylic acid or crotonic acid, respectively, with vinyl acetate and optionally one or more vinyl alkanoates and subsequent hydrolysis to produce alcohol functionality at any desired degree of hydrolysis, and is known to form lactones with alcohol functionality pendant to the polyvinyl alcohol polymer. For this reason, steps are sometimes taken to inhibit lactone formation. However, we have unexpectedly and unexpectedly found that the lactone form is beneficial, particularly in the context of providing high humidity curl retention (HHCR).

[0131] In addition to the polyvinyl alcohol described herein, the hair styling formulation may additionally include other film-forming polymers, especially (but not limited to) when the intended use is hair care. By way of example only, such other film-forming polymers may be selected from: polyglucose polymers based on starch esters, such as described in US11,135,148, the entire contents of which are hereby incorporated herein by reference; polyesters, such as described in US2021 / 0259930, US2021 / 0259945 and US2021 / 0259946, the entire contents of which are hereby incorporated herein by reference; and N-alkyl (meth) acrylamide copolymers, such as described in US20180098930, the entire contents of which are hereby incorporated herein by reference. Other examples of suitable other film-forming polymers include: film-forming polymers comprising at least 5% by weight of acid-containing monomers, based on the total weight of the film-forming polymer. In a preferred embodiment, the film-forming polymer comprises at least 5% by weight of carboxylic acid-containing monomers. Non-limiting examples of these monomers are acrylic acid, crotonic acid, methacrylic acid, maleic acid, itaconic acid, and combinations and mixtures thereof. Other film-forming polymers, whether synthetic or natural, may be used with the acid-containing polymers described above. Non-limiting examples of these other film-forming polymers are: and LV-71 polymer (octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer), Polymer (Acrylates / Octyl Acrylamide Copolymer), 0 / 55 and BALANCE Polymer (Acrylate Copolymer), 47 polymer (octylacrylamide / butylaminoethyl methacrylate copolymer), 28-2930 polymer (VA / crotonate / vinyl neodecanoate copolymer), 28-1310 polymer (VA / crotonate copolymer), Polymer (Sodium Polystyrene Sulfonate), DynamX Polymer (Polyurethane-14 (and) AMP-Acrylates Copolymer), RESYN Polymer (Acrylates / Octyl Acrylamide Copolymer), STRUCTURE 2001 (Acrylates / Steareth-20 Itaconate Copolymer) and 3001 (Acrylates / Ceteth-20 Itaconate Copolymer); from ISP (PVM / MA half ethyl ester copolymer), GANEX (Butyl PVP), GANEX (PVP / hexadecene copolymer), V-220 (PVP / eicosene copolymer), WP-660 (triathionyl PVP), A425 (butyl ester of PVM / MA copolymer), AN-119PVM / MA copolymer, GANTREZ ES (ethyl ester of PVM / MA copolymer), GANTREZES425 (butyl ester of PVM / MA copolymer), GAFFIX (vinyl caprolactam / PVP / dimethylaminoethyl methacrylate copolymer), (Polyquaternium-11), GAFQUAT (Polyquaternium-28), AQUAFLEX XL-306 (Polyimide-1), AQUAFLEX (PVP / vinyl caprolactam / DMAPA acrylate copolymer), AQUAFLEX (isobutylene / ethylmaleimide / hydroxyethylmaleimide copolymer), ALLIANZ (Acrylates / C1-2 Succinate / Hydroxyacrylate Copolymer), STYLEZE (PVP / DMAPA acrylate copolymer), STYLEZE (VP / Acrylates / Lauryl Methacrylate Copolymer), STYLEZE (Polyquaternium-55), copolymer series (PVP / dimethylaminoethyl methacrylate copolymer), ADVANTAGE and ADVANTAGE (vinyl caprolactam NP / dimethylaminoethyl methacrylate copolymer), ADVANTAGE PLUS (VA / butyl maleate / isobornyl acrylate copolymer), Antaron ECo (ethyl cellulose); BASF's ULTRAHOLD STRONG (acrylic acid / ethyl acrylate / tert-butyl acrylamide), LUVIMER (tert-butyl acrylate / ethyl acrylate / methacrylic acid), LUVIMER 36D (ethyl acrylate / tert-butyl acrylate / methacrylic acid), LUVIQUAT (Polyquaternium-16), LUVIQUAT (Polyquaternium-16), LUVISKOL K30(PVP), LUVISKOL (PVP), LUVISKOL (PVP / VA copolymer), LUVISKOL (PVPNA copolymer), LUVISKOL LUVISET (Polyurethane-1), Clear (VP / methacrylamide dimethylimidazole copolymer), LUVIFLEX (Acrylate Copolymer), ULTRA HOLD (acrylate / acrylamide copolymer), Plus(polyvinyl caprolactam), Silk (PEG / PPG-25 / 25 Dimethicone / Acrylates Copolymer); from Amerchol DR-25 (acrylic acid / methacrylic acid / acrylate / methacrylate); ACUDYNE from Rohm & Haas (Acrylic acid / methacrylic acid / acrylate / methacrylate / hydroxy ester acrylate; DIAFORMER from Mitsubishi and distributed by Clariant DIAFORMER and DIAFORMER (Methacryloylethyl Betaine / Acrylates Copolymer), ACUDYNE (acrylates / hydroxy acrylates copolymer), ACUDYNE SCP (vinyl carboxamide / AMPSA / methacrylates copolymer) and Rheology modifiers; FIXOMER from ONDEO Nalco and FIXOMER (INCI name: Methacrylic Acid / Sodium Acrylamidomethylpropane Sulfonate Copolymer); FIXATE from Noveon (AMP-acrylate / allyl methacrylate copolymer), FIXATE (polyacrylate-X), Ultrez 10 (Carbomer), CARBOPOL Ultrez (Acrylates / C10-30 Alkyl Acrylate Copolymer), AVALLTRE Series (acrylate copolymers), AVALURE series (polyurethane-2, polyurethane-4, PPG-17 / IPDI / DMPA copolymer); polyethylene glycol; water-soluble acrylic compounds; water-soluble polyesters; polyacrylamide; polyamine; polyquaternary amine; styrene maleic anhydride (SMA) resin; polyvinyl amine; from Covestro C 2000 (polyurethane solution in ethanol (INCI-Polyurethane-64)), eco E 1000 (water-based polyurethane), C1010(water-based polyurethane), C 1008(waterborne polyurethane), C 1001 (aqueous polyurethane); Inolex Lexfilm Sun (INCI-Polyester-7 (and) Neopentyl Glycol Diheptanoate), Inolex Lexfilm Sun Natural MB (INCI-Caprylyl Glycerin / Sebacic Acid Copolymer), Inolex WetFilm MB (INCI-Trimethylpentanediol / Adipic Acid / Glycerin Crosspolymer), Inolex Lexfilm Spray (INCI-Polyester-10 (and) Propylene Glycol Dibenzoate) and Inolex Lexorez 100 MB (INCI-Adipic Acid / Diethylene Glycol Crosspolymer) from Inolex; and other conventional polymers that are soluble in polar solvents or can be dissolved by neutralization with an appropriate base.

[0132] In one embodiment, the hair styling formulation comprises, in addition to the polyvinyl alcohol described herein, at least one biodegradable polydextrose film-forming polymer based on starch esters.

[0133] In another embodiment, the hair styling formulation comprises, in addition to the polyvinyl alcohol described herein, at least one biodegradable polyester film-forming polymer.

[0134] When the hair fixative comprises other film-forming polymers in addition to the polyvinyl alcohol described herein, these other film-forming polymers may also be present in the hair fixative formulation in an amount of 0.1 to 10% by weight, based on the total weight of the formulation.

[0135] In a preferred embodiment, such further film-forming polymers are incorporated into the hair styling formulation in an amount of 0.5 to 5% by weight, based on the total weight of the formulation.

[0136] In another preferred embodiment, the total amount of all other such film-forming polymers and the polyvinyl alcohol described herein is from 0.1 to 10 wt. %, based on the total weight of the formulation.

[0137] In an especially preferred embodiment, the total amount of all other such film-forming polymers and the polyvinyl alcohol described herein is from 0.5 to 5% by weight, based on the total weight of the formulation.

[0138] The disclosed hair styling formulations may contain a variety of additional, optional ingredients, which are referred to herein as "cosmetic ingredients," but may also include ingredients commonly referred to as pharmaceutical actives. The CTFA Cosmetic Ingredient Handbook, Seventh Edition, 1997, and Eighth Edition, 2000, which are incorporated herein by reference in their entirety, describe a variety of cosmetic and pharmaceutical ingredients commonly used in skin care compositions, which ingredients are suitable for use in the compositions of the present disclosure. Examples of these functional classes disclosed in the reference include absorbents, abrasives, anti-caking agents, defoaming agents, antioxidants, binders, biological additives, buffers, fillers, chelating agents, chemical additives, colorants, cosmetic astringents, cosmetic antimicrobial agents, denaturants, pharmaceutical astringents, topical analgesics, film formers, fragrance components, humectants, sunscreens, pH adjusters, plasticizers, reducing agents, skin bleaching agents, skin conditioners (emollients, moisturizers, miscellaneous and occlusives), skin protectants, solvents, foam boosters, hydrotropes, solubilizers, suspending agents (non-surfactants), SPF boosters, water repellents and viscosity enhancers (aqueous and non-aqueous).

[0139] It has been found that polyvinyl alcohol polymers can provide hair styling polymers that are not only biodegradable, but can also provide equivalent or better hair styling performance (especially as hair spray polymers) at a cost comparable to their non-biodegradable alternatives, for example in terms of spray rate, viscosity and hardness. The polymers of the present invention are soluble in alcohol-based solvent systems and, optionally, are also compatible with hair styling propellants.

[0140] As is well known in the art, solution viscosity is an important property of aerosol hair fixatives, where the balance between aerosol spray characteristics (affected by solution viscosity) and the performance of the hair fixative on hair (affected by the presence of water) in low VOC hair fixatives is problematic. Having a low viscosity allows the polymer solution to be sprayed out of solution and provide uniform coverage and small droplet size. In a solvent system consisting of water and ethylene glycol dimethyl ether (EGDME) in a relative weight percentage of 67 / 33, the viscosity of the solution of the optionally partially neutralized polymer at 25° C. with a polymer solids content of 5% is preferably in the range of about 2 to about 10 cps, more preferably in the range of about 2 to about 7 cps, and even more preferably less than 5 cps.

[0141] In one embodiment, the polyvinyl alcohol polymer of the present invention may be present in the hair styling composition in an amount of about 1 wt% to about 10 wt%, based on the weight of the hair styling composition. In another embodiment, the polyvinyl alcohol polymer is present in an amount of about 2 wt% to about 8 wt%. In yet another embodiment, the polyvinyl alcohol polymer is present in an amount of about 2 wt% to about 6 wt%.

[0142] In one embodiment of the present invention, the hair styling composition will contain no more than about 80% volatile organic compounds (VOCs), such as alcohol and / or propellants, with the remainder being the solvent water. In another embodiment, the hair styling composition will contain no more than about 55% volatile organic compounds.

[0143] In one embodiment of the present invention, the hair styling composition optionally further comprises at least one neutralizing agent. Suitable alkaline neutralizing agents compatible with the composition may be used, even inorganic materials such as sodium hydroxide or potassium hydroxide. Generally, organic amines or alkanolamines are easily used for neutralization. In one embodiment, neutralizing agents include, but are not limited to: ammonia; primary, secondary and tertiary amines; alkanolamines; and hydroxylamines (such as 2-amino-2-methyl-propanol and 2-amino-2-methyl-1,3-propanediol); C4 to C 24 Hydrocarbon chain mono-, di- and tri-long chain fatty amines; ethoxylated and propoxylated long chain (C4 to C 24 ) fatty amines and mixtures thereof. In another embodiment, the neutralizing agent comprises aminomethyl propanol and dimethyl stearylamine, inorganic materials (e.g., sodium hydroxide and potassium hydroxide) and triethanolamine. In one embodiment of the present invention, the neutralizing agent is an organic amine or an alcohol amine. In one embodiment, a combination of neutralizing agents may also be used.

[0144] In one embodiment, the spray rate of the hair styling composition in a system of 3% solids and 40% DME with a VOC>95% ranges from about 0.3 to about 1.5 g / sec, in another embodiment, preferably from about 0.5 to about 1.2 g / sec, and in another embodiment, more preferably from about 0.7 to about 0.9 g / sec.

[0145] Other optional cosmetically acceptable additives may also include one or more additives selected from hair styling polymers, plasticizers, UV absorbers, dyes, fragrances, preservatives, viscosity modifiers, vitamins, moisturizers, antipruritic and anti-dandruff ingredients. Mixtures of these optional additives may also be included. As previously mentioned, the polymeric binders of the present invention will have little or no adverse chemical reaction with these additives.

[0146] The present disclosure will now be described in more detail with reference to the following non-limiting examples.

[0147] Example

[0148] Example 1: Effect of Hydrolysis Degree on Solubility

[0149] Attempts were made to dissolve polymers of various degrees of hydrolysis as shown in Table 1 in a formulation containing 63% anhydrous ethanol and 37% organic matter.

[0150] The desired result is a clear, single-phase and complete solution, which indicates that the formulation is completely soluble. On the other hand, if the solution is turbid or contains precipitates, it indicates that the formulation is at least partially insoluble. Evaluations were performed immediately after mixing ("initial solubility") and after 24 hours ("24 hour solubility").

[0151] Table 1

[0152] # Film-forming polymers Degree of hydrolysis (%) Initial solubility 24 hours solubility 2 <![CDATA[Poval TM LM-10HD 1 ]]> 38-42 clarify clarify 3 <![CDATA[Poval TM LM-20 2 ]]> 38-42 clarify clarify 4 <![CDATA[Active 35 3 ]]> 32.7 clarify clarify 5 <![CDATA[Active 45 4 ]]> 44-46 clarify clarify 6 <![CDATA[Active 55 5 ]]> 55.5-57.5 clarify clarify 7 <![CDATA[Ethapol XS 6 ]]> 66.7 Slightly turbid precipitation 8 <![CDATA[Other PVOH 7 > 70-99.9 Insoluble Insoluble

[0153] 1,2 Polyvinyl alcohol from Kuraray

[0154] 3,4 ,5 ,6 Polyvinyl alcohol, from Nouryon

[0155] 7 We tested (1) Poval TM 5-74 (DH=72.5-74.5%); (2) Poval TM 4-88 (DH = 86.7-88.7); and (3) Poval TM 4-98 (DH = 98.0-98.8%), in each case the polymer was completely insoluble in absolute ethanol at 5 wt%, 2.5 wt% and 1 wt%.

[0156] The results showed a clear correlation between the degree of hydrolysis of the film-forming polymer and the solubility of the formulation in anhydrous ethanol.

[0157] In general, the solubility of any disclosed film-forming polymer in any particular solvent or solvent system can be determined in a straightforward manner analogous to this Example.

[0158] Embodiment 2:

[0159] The derivatives shown in Table 2 were prepared and tested similarly to Example 1.

[0160] The succinate esters are prepared by reacting a base polyvinyl alcohol polymer with succinic anhydride.

[0161] Caprolactone condensation products are prepared by reacting a base polyvinyl alcohol polymer with caprolactone.

[0162] The vinyl pivalate was prepared as described in Example 11 below.

[0163] The 2-ethylhexanoate was prepared as described in Example 10 below.

[0164] The vinyl laurate was prepared as described in Example 9 below.

[0165] Table 2

[0166] # Film-forming polymers Initial solubility 24 hours solubility 9 PVA LM-20 succinate (80:20) clarify clarify 10 PVA LM-20 succinate (70:30) clarify clarify 11 PVA LM-10HD succinate (80:20) clarify clarify 12 PVA LM-10HD succinate (70:30) clarify clarify 13 PVA LM 10HD + Caprolactone (80:20) clarify clarify 14 PVA LM 10HD + Caprolactone (90:10) clarify clarify 15 PVA LM-20+caprolactone (90:10) clarify clarify 16 PVA LM-20+caprolactone (80:20) clarify clarify 17 PVOH vinyl neopentanoate (93:7; DH 32%) clarify clarify 18 PVOH vinyl neopentanoate (93:7; DH 55%) clarify clarify 19 PVOH vinyl neopentanoate (93:7; DH 73%) clarify clarify 20 PVOH vinyl neopentanoate (93:7; DH 83%) clarify clarify 21 PVOH 2-ethylhexanoate (95:5; DH 19%) clarify clarify 22 PVOH 2-ethylhexanoate (95:5; DH 36%) ND ND 23 PVOH 2-ethylhexanoate (95:5; DH 52%) ND ND 24 PVOH 2-ethylhexanoate (95:5; DH 73%) clarify clarify 25 PVOH Vinyl Laurate (96:4; DH 35%) clarify clarify 26 PVOH vinyl laurate (96:4; DH 61%) clarify clarify 27 PVOH vinyl laurate (96:4; DH 80%) clarify clarify

[0167] ND = Not Determined

[0168] Embodiment 3:

[0169] Selected polymer samples (using the numbers in the table above) were prepared in ethanol solvent and blended with the propellant according to the following procedure to understand the compatibility with the propellant.

[0170] Preparation procedure:

[0171] 1. Charge all of the ethanol in the formulation into the main mixing vessel.

[0172] 2. Start mixing by propeller agitation (adjust mixing speed until there is a vortex 2 / 3 of the way up the agitator shaft).

[0173] 3. Slowly add the polymer powder through the sifter to one side of the vortex. Allow the polymer to disperse completely.

[0174] 4. Fill the concentrate into an aerosol container and add the propellant.

[0175] 5. Observe the charged aerosol for clarity, phases, and any precipitate that may have formed initially and over time.

[0176] In the following examples, the propellant is dimethyl ether (DME) at 30% or 40% of the total formulation. When the propellant is 30% by weight DME, the test formulation contains 3% by weight polymer, up to 1% by weight aminomethyl propanol, q.s. to 70% by weight ethanol, and 30% by weight dimethyl ether propellant. When the propellant is 40% by weight DME, the test formulation contains 3% by weight polymer, up to 1% by weight aminomethyl propanol, q.s. to 60% by weight ethanol, and 40% by weight dimethyl ether propellant.

[0177] The desired result is a clear, single-phase and complete solution, which indicates that the formulations are compatible. On the other hand, if the solution is cloudy or opaque or contains precipitates, it indicates that the formulations are at least partially incompatible.

[0178] Table 3

[0179]

[0180] 1 Dimethyl ether (DME)

[0181] ND = Not Determined

[0182] The results indicate that the solubility of the base polymer in anhydrous ethanol does not guarantee compatibility with the propellant. However, many of the disclosed film-forming polymers are compatible with 30% and 40% DME.

[0183] In general, the compatibility of any disclosed film-forming polymer with a particular propellant or solvent-propellant system can be determined in a straightforward manner analogous to this example.

[0184] Embodiment 4:

[0185] Several embodiments of the present disclosure have been tested by OECD Biodegradability Method 301 D, details of which are readily available. Testing was performed in both river water and activated sludge.

[0186] Table 4

[0187]

[0188] Table 5

[0189]

[0190] OECD 301D ratings include (1) “ultimately biodegradable”, which means a biodegradation rate of ≥ 60% within 60 days; (2) “readily biodegradable”, which means a biodegradation rate of > 60% within 28 days; (3) “inherently biodegradable”, which means a biodegradation rate of 20% to 60% within 28 days; and (4) “non-biodegradable”, which means a biodegradation rate of less than 20% within 28 days.

[0191] Embodiment 5:

[0192] The polymers according to the present disclosure were tested in a half wig evaluation test for an aerosol hair spray.

[0193] Equipment / Materials

[0194] Head, Sandy, Root turned manikin, #351, Bur Max Co.

[0195] Wig Stand

[0196] Comb: Ace, black, hard rubber, 5" x 1" or equivalent

[0197] Test Formulations - Hairsprays to be Evaluated

[0198] Control formula

[0199] Testing Procedure

[0200] 1) Place head on wig stand; comb hair to remove any tangles or knots.

[0201] 2) Use a comb to divide the wig into equal parts (left and right sides).

[0202] 3) Place dividers in the middle of the head to prevent overspray on each side.

[0203] 4) Hold the hair spray 6 inches from the hair and spray the test formula on one side of the head for 10 seconds and the control formula on the other side of the head for 10 seconds. Allow the head to dry at room temperature for 45 minutes.

[0204] 5) For each formulation to be tested, spray two heads (alternating between the two heads randomly spraying the alternative sides with the test formulation and the control).

[0205] 6) Each head was then blindly evaluated by four panelists.

[0206] 7) The panelists then evaluate a series of criteria and choose which side has more of each performance (see below).

[0207] 8) When it is selected two to six times out of eight times, the difference in a certain performance characteristic between the two samples is considered to be "no significant difference"; when it is selected zero or one time out of eight times, it is considered to be "significantly inferior"; when it is selected seven or eight times out of eight times, it is considered to be "significantly superior".

[0208] Blind panel review:

[0209] Beading: Visually inspect each side of the head for dried polymer beads. Choose the side with more beads.

[0210] Glossiness: Visually inspect the glossiness of both sides of the wig. Determine which side is shinier / glosser.

[0211] Stiffness: Gently touch each side of the head to feel the difference in stiffness. Choose which side is harder or more rigid.

[0212] Resilience: Hold the strands in one hand and gently pull the edge three times with the other hand. Observe the resilience and elasticity. Choose the side with more elasticity and resilience.

[0213] Web Formation: Hold the strands in both hands and gently pull each edge outward about 4 inches (repeat three times to avoid damaging the bond). The more web-like it is, the better the web formation.

[0214] Feel: Run your fingers down each side of your head and determine preference. Choose the side that feels silkier / cleaner.

[0215] Valve Specifications for Aerosol Hairspray Testing (Purchased from Aptar)

[0216] Product:VX-81 229mm

[0217] Shell: VX BARB ARIANE---0,33-0,00-PA

[0218] Valve stem: VX80-4, 03-1-0, 33-8, 70-NATU-1

[0219] Valve gasket:BUT U133-2,54-8,00-1,14-BUT

[0220] Spring: VX80—INOX—VX OPEN COIL

[0221] Valve Fixture:SUB-AL-CLCL-DR-32,64—S-GA

[0222] Immersion pipe: PE-NATU-4,07-3,10-RL---0.122STD

[0223] Actuator Specifications (from Aptar)

[0224] Product:XL200 3302-05480-23

[0225] Actuator:XL200-PP—3,90-WHIT-POLISH-SPRAY

[0226] Poor entry (INSERT):MS23---POM-BLAC—RBK000568-MS.023MISTY BLACK

[0227] Testing and Results

[0228] The polymers according to the present disclosure were formulated and tested with 3% polymer, 40% DME and the balance ethanol and compared with the control. The results are shown in Table 6 below.

[0229] Data analysis / evaluation:

[0230] Samples exhibit this property less frequently: 0 to 1 of the 8 selected experimental samples show statistically significant differences from the reference at the 95% confidence level;

[0231] The samples showed no statistical difference compared with the standard: 2 to 6 out of 8 selected experimental samples showed statistically significant differences at the 95% confidence level;

[0232] The samples showed this performance more often: 7 to 8 out of 8 selected experimental samples showed statistically significant differences from the reference at the 95% confidence level.

[0233] In addition to beading, more performance is expected.

[0234] Table 6

[0235]

[0236]

[0237] It is clear from the foregoing that we are surprisingly able to achieve performance on hair with the disclosed polymers that is comparable to, and in many cases superior to, commercially available standards.

[0238] Example 6: Preparation of an intermediate copolymer with pendant acetate functional groups; this intermediate copolymer is a precursor to a PVOH copolymer esterified with lauric acid.

[0239] A four-necked 1 L round bottom flask was equipped with a mechanical stirrer; a Claisen adapter equipped with a temperature probe and a reflux condenser; a 500 mL addition funnel (non-pressure balanced type); and a 125 mL addition funnel (non-pressure balanced type). The flask was charged with 7.50 g of vinyl laurate, 67.5 g of vinyl acetate, 51.15 g of ethyl acetate, and 2.91 g of 98% tert-butyl peroxyoctanoate. The 500 mL addition funnel was charged with a mixture of 22.50 g of vinyl laurate and 202.50 g of vinyl acetate (monomer SA-1). The 125 mL addition funnel was charged with a mixture of 2.91 g of 98% tert-butyl peroxyoctanoate and 67.95 g of ethyl acetate (initiator SA-2).

[0240] The reaction mixture was refluxed using a hot water bath under stirring. After the reaction mixture refluxed for 5 minutes, the contents of monomer SA-1 were uniformly added to the reaction mixture over a period of 4 hours. When the addition of monomer SA-1 was complete, the feed hopper was rinsed (flushed into the reactor) with 4.61 g of ethyl acetate. After the reaction mixture refluxed for 1 hour, the contents of initiator SA-2 were uniformly added to the reaction over a period of 5 hours.

[0241] After the addition of initiator SA-2 was complete, the reaction was refluxed for another 2 hours (total reaction time was 8 hours). The reaction was then cooled to below reflux and 70.0 g of ethanol was added. After a uniform solution was obtained, the reaction was left overnight.

[0242] After standing overnight, the reaction was brought back to reflux and a solution of 0.90 g of t-butyl peroxyoctanoate in 7.50 g of ethanol was added in one go. After the initiator was added in one go, heating at reflux was continued for 2 hours. The reaction was then allowed to cool below reflux and 104.0 g of ethanol was added. The reaction was stirred until a uniform polymer solution was obtained and then allowed to cool. A clear, colorless, viscous polymer solution was obtained. Solids (determined gravimetrically): 49.94%.

[0243] Examples 7 and 8: Preparation of intermediate copolymers with pendant acetate functional groups; the intermediate copolymers are precursors to PVOH copolymers esterified with 2-ethylhexanoic acid and pivalic acid, respectively.

[0244] Other intermediate copolymers were prepared using different hydrophobic esters of vinyl alcohol following the general procedure described in Example 6. The compositions of all intermediate copolymers estimated based on the feed ratio of the two monomers are summarized in Table 7 below.

[0245] Table 7.

[0246]

[0247] Example 9: The intermediate copolymer of Example 6 was partially hydrolyzed to obtain a PVOH polymer esterified with lauric acid.

[0248] A four-necked 1L round bottom flask was equipped with a mechanical stirrer, a Claisen adapter, a septum and a stopper equipped with a temperature probe and a Barrett trap with a reflux condenser on top. 250.5g of the polymer solution prepared in Example 6 (125.0g, solid basis) and 146g of ethanol were added to the flask. The resulting mixture was stirred until a uniform solution was obtained, and then 2.25g of 98% sulfuric acid was added to the reaction mixture. A hot water bath was used to reflux the reaction vigorously, and a total of 40g of ethanol was distilled from the reaction through the Barrett trap. Heating was continued at a gentle reflux (no more ethanol was distilled) for 7 hours. At a reaction time of 2 hours and 4.5 hours, about 65g of the reaction mixture was taken out, stirred with about 4.5g of Amberlyst A21 weakly basic ion exchange resin for about 1 hour, filtered to remove the ion exchange resin, and then dried on a baking tray in a forced air oven at 60°C to constant weight. A sample of the reaction mixture was treated in the same manner at the end of the reaction (7 hours). In this way, three partially hydrolyzed laurate-esterified PVOH polymers with different degrees of hydrolysis were obtained. Their compositions are summarized in Table 8.

[0249] Examples 10 and 11: The intermediate copolymers of Examples 7 and 8 were partially hydrolyzed to obtain PVOH polymers esterified with 2-ethylhexanoic acid and pivalic acid, respectively.

[0250] The precursor polymers in Examples 7 and 8 were partially hydrolyzed following the same general procedure described in Example 9. Unless otherwise stated, 1 The compositions determined by H NMR (400 MHz; DMSO-d6 solvent) are summarized in Table 8 below.

[0251] Table 8

[0252]

[0253]

[0254] *Composition: C- 13 NMR (DMSO-d6 solvent) measurement

[0255] Example 12: Effect of polyvinyl alcohol with internal gamma-lactone (cyclic) functional groups on high humidity curl retention

[0256] Following the general procedure described in Example 6, a series of intermediate copolymers with carboxylic acids pendant on the backbone (precursors of PVOH copolymers modified with internal γ-lactones (cyclic esters)) were prepared by copolymerizing vinyl acetate and crotonic acid in different relative amounts. 13 The compositions of these intermediate copolymers determined by NMR (DMSO-d6 solvent) are summarized in Table 9 below.

[0257] Table 9

[0258]

[0259] Following the same general procedure described in Example 9, the intermediate (precursor) copolymer was partially hydrolyzed. 13 The compositions determined by NMR (DMSO-d6 solvent) are summarized in the following Table 10. It should be noted that under the conditions used to partially hydrolyze the intermediate (precursor) copolymer, most of the carboxylic acid moieties pendant to the intermediate (precursor) copolymer spontaneously formed (cyclic) esters (internal γ-lactones) with the alcohol pendant to the nascent PVOH copolymer; in some cases, a small portion (<40%) of the carboxylic acid moieties pendant to the intermediate (precursor) copolymer did not form (cyclic) esters with the alcohol from the pendant to the nascent PVOH copolymer.

[0260] Table 10

[0261]

[0262] a Intermediate (precursor) polymer: 34

[0263] b Intermediate (precursor) polymer: 35

[0264] c Intermediate (precursor) polymer: 36

[0265] d Intermediate (precursor) polymer: 37.

[0266] Hair spray formulations containing polymers 29, 30, 31 and 32 were prepared as described in Example 3, except that 95% ethanol (5% H2O) was used as the solvent and then compared with similarly formulated Poval TM LM-20+5% H2O (Kuraray) and anhydrous Resyn TM 28-2930 (Nouryon) for comparison. Poval TM LM-20 has been discussed above. TM 28-2930 polymer is a film-forming hair fixative that provides rigidity and flexibility at a low cost in high alcohol hairspray formulations. It also provides strong hold, manageability, shine and adhesion to the hair without flaking.

[0267] Procedure for Determining High Humidity Curl Retention (HHCR)

[0268] The objective performance of the polymers of the present invention was evaluated in terms of High Humidity Curl Retention using the following procedure. The High Humidity Curl Retention of hair shaping compositions comprising the polymers of the present invention was measured. Each test was conducted at 72°F (22°C) and 90% relative humidity for 24 hours. The tests were conducted on 10 inch long x 2 gram European virgin brown hair swatches (9 replicates per hair swatch). The curl retention test lasted a total of 24 hours in a humidity chamber set at 70°F / 90% relative humidity. The curl retention readings were taken and recorded at time intervals of 15, 30, 60, 90 minutes, 2, 3, 4, 5 and 24 hours.

[0269] The hair styling compositions were tested according to the following procedure:

[0270] 1. Wet hair and comb through to remove tangles and squeeze out excess water (run hair between thumb and index finger).

[0271] 2. Apply sample to hair sample, gently "rub into" hair sample and comb through.

[0272] 3. Roll the hair sample onto a 0.5" diameter Teflon mandrel. Carefully remove the rolled hair sample from the mandrel and secure it with two hairpins.

[0273] 4. Place the curls on a tray and dry in the oven overnight.

[0274] 5. Remove the dried curls from the oven and cool to room temperature.

[0275] 6. Hang the curls from the ends of the sample hair on a clear, transparent curl holding board with scales.

[0276] 7. Remove the clip from the curl and gently untwist with a glass rod to ensure you "break" the curl.

[0277] 8. Read the initial curl length and then place the plate and curls into an environmental chamber (70°F, 90% relative humidity).

[0278] 9. Record the curl length at time intervals of 15, 30, 60, 90 minutes, 2, 3, 4, 5 and 24 hours.

[0279] 10. At the end of the test, remove the plates and curlers from the environmental chamber.

[0280] 11. Clean the used hair samples.

[0281] 12. Calculate the Curl Retention % and compare the samples.

[0282] The samples were prepared as follows:

[0283] HHCR was performed in a constant temperature and humidity chamber. The curls were rolled on a mandrel and allowed to dry overnight. The polymer solution (3 wt% polymer using 95% VOC ethanol-water and 40% DME) was then sprayed on the curls and allowed to dry. The curls were then hung on a plate placed in an oven and the percentage of curl loss was tracked over 24 hours.

[0284] The high humidity curl retention performance of hair styling compositions containing the polymers of the present invention according to the examples shown in Tables 11 and 12 below was measured and compared with the results of the tests using Poval TM LM-20 and Resyn TM The same hair styling composition containing 28-2930 polymer was compared.

[0285] Table 11: With Poval TM High humidity curl retention compared to LM-20

[0286]

[0287] These data show that at all times the polymers of the present invention exhibit at least as good a TMLM-20 showed comparable high humidity curl retention. Surprisingly and unexpectedly, all of the inventive samples provided statistically significant (95% confidence) superior high humidity curl retention starting at 1 hour. Surprisingly and unexpectedly, polymers 29 and 30, characterized by the highest levels of crotonic acid tested, began to achieve this statistically significant advantage even earlier.

[0288] Table 12: Resyn TM High humidity curl retention compared to 28-2930

[0289]

[0290] The above data show that Poval TM LM-20 has the same efficacy as Resyn TM 28-2930 showed statistically significantly worse high humidity curl retention than Resyn 28-2930. In contrast, surprisingly and unexpectedly, the inventive polymers showed significantly lower high humidity curl retention than Resyn 28-2930 within the first 4 hours. TM 28-2930 were equivalent, and those polymers with higher crotonic acid content also maintained equivalence for longer periods of time.

[0291] Embodiment 13:

[0292] The polymers according to the present disclosure were formulated with 3% polymer, 40% DME and 5 parts water with the balance being ethanol and tested and compared with Poval TM The results are shown in Table 13 below.

[0293] The test was performed in the same manner as described in Example 5.

[0294] Data analysis / evaluation:

[0295] Samples exhibit this property less frequently: 0 to 1 of the 8 selected experimental samples show statistically significant differences from the reference at the 95% confidence level;

[0296] The samples showed no statistical difference compared with the standard: 2 to 6 out of 8 selected experimental samples showed statistically significant differences at the 95% confidence level;

[0297] The samples showed this performance more often: 7 to 8 out of 8 selected experimental samples showed statistically significant differences from the reference at the 95% confidence level.

[0298] In addition to beading, more performance is expected.

[0299] Table 13. Subjective evaluation of half head vs 3% POVAL TM LM-20 + 5% water (all samples were not neutralized)

[0300] Film-forming polymers Beading luster Stiffness Resilience Networking Feel 29 8 / 8 3 / 8 8 / 8 8 / 8 7 / 8 0 / 8 30 8 / 8 3 / 8 6 / 8 8 / 8 8 / 8 1 / 8 31 2 / 8 4 / 8 4 / 8 6 / 8 4 / 8 3 / 8 32 5 / 8 5 / 8 3 / 8 8 / 8 8 / 8 4 / 8

[0301] The value in each cell indicates the performance of each attribute in the test. TM LM-20 has more properties than the number of selected experimental samples.

[0302] We observed the following trends in the data:

[0303] As the crotonic acid content increases, the degree of pearling is higher;

[0304] As the crotonic acid content increases, hardness increases;

[0305] As the crotonic acid content increases, the sensation worsens;

[0306] Glossiness is effectively independent of crotonic acid content;

[0307] Resilience and web-forming properties - Most of the polymers tested were significantly better than Poval TM LM-20.

[0308] Embodiment 14

[0309] Selected polymer samples having the compositions in the table below were prepared in ethanol solvent and blended with propellants according to the procedure of Example 3 to understand the compatibility with the propellants.

[0310] In the following examples, the propellant was 40% of the total formulation HPC 152A. In each case, the test formulation contained 3% polymer, 5% water, q.s. ethanol and 40% hydrofluorocarbon 152A propellant.

[0311] The desired result is a clear, single-phase and complete solution, which indicates that the formulations are compatible. On the other hand, if the solution is cloudy or opaque or contains precipitates, it indicates that the formulations are at least partially incompatible.

[0312] Table 14

[0313]

[0314] In all cases, the copolymers proved to be compatible with the formulations, resulting in very slightly turbid single-phase aerosols.

[0315] Although the present disclosure has been described in conjunction with the above specific embodiments, many substitutions, modifications and other variations thereof are apparent to those skilled in the art. All such substitutions, modifications and variations are intended to fall within the spirit and scope of the present disclosure.

Claims

1. A hair styling formulation comprising: (a) volatile solvents; and (b) at least one film-forming polymer comprising at least one of: (i) polyvinyl alcohol or (ii) a polyvinyl alcohol ester having ester functionalities in addition to the proprietary acetate, and (i) and (ii) are soluble in a volatile solvent; provided that if the at least one film-forming polymer comprises polyvinyl alcohol, the degree of hydrolysis of the polyvinyl alcohol is less than about 60%.

2. The hair styling formulation according to claim 1, wherein the volatile solvent is an alcohol-based solvent system, wherein the alcohol-based solvent system comprises at least one C 1-6 Straight or branched chain alcohols.

3. The hair styling formulation according to claim 2, wherein the alcohol-based solvent system comprises ethanol.

4. A hair styling formulation according to any preceding claim comprising 0-20% by weight of water.

5. A hair styling formulation according to any preceding claim which is free of water.

6. A hair styling formulation according to claim 5, comprising ethanol but not any other alcohol.

7. A hair styling formulation according to any one of the preceding claims, wherein the at least one film-forming polymer comprises polyvinyl alcohol having a degree of hydrolysis of from about 35% to about 58%.

8. A hair styling formulation according to any one of the preceding claims, wherein the at least one film-forming polymer comprises an ester of polyvinyl alcohol.

9. A hair styling formulation according to any one of the preceding claims, wherein the at least one film-forming polymer comprises a partially hydrolyzed vinyl acetate-crotonic acid copolymer comprising pendant carboxylic acid groups and pendant hydroxyl groups condensed together to form an internal gamma-lactone functionality.

10. The hair styling formulation according to claim 9, wherein the at least one film-forming polymer comprises polyvinyl alcohol derivatized with 10-18 wt% crotonic acid, based on 100 wt% of the at least one film-forming polymer, and the degree of hydrolysis of the polyvinyl alcohol is 35-50%.

11. A hair styling formulation according to any one of the preceding claims which is a sprayable hair styling formulation.

12. The hair styling formulation according to claim 11, further comprising one or more additives selected from hair styling polymers, plasticizers, UV absorbers, dyes, fragrances, preservatives, viscosity modifiers, vitamins, moisturizers, anti-itch and anti-dandruff ingredients.

13. The hair styling formulation according to claim 12, further comprising one or more additives selected from film-forming polymers, plasticizers, UV absorbers, dyes, fragrances, preservatives, viscosity modifiers, vitamins, moisturizers and anti-itch ingredients.

14. A hair fixative formulation according to any preceding claim which is an aerosol formulation and further comprises a propellant.

15. The hair styling formulation according to claim 14, wherein the propellant is dimethyl ether (DME).

16. The hair styling formulation of claim 14, comprising a dual valve bag device comprising an insert containing the hair styling formulation and a propellant surrounding the insert.

17. A method of styling hair comprising spraying the hair with a hair styling formulation according to any preceding claim.

Images