Aerosol dispenser containing a hairspray composition and a nitrogen propellant

Abstract

An aerosol hairspray product having an atomizing device and an environmentally friendly pressurizable container, the container including a container wall enclosing a reservoir for storing a compressed gas propellant and a hairspray composition, wherein the spray characteristics of the product, such as spray rate, median droplet size, and spray diameter, are maintained throughout the life of the product.

Description

[Technical Field]

[0001] An aerosol hairspray product comprising an environmentally friendly pressurized container enclosing a hairspray composition and a reservoir for storing a compressed gas propellant. [Background technology]

[0002] Hair styling products such as hair sprays can be used to hold hair in place, protect hair from moisture, and create volume. Hair sprays are generally packaged in aerosol containers, which contain a release valve that is under pressure and is used to release the pressurized hair spray into the air as a fine mist propelled by a gas propellant. Typically, the propellant is a liquefied hydrocarbon propellant. The advantage of hydrocarbon propellants is that they have sufficient pressure to turn the gas into a liquid within the container. When the hair spray product is dispensed, the product level within the container decreases, and more propellant evaporates into the headspace above the product, maintaining a nearly constant pressure, which results in consistent spray characteristics such as atomization rate and average particle size distribution.

[0003] Although hydrocarbon propellants offer substantial benefits, some consumers would prefer hairspray products in aerosol dispensers with non-hydrocarbon propellants, such as compressed gases, which may include, but are not limited to, compressed air, nitrogen, inert gases, and carbon dioxide. Nitrogen may be particularly desirable because it is non-toxic, non-flammable, relatively low cost, and generally inert.

[0004] However, unlike liquefied hydrocarbons, nitrogen propellants are always in a vapor state, and therefore, it can be difficult to produce consumer-acceptable aerosol hairspray products using nitrogen propellants, because as the product is dispensed, the pressure inside the container decreases, making it difficult to dispense the hairspray composition with a consumer-acceptable particle size distribution and spray rate over the life of the container.As the pressure inside the container decreases, the average particle size distribution increases, and eventually, it releases clumps of hairspray that take too long to dry and can make hair look dull, sloppy, and stiff.Eventually, the pressure can become so low that no product is released at all, even if there is product remaining in the can. Summary of the Invention [Problem to be solved by the invention]

[0005] The relationship between the various mechanical components of a hairspray product (nozzle, valve, valve stem, dip tube, etc.) and the rheological properties of the hairspray composition can also affect product performance, such as clumping, low spray rate, and undesirable spray pattern. Therefore, there is a need to provide a hairspray product in which the mechanical and rheological elements of the hairspray product are tailored to provide adequate product performance.

[0006] In addition to good product performance, many consumers also prefer environmentally friendly product ingredients and packaging. However, traditional hair styling products continue to be made from raw and / or petrochemical-derived materials.

[0007] Therefore, there is a need for a hairspray product and an aerosol dispenser containing a nitrogen gas propellant that have consistent spray characteristics, such as spray rate and average particle size distribution, throughout the life of the container. There is also a need for providing hairspray products in environmentally friendly containers. [Means for solving the problem]

[0008] Disclosed herein is an aerosol hairspray product comprising an environmentally friendly pressurized container containing a compressed gas propellant and a hairspray composition. The hairspray composition comprises a carrier present at 30% to 98.5% and a hair styling polymer present at 5% to 8%. The hairspray product also includes a spray device clamped to the container. The spray device includes a valve assembly and a nozzle. The valve assembly includes a housing having an interior wall defining a valve chamber. The valve chamber includes a liquid inlet in fluid communication with the hairspray composition and a gas inlet in fluid communication with the compressed gas propellant. The spray device also includes a valve stem. The proximal end of the valve stem is received within the valve chamber, and the distal end of the valve stem protrudes through a sealed opening in the valve chamber. The valve stem further includes an outlet flow conduit having an outlet opening at the distal end, a first stem inlet for the liquid, and a second stem inlet for the gas. The housing includes a rim that protrudes inward from the inner wall around the periphery of the valve stem to form a seal around the valve stem. The valve stem is movable between a closed position and an open position. In the closed position, the first stem inlet is at the distal end of the rim and the second stem inlet is at the distal end of the sealed opening in the valve chamber, such that neither the first nor the second stem inlet is in fluid communication with their respective liquid or gas inlets. In the open position, the first stem inlet is at the proximal end of the rim and in fluid communication with the valve chamber liquid inlet, and the second stem inlet is at the proximal end of the sealed opening in the valve chamber and in fluid communication with the valve chamber gas inlet. When in the open position, a bubble-containing flow of the hairspray composition is produced in the outlet flow conduit. [Brief explanation of the drawings]

[0009] [Figure 1] 1 shows an exploded view of the spray device. [Figure 2] 1 shows the spray device clamped to the container. [Figure 3A] 1A and 1B show schematic views of the spray device in closed and open positions, respectively. [Figure 3B] 1A and 1B show schematic views of the spray device in closed and open positions, respectively. [Figure 3C] FIG. 3C is a detailed view of a portion of FIG. 3B showing the relative positions of the annular rim and the stem gas inlet. [Figure 4A] FIG. 10 is a perspective view of the cap portion of the valve housing showing the gas flow conduits. [Figure 4B] FIG. 10 is a perspective view of the cap portion of the valve housing showing the gas flow conduits. [Figure 5A] FIG. 1 is a perspective view of a stem forming part of the spray device. [Figure 5B] FIG. 5B is a cross-sectional view of the stem of FIG. 5A. [Figure 6] 1 is a cross-sectional view of a hairspray product having an actuator. [Figure 7] FIG. 1 is a top view of a hairspray product with an overcap. DETAILED DESCRIPTION OF THE INVENTION

[0010] Many consumers would be interested in aerosol hairspray products with non-hydrocarbon propellants, such as compressed gases, that have excellent spray characteristics that are maintained throughout the life of the product (i.e., from 100% product (full can) to when 25% product remains in the can (end of can)). Compressed gases, including air, nitrogen, carbon dioxide, and other inert gases, may be desirable because they are non-toxic and non-flammable. In some instances, nitrogen gas may be preferred.

[0011] Hydrocarbon propellants are commonly used in aerosol hairspray products. These propellants exist (in the aerosol spray device) in both a gas phase and a liquid phase that is miscible with the liquid hairspray composition. Examples of hydrocarbon propellants can include butane, propane, dimethyl ether, isobutane, 1,1-difluoroethane, or mixtures thereof. Upon release, the gas phase propellant "pushes" the liquid in the container (including the dissolved liquid phase propellant through the nozzle).

[0012] One reason hydrocarbon propellants are popular is that they can produce finer sprays than compressed gas aerosols, because most of the liquefied gas "flash-evaporates" during the release of the liquid from the aerosol sprayer, and this rapid expansion creates a fine spray. It is difficult to obtain these fine sprays using compressed air.

[0013] It has been discovered that aerosol hairspray products with an aerosol dispenser having a valve assembly, as described herein, can be combined with ethanol-based and / or ethanol-free hairspray compositions and compressed air propellants such as nitrogen to maintain consumer-preferred spray characteristics (e.g., spray rate, particle size, spray diameter) throughout the product's life, even when the container contains 25% or less by weight of hairspray composition. By providing an appropriate spray rate and Dv50 droplet size, sufficient hairspray composition can be delivered to hold hair in place, provide desired hold, and / or create volume, while maintaining a non-sticky and natural-looking hair look and feel. Because ethanol-free hairsprays typically contain high levels of water (e.g., 30-60%), as opposed to volatile ethanol, which dissipates quickly, excessive hairspray composition can be delivered to hair, potentially overwetting it. Overwetting hair not only takes longer to dry (which is undesirable), but the hairspray composition can disrupt the hair's internal ionic interactions, causing it to become loose and lose its desired style. Dispensing problems can be exacerbated as propellant is released from the can throughout the life of the product.

[0014] The hairspray products described herein are aerosol hairspray products and do not include mousse products or any pump spray products. The aerosol hairspray products may include ethanol-based or ethanol-free (e.g., water-based) hairspray compositions.

[0015] Table 1 below shows the desired spray characteristics for ethanol-based and ethanol-free hairspray products. In particular, these characteristics are desirable during the initial spray when the container is full and when 25% or less of the hairspray composition remains in the container. Thus, the spray characteristics in Table 1, collectively or individually, should vary by no more than 30% (e.g., no more than 25%, 20%, 15%, or even 10%) between the initial / full container measurement and when 25% of the product remains. In some embodiments, it may be desirable for the spray droplet size to vary by no more than 30 μm (e.g., no more than 25 μm, 20 μm, 15 μm, or even 10 μm). The spray characteristics shown in Table 1 can be determined according to the respective test methods described in more detail below.

[0016] [Table 1]

[0017] "About" modifies a particular value by indicating a range of ±20% or less (eg, ±15% or less, 10% or less, or 5% or less) of the stated value.

[0018] "Hair" means hair on the head and scalp of a human, more preferably including scalp hair, facial hair and body hair. "Hair shaft" means an individual strand of hair and may be used interchangeably with the term "hair".

[0019] "Product life" means the time from when the container contains 100% of the hairspray composition originally placed in the container to when it contains 25% or less of the hairspray composition originally placed in the container.

[0020] "Molecular weight" or "M.Wt." refers to weight average molecular weight, unless otherwise specified. Molecular weight may be determined according to gel permeation chromatography (GPC), an industry standard method.

[0021] As used herein, "substantially free" means about 2% or less (e.g., 1% or less, 0.5% or less, or 0.1% or less) of the listed component. "Free" means an undetectable amount of the listed component or components.

[0022] "Water-soluble" refers to any material that is sufficiently water-soluble to form a single-phase aqueous solution to the naked eye at a concentration of 0.1% by weight of the material in water at 25°C. To achieve water solubility, it may be necessary to adjust the pH of the mixture or completely neutralize the mixture after adding the material to water. These methods are known, for example, in the water-soluble hair styling polymer application industry, and are typically indicated with the material sample provided. Water solubility is typically measured by the following protocol: 0.1% by weight of the material is added to distilled water at 25°C, and a pH adjuster / neutralizer is added as needed. This is vigorously stirred for 30 minutes with a magnetic stirrer set at 600 rpm. The solution is then allowed to settle for 1 hour, and the number of phases is observed with the naked eye. For example, if a solid material can be seen in an otherwise single-phase solution, it is considered to be two-phase.

[0023] Unless otherwise specified, all percentages are by weight of the total composition. All ratios are by weight unless specifically stated otherwise. All ranges are inclusive and combinable. Significant figures do not represent limitations on the indicated amounts or on the precision of the measurements. Unless specifically indicated otherwise, all quantities are understood to be modified by the word "about."

[0024] Unless otherwise indicated, all measurements are understood to be made at 25°C and ambient conditions, by which "ambient conditions" is meant conditions of 1 atmosphere pressure and 50% relative humidity. All such weights as they pertain to listed ingredients are based on the active level and do not include carriers or by-products that may be included in commercially available materials, unless otherwise specified.

[0025] It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification includes every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.

[0026] pressurizable container The aerosol hairspray product includes a pressurizable container. The type of container is not particularly limited and may include a can, a bottle, or other suitable container type known for use with hairspray products. The container may be formed from any suitable material, including metal, plastic, pulp, glass, and combinations thereof. The pressure within the reservoir can be measured with a pressure gauge (GCAS#60001439). The internal compressed gas (e.g., nitrogen) pressure can be determined based on DOT 2Q regulations for aerosol cans. In some embodiments, the pressure within the container can be 100-159 PSIG (e.g., 110-150 PSIG, 120-140 PSIG, or even 130-135 PSIG) at 70°F.

[0027] spray device Figure 1 is an exploded view of an exemplary spray device for dispensing a hairspray composition, and Figure 2 shows the spray device clamped to a container. The aerosol hairspray product includes a spray device attached to a container 118 for dispensing a hairspray composition from a reservoir 204 of the container 118. The spray device includes a valve assembly 205 and a nozzle. The valve assembly 205 includes a valve housing 109, a stem 107, and a spring 108. The housing 109 includes a lower cup portion 306 and an upper cap portion 308. In this example, the valve assembly 205 is in liquid communication with the hairspray composition in the reservoir 204.

[0028] The valve housing 109 can have a valve tail 115 that has a bore for receiving a dip tube 116 that can be in fluid communication with the hairspray in the reservoir 204. The bore in the valve tail 115 (that receives the dip tube 116) can have an inner diameter of 0.762 mm to 1.778 mm (e.g., 0.889 mm to 1.651 mm, 1.016 mm to 1.524 mm, 1.143 mm to 1.397 mm, or 0.889 mm to 1.143 mm).

[0029] Stem 107 has stem bore 105 which serves as an outlet for the contents of the container (i.e., hairspray composition and propellant). Stem bore 105 can have an inner diameter of 0.127 mm to 0.635 mm (e.g., 0.203 mm to 0.340 mm, or 0.279 mm to 0.356 mm).

[0030] The valve assembly 205 may include a stem gasket 104 that seals against a seat for the stem gasket on the stem 107 and optionally covers a side hole in the stem that leads to the stem bore 105. In some embodiments, the stem gasket 104 may be pre-assembled onto the stem 107. The stem 107 and valve housing 109 may be made of polyphenylene sulfone.

[0031] The spring 108 may be pre-attached to the base of the stem molding. The spring may be made of a material (e.g., plastic or stainless steel) that is resistant to corrosion or oxidation. The mounting cup 102 may be pre-fitted with a cup gasket 103 to form an airtight seal against the container curl 117 when the assembled valve is fastened to the container. The above-described subassemblies are crimped together using a base crimping tool to create the fully assembled valve assembly 205. The stem gasket 104 is compressed by approximately 50% of its thickness during the crimping procedure, and the base of the mounting cup 102 is deformed during crimping to engage and hold the surface of the valve housing 109. A dip tube 116 (e.g., made of polyethylene) is pressed into sealing engagement with the tail 115 to complete the valve assembly 205.

[0032] The hairspray composition and compressed gas propellant are placed into the container 118 before clamping the valve assembly 205 and dip tube 116 onto the container curl 117 using conventional clamping equipment to form an airtight seal between the valve assembly 205 and the container 118. The container 118 is then pressurized to a desired operating pressure by supplying gas through the stem bore 105. When the stem 107 is depressed more than about 1 mm by application of an external force (e.g., to an actuator coupled to the stem), the stem gasket 104 deforms away from the side bore in the area of ​​the stem gasket seat 106, opening a path between the container 118 and the external environment. When the external force is released, the spring 108 returns the stem to its fully closed position.

[0033] As shown in FIG. 2, the valve assembly 205 is fastened to the top of the container 118 after it has been filled with the hairspray composition. The stem hole 105 is the outlet for the stem 107. The container wall 201 defines a reservoir 204 for storing the hairspray composition and compressed gas propellant. Actuation of the valve assembly 205 is achieved by application of an external force to depress the engaged stem 107, thereby releasing the hairspray composition and propellant into the external environment through a nozzle (not shown). The valve assembly 205 includes a housing 109 that mounts the dip tube 116 and allows propellant gas from the reservoir 204 to flow into the stream of hairspray composition ascending the dip tube 116 upon opening of the valve assembly 205.

[0034] Figures 3A and 3B show another example of a valve assembly. Figure 3C is an enlarged view of element C in Figure 3B. The valve assembly 200 shown in Figures 3A and 3B can be incorporated into the aerosol spray device of Figures 1 and 2. The valve assembly 200 includes a housing 202 having an interior wall defining a valve chamber 304 and a valve stem 220. The housing 202 is formed of two portions: a lower cup portion 206 and an upper cap portion 208. The valve assembly 200 can be crimped into place on top of a container (e.g., container 118 of Figures 1 and 2), with the distal end of the valve stem 220 protruding from the top of the container for connection to an actuator.

[0035] The cup portion 206 has a lower wall 210 with an opening 212 therethrough. A tubular spigot 214 extends from the lower wall 210. A dip tube (not shown), typically by an enlarged lower end, can be connected to the tubular spigot 214, the dip tube extending to the base of the container into which the valve assembly 200 is fitted. It will be appreciated that the lower region of the container into which the valve assembly 200 is fitted is in fluid communication with the valve chamber 304 via the dip tube, the spigot 214, and the opening 212 (which provides a liquid inlet for the valve chamber).

[0036] 3C, stem gas inlet 286 is moved to a position slightly offset distally from rim 226, i.e., so that the central axis 287 of stem gas inlet 286 is directly above the centerline 227 of rim 226. This allows gas from valve chamber gas inlet 234a to enter stem gas inlet 286, as well as a small amount of liquid from valve chamber liquid inlet 212.

[0037] In some embodiments, the stem gas inlet 286 is stepped, with the outer portion 286a (opening to the stem surface 272) having a larger diameter than the inner portion 286b (opening to the outlet conduit 280). Alternatively, the stem gas inlet 286 may have a conical cross-section tapering from the larger outer portion to the smaller inner portion. In the configuration of the valve assembly 200, the total cross-sectional area of ​​the gas bleed passages 240, 238, 234, 286 should not be so large that excess gas is bled into the outlet conduit 280, causing the container to run out of pressurized propellant before all of the hairspray composition is released. The total cross-sectional area of ​​the gas bleed inlet passages may be equivalent to the total cross-sectional area of ​​a single circular cross-section inlet having a diameter of 0.15 to 0.8 mm.

[0038] Figure 4A shows an example of the cap portion 208 from Figures 3A and 3B. As shown in Figure 4A, the cap portion 208 has a generally cylindrical inner wall 224 with a rim 226 protruding inwardly at its upper end. The cap portion's lower end 228 has a narrower outer diameter so as to fit with an interference fit inside the cup portion 206. At the upper end of the cap portion 208, an annular rim 230, together with an upper surface 232, defines a ledge upon which an annular sealing gasket 260 rests.

[0039] 4B shows a plurality of radial grooves 234 defined between corresponding radial ribs 236 on upper surface 232. Inner ends 234a of grooves 234 open above rim 226 and into the upper end of the valve chamber. Outer ends 234b of grooves 234 open into a circumferential groove 238 that surrounds upper surface 232 just inside rim 230. The lower and side surfaces of each groove 234, 238 are formed by the cup portion itself, while the upper surface is formed by the lower surface 262 of gasket 260.

[0040] A conduit 240 is formed through the cap portion 208, with its upper end opening into the circumferential groove 238 via a hole 242 and its lower end exiting the side of the cup portion 206 via an outer hole 244. It will be appreciated that the headspace of a container into which the valve assembly 200 is fitted is in communication with the valve chamber 304 via the conduit 240, the circumferential groove 238, and the radial groove 234 (which together provide a gas inlet for the valve chamber).

[0041] Valve stem 220 is generally cylindrical with an outer surface 272 having a diameter equal to the inner diameter of rim 226 such that rim 226 forms a seal around the circumference of valve stem 220. A proximal end 274 of the valve stem is received within valve chamber 304, and a distal end 276 protrudes through the center 264 of annular sealing gasket 260, which is dimensioned to seal against outer surface 272 of valve stem 220. A lower surface 262 of gasket 260 defines an upper portion of valve chamber 304.

[0042] 5A and 5B show an exemplary valve stem 320 for use in the present hairspray product. The valve stem 320 includes an outlet flow conduit 280 having a hole 282 at its distal end 276 and, more proximally, at least one first stem inlet 284 for liquid and at least one second stem inlet 286 for gas. As shown, there is a single stem inlet 284 for liquid and a single stem inlet 286 for gas, positioned approximately in the center of the valve stem, with the gas inlet 286 slightly distal to the liquid inlet 284. It will be understood that alternative configurations are envisioned. For example, there may be multiple liquid inlets 284 and / or multiple gas inlets 286. The inlets 284, 286 may be positioned more proximal or distal than shown, and the axial separation between the respective liquid and gas inlets may be greater than shown.

[0043] 5A and 5B, an enlarged shoulder 290 protrudes radially from the cylindrical valve stem 220 toward the proximal end 274 of the valve stem 220. The diameter of the shoulder 290 is substantially equal to the diameter of the valve chamber 304. A bore 292 extends centrally from the proximal end face 275 of the valve stem 220 to the shoulder 290. Four conduits 294 extend radially outward within the shoulder 290 from the center where they open into the bore 292. At their outer ends, the radial conduits 294 open into respective axial grooves 296 in the outer surface of the shoulder 290 that extend parallel to the bore 292 and the outlet conduit 280.

[0044] As shown in the drawings, valve stem 220 is biased upwardly of the valve assembly (and therefore the aerosol device) by a coil spring 222. The lower end of coil spring 222 is positioned around opening 212 in cup portion 206 of housing 202. In the closed position of the valve, as shown in FIG. 3A , shoulder 290 abuts rim 226 under the force of spring 222, blocking the flow path defined by bore 292, radial conduit 294, and axial groove 296 when the top of axial groove 296 abuts the underside of rim 226. Furthermore, liquid inlet 284 is distal to sealing gasket 260. Therefore, there is no fluid communication between valve chamber liquid inlet 212 and outlet conduit 280. Furthermore, because gas inlet 286 is distal to sealing gasket 260, which seals against valve stem outer surface 272, there is also no fluid communication between valve chamber gas inlet 234a and outlet conduit 280.

[0045] The abutment of shoulder 290 against edge 226 acts as an upper stop, preventing valve stem 220 from being pushed further out of valve housing 202 .

[0046] 3B, when the valve stem is moved to the open position, the valve stem liquid inlet 284 moves below (i.e., proximal to) the rim 226 to fluidly communicate with the valve chamber liquid inlet 212 via a flow path defined by the bore 292, the radial conduit 294, and the axial groove 296 through the valve stem shoulder 290. The stem gas inlet 286 also moves below (i.e., proximal to) the sealing gasket 260 to a position at the upper end of the valve chamber 304 where it fluidly communicates with the valve chamber gas inlet 234a. At least a portion of the stem gas inlet 286 must open to the upper portion of the valve chamber 304 (i.e., above the rim 226). The abutment of the bottom surface 275 of the valve stem 220 against the lower wall 210 of the cup portion 206 defines a lower stop.

[0047] Thus, to activate the device, the actuator cap is depressed, causing the valve stem 220 to move downward from the closed position to the open position against the bias of the spring 222. As a result, the liquid stem inlet 284 and the gas stem inlet 286 are displaced past the gasket 260 and are in fluid communication with the liquid hairspray composition from the container 2 and the compressed gas from the headspace, respectively.

[0048] The compressed gas may enter the outlet conduit 280 by passing through the holes 244 in the exterior surface of the cap portion 208 , the conduit 240 , the holes 242 , the circumferential groove 238 and the radial groove 234 and through the stem gas inlet 286 .

[0049] The hairspray composition may then flow upward along the dip tube 20 through the inlet 212, holes 292, radial conduits 294, and axial grooves 296 into the upper portion of the valve chamber 304. The hairspray composition introduced into the top of the valve chamber 304 enters the flow conduit 280 via the stem liquid inlet 284, where it mixes with compressed gas bled through the stem gas inlet 286. A bubble-laden stream of uniform bubbles having similar diameters (Dv50) and without significant coalescence or stratification is formed in the outlet flow conduit 280. The bubble stream may flow, preferably undisturbed, through the stem bore and actuator.

[0050] A non-limiting example of a spray device suitable for use with the present hairspray products is the Ecovalve® device offered by Salvalco of York, U.K. Such a valve is disclosed in U.S. Patent No. 10,071,849.

[0051] Actuator FIG. 6 shows an exemplary hairspray product 600 including a container 601, a spray device 605, and a spray actuator 610. As shown in FIG. 6, a container wall 608 encloses a reservoir 618 containing a compressed gas propellant 620 and a hairspray composition 606. The spray device 605 can be one of the spray devices described herein. A dip tube 619 extends into the reservoir 618 and provides fluid communication between the reservoir and a valve assembly of the spray device 605. The valve assembly and valve stem of the spray device 605 are configured to provide fluid communication between the dip tube and the spray actuator 610. When sufficient force is applied to the spray actuator 610, the hairspray composition 606 travels upward through the dip tube aperture 615 and the dip tube 619 and exits through the actuator exit aperture 612.

[0052] In some embodiments, it may be desirable to use a button-type actuator to provide a short flow path for the hairspray composition to travel through the actuator. Additionally or alternatively, it may be desirable to provide a spray-through cap type actuator to eliminate the need for a separate overcap. While the type of actuator is not particularly limited, it may be important to configure the actuator to work with (e.g., seat on) a vertically configured valve assembly and / or valve stem, as shown in Figures 1 and 2. In this configuration, the valve is actuated by applying a downwardly directed actuation force, rather than a sidewardly directed force as used, for example, in a tilted valve configuration.

[0053] In some instances, it may be desirable to configure the valve stem and actuator to have a ratio of valve stem orifice area to actuator outlet orifice area of ​​less than 10 (e.g., less than 9, 8, 7, or even less than 5). If an actuator outlet insert is optionally used, the ratio of valve stem orifice area to actuator insert area can be less than 10. It has been found that there can be a significant difference in the ability of the valve assembly and actuator nozzle to spray the hairspray composition. Without being bound by any theory, it is believed that keeping the actuator outlet orifice area closer to the valve stem orifice area avoids rushing the hairspray composition through the actuator, which can become "bottlenecked" at the outlet. If the hairspray composition becomes bottlenecked at the outlet orifice, the hairspray composition loses the energy necessary for atomization. The valve stem orifice refers to the orifice through which the hairspray composition passes. Some spray devices may have a second orifice through which only compressed gas passes.

[0054] Overcap 7 shows an example of a hairspray product 700 having an overcap 750 to prevent inadvertent release of the hairspray composition, provide tamper resistance or function as a tamper-evident seal, protect the actuator from damage, and / or harmonize the aesthetic appeal of the hairspray product. The overcap 750 covers the top of the hairspray product 700 (e.g., the spray actuator 710, valve stem, and valve assembly). The overcap 750 may be releasably attached to the container 701 or container neck 705 by an outwardly protruding ridge that surrounds the interior lower edge of the overcap and interacts with a bead or seam that surrounds the top of the container 701. When the overcap 750 is placed on top of the container 701, downward pressure can be applied to the overcap 750, causing the ridge to overcome the outer edge of the seam and latch under a ledge defined by the underside of the seam. The overcap 750 may be transparent, translucent, opaque, colored, or colorless, as desired. As shown in Figure 7, the overcap 750 is colorless and transparent so that the actuator exit aperture 712 is generally visible to the user.

[0055] The container, sprayer, actuator, and / or overcap may be made from any suitable material desired. Particularly suitable materials for making these features include recyclable, recycled, and / or sustainably sourced materials. For example, one or more of the container, sprayer, actuator, and / or overcap may be constructed from materials that include 10% to 100% (e.g., 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or even 100%) recyclable, recycled, or sustainably sourced materials. Some non-limiting examples of recyclable materials include metal, glass, plastic, and paper. Some non-limiting examples of recycled materials include plastics made from post-consumer recycled (PCR) resin, recycled aluminum, and recycled glass. Some non-limiting examples of sustainably sourced container materials include bio-based plastics, which are polymeric materials made from renewable carbon feedstocks such as plants (e.g., soybeans, corn, or sugarcane). Bio-based plastics suitable for use herein have a modern carbon percentage value of at least 10% (e.g., 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or even 100%) according to ASTM D6566-10 Method B. Further examples and descriptions of bio-based plastics and modern carbon percentages can be found in U.S. Patent Nos. 11,433,158 and 10,166,312.

[0056] Hairspray composition and compressed gas propellant The aerosol hairspray products herein comprise a hairspray composition and a compressed gas propellant stored in a reservoir of a container. The compressed gas propellant and hairspray composition may be stored in the same compartment or in separate compartments. The reservoir may contain 50% to 65% by volume (e.g., 55% to 60% by volume) of the hairspray composition. The reservoir may contain 35% to 70% by volume (e.g., 40% to 60% by volume, 45% to 55% by volume, or 45% to 50% by volume) of the propellant. As used herein, unless otherwise specified, the specifications for the hairspray composition and propellant refer to the composition prior to filling into the can.

[0057] The hairspray composition is dispensed as multiple droplets having an average particle size distribution (Dv50) of 40 microns to 100 microns (e.g., 40 microns to 90 microns, 60 microns to 80 microns) as determined by the Particle Size Distribution Test described below. The spray delivery rate of the ethanol-based hairspray is: The spray delivery rate of the ethanol-free hairspray can be 0.2 g / sec to 0.6 g / sec (e.g., 0.25 g / sec to 0.55 g / sec or 0.3 g / sec to 0.5 g / sec) as determined by the Delivery Rate Test Method.

[0058] The kinematic viscosity of the propellant-free, ethanol-free hairspray compositions herein can be from 0.5 cSt to 5.5 cSt (e.g., from 1 to 5 cSt, from 1.25 to 4.5 cSt, from 1.5 to 4.0 cSt, from 1.75 to 3.5 cSt, from 1.8 to 3 cSt, or even from 2.0 to 2.5 cSt). The kinematic viscosity of the propellant-free, ethanol-based hairspray compositions herein can be from 1 to 20 cSt (e.g., from 3 to 18 cSt, or from 5 to 15 cSt).

[0059] The hairspray composition may comprise 1.5% to 10% by weight of the hairspray composition of hair styling polymer. The amount of hair styling polymer is important to balance hold performance and wettability on the hair. The amount of hair styling polymer promotes hold performance but is limited by the maximum sprayable viscosity. The hairspray composition may comprise 2% to 8% by weight of the hairspray composition of hair styling polymer (e.g., 3% to 7% or 3.5% to 6% by weight). These amounts may be the total amount of hair styling polymer in the hairspray composition.

[0060] The hair styling polymer or mixture of hair styling polymers can be a water-soluble hair styling polymer and / or an ethanol / alcohol-soluble hair styling polymer that can provide a viscosity of 6 cSt or less when measured before adding the propellant.The hair spray composition containing the soluble hair styling polymer is then pressurized in a canister using a gas propellant.In some examples, the user may shake the canister before dispensing to mix the hair spray composition with the hair styling polymer and the propellant.

[0061] The hair styling polymer may be any water-soluble or alcohol-soluble film-forming polymer or mixture of such polymers, including homopolymers or copolymers of natural or synthetic origin having functionality that renders the polymer water-soluble, such as hydroxyl, amine, amide, or carboxyl groups.

[0062] Soluble hair styling polymers can form clear or translucent stable solutions when diluted within the claimed range. Depending on the type of specific polymer, it may be necessary to adjust the pH of the formulation or neutralize the formulation after adding the polymer to water to achieve water solubility. Hair styling polymers can be classified into two categories: (fully) synthetic polymers and natural products, and their chemically modified derivatives, and further into three major headings: naturally occurring polymers, semi-synthetic polymers, and fully synthetic polymers. Hair styling polymers can be selected from the group consisting of cationic hair styling polymers, anionic hair styling polymers, nonionic hair styling polymers, and amphoteric hair styling polymers. The molecular weight of the hair styling polymer should be such that the propellant-free hair spray composition meets the specified viscosity requirement range. Hair styling polymers can be linear or branched.

[0063] The hair styling polymer may be a cationic hair styling polymer, an anionic hair styling polymer, a nonionic hair styling polymer, an amphoteric hair styling polymer, or a mixture thereof. The cationic hair styling polymer may be selected from the group consisting of quaternized acrylates or methacrylates, quaternary homopolymers or copolymers of vinylimidazole, homopolymers or copolymers containing quaternary dimethyallylammonium chloride, non-cellulosic cationic polysaccharides, cationic cellulose derivatives, chitosan and its derivatives, and mixtures thereof.

[0064] The hair styling polymer may be an anionic hair styling polymer or a mixture of anionic hair styling polymers. The anionic hair styling polymer may be selected from those containing groups derived from carboxylic or sulfonic acids. The copolymers containing acid units are generally used in a partially or fully neutralized form, more preferably in a fully neutralized form.Anionic hair styling polymers comprise at least one monomer derived from (a) a carboxylic acid, such as acrylic acid, or methacrylic acid, or crotonic acid, or a salt thereof, or a C4-C8 monounsaturated polycarboxylic acid or anhydride (e.g., maleic acid, fumaric acid, itaconic acid, and their anhydrides), and (b) an ester of acrylic acid and / or methacrylic acid (e.g., C1-C4 alkyl acrylates, methyl acrylate, ethyl acrylate, tert-butyl acrylate, and their methacrylate derivatives); acrylate esters grafted to polyalkylene glycols, such as polyethylene glycol (e.g., poly(ethylene glycol) acrylate); hydroxyester acrylates (e.g., hydroxyethyl methacrylate); acrylamides, methacrylamides, which may or may not be substituted on the nitrogen with lower alkyl groups (C1-C4); N-alkylated acrylamides (e.g., N-tert-butyl acrylamide); hydroxyalkylated acrylamides; aminoalkylated acrylamides (e.g., hydroxyethyl methacrylate); For example, the anionic hair styling polymer may comprise one or more monomers selected from the group consisting of dimethylaminopropyl methacrylamide; alkylacrylamides (e.g., tert-butylamino-ethyl methacrylate, dimethylaminoethyl methacrylate); alkyl ether acrylates (e.g., 2-ethoxyethyl acrylate); monoethylenic monomers such as ethylene, styrene, etc.; vinyl esters (e.g., vinyl acetate or vinyl propionate, vinyl tert-butyl-benzoate); vinyl esters grafted to polyalkylene glycols such as polyethylene glycol; vinyl ethers; vinyl halides; phenylvinyl derivatives; allyl esters or methallyl esters; vinyl lactams such as vinyl pyrrolidone or vinyl caprolactam; alkyl maleimides, hydroxyalkyl maleimides (e.g., ethyl / ethanol maleimide). If present, the anhydride functional groups of these polymers may optionally be monoesterified or monoamidated. The anionic hair styling polymer may comprise a monomer derived from a sulfonic acid.The anionic polymers may comprise (a) at least one monomer derived from a sulfonic acid, such as vinyl sulfonic acid, styrene sulfonic acid, naphthalene sulfonic acid, acryl alkyl sulfonic acid, acrylamido alkyl sulfonic acid, or a salt thereof, and (b) an ester of acrylic acid and / or methacrylic acid (e.g., C1-C4 alkyl acrylate, methyl acrylate, ethyl acrylate, tert-butyl acrylate, and their methacrylate derivatives); an acrylate ester grafted to a polyalkylene glycol, such as polyethylene glycol (e.g., poly(ethylene glycol) acrylate); a hydroxy ester acrylate (e.g., hydroxyethyl methacrylate); an acrylamide, methacrylamide, which may or may not be substituted on the nitrogen with a lower alkyl group (C1-C4); N-alkylated acrylamide (e.g., N-tert butyl acrylamide); a hydroxyalkylated acrylamide; an amino alkylated The polymer may comprise one or more monomers selected from the group consisting of acrylamides (e.g., dimethylaminopropyl methacrylamide); alkylacrylamines (e.g., tert-butylamino-ethyl methacrylate, dimethylaminoethyl methacrylate); alkyl ether acrylates (e.g., 2-ethoxyethyl acrylate); monoethylenic monomers such as ethylene, styrene, etc.; vinyl esters (e.g., vinyl acetate or vinyl propionate, vinyl tert-butyl-benzoate); vinyl esters grafted to polyalkylene glycols such as polyethylene glycol; vinyl ethers; vinyl halides; phenylvinyl derivatives; allyl esters or methallyl esters; vinyl lactams such as vinyl pyrrolidone or vinyl caprolactam; alkyl maleimides, hydroxyalkyl maleimides (e.g., ethyl / ethanol maleimide). If present, the anhydride functionality of these polymers may optionally be monoesterified or monoamidated.

[0065] Anionic hair styling polymers include copolymers derived from acrylic acid, for example acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers such as those sold by BASF® as Ultrahold 8; octylacrylamide / acrylate / butylaminoethyl / methacrylate copolymers such as those sold by Akzo Nobel® as Amphomer®; methacrylic acid / ester acrylate / ester methacrylate such as those sold by Akzo Nobel® as Balance® CR; octylacrylamide / acrylates / butylaminoethyl methacrylate copolymers such as those sold by Nobel® as Balance® 47; methacrylic acid / hydroxyethyl methacrylate / various acrylate esters such as those known as Acudyne™ 1000 sold by Dow® Chemical; acrylates / hydroxyethyl methacrylates such as those sold by Dow® Chemical as Acudyne™ 180; methacrylic acid / hydroxyethyl methacrylate / various acrylate esters such as those sold by Dow® Chemical as Acudyne™ DHR; n-butyl methacrylate / methacrylic acid / ethyl acrylate copolymers such as those sold by DSM® as Tilamar® Fix A-1000; copolymers derived from crotonic acid, e.g., Akzo It may be selected from vinyl acetate / vinyl tertbutyl benzoate / crotonic acid terpolymers and crotonic acid / vinyl acetate / vinyl neodecanoate terpolymers, such as those sold as Resyn™ 28-2930 by Nobel®.Hair styling polymers derived from sulfonic acids can include sodium polystyrene sulfonate sold by Ashland™ as Flexan® 130; sulfopolyesters (also known as polyester-5) such as those sold by Eastman as Eastman AQ 48; sulfopolyesters (also known as polyester-5) such as those sold by Eastman as Eastman AQ S38; sulfopolyesters (also known as polyester-5) such as those sold by Eastman as Eastman AQ 55.Anionic hair styling polymers include copolymers derived from acrylic acid, such as acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers (such as those sold by BASF® as Ultrahold® 8); octylacrylamide / acrylate / butylaminoethyl / methacrylate copolymers, such as those sold as Amphomer; methacrylic acid / ester acrylate / ester methacrylate, such as those sold by Akzo Nobel® as Balance® CR; octylacrylamide / acrylates / butylaminoethyl methacrylate copolymers such as those sold by Nobel® as Balance® 47; methacrylic acid / hydroxyethyl methacrylate / various acrylate esters such as those known as Acudyne® 1000 sold by Dow® Chemical; acrylates / hydroxyethyl methacrylates such as those sold by Dow® Chemical as Acudyne® 180; methacrylic acid / hydroxyethyl methacrylate / various acrylate esters such as those sold by Dow® Chemical as Acudyne® DHR; n-butyl methacrylate / methacrylic acid / ethyl acrylate copolymers such as those sold by DSM® as Tilamar® Fix A-1000; copolymers derived from crotonic acid, for example, Akzo It may be selected from vinyl acetate / vinyl tertbutyl benzoate / crotonic acid terpolymers and crotonic acid / vinyl acetate / vinyl neodecanoate terpolymers, such as those sold as Resyn™ 282930 by Nobel®.Hair styling polymers derived from styrene sulfonic acid may include sodium polystyrene sulfonate sold by Ashland™ as Flexan® 130; sulfopolyesters (also known as polyester-5) such as those sold by Eastman as Eastman AQ 48; sulfopolyesters (also known as polyester-5) such as those sold by Eastman as Eastman AQ S38; sulfopolyesters (also known as polyester-5) such as those sold by Eastman as Eastman AQ 55.

[0066] The hair styling polymer can be an anionic hair styling polymer selected from copolymers derived from acrylic acid, such as acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymer; octylacrylamide / acrylate / butylaminoethyl / methacrylate copolymer; methacrylic acid / ester acrylate / ester methacrylate; octylacrylamide / acrylate / butylaminoethyl methacrylate copolymer; methacrylic acid / hydroxyethyl methacrylate / various acrylate esters; acrylate / hydroxyethyl methacrylate; methacrylic acid / hydroxyethyl methacrylate / various acrylate esters; n-butyl methacrylate / methacrylic acid / ethyl acrylate copolymer; copolymers derived from crotonic acid, such as vinyl acetate / vinyl tertbutyl benzoate / crotonic acid terpolymer; and crotonic acid / vinyl acetate / vinyl neododecanoate terpolymer; and mixtures thereof.

[0067] The hair styling polymer may be a polyurethane dispersed or dissolved in a solvent (for example, water, ethanol, or another alcohol). Such polyurethanes may include adipic acid, 1-6 hexanediol, neopentyl glycol, isophorone diisocyanate, isophorone diamine, N-(2-aminoethyl)-3-aminoethanesulfonic acid, sodium salts such as those sold by Bayer® under the name Baycusan® C1008 (also known as polyurethane-48); and isophorone diisocyanate, dimethylolpropionic acid, 4,4-isopropylidenediphenol / propylene oxide / ethylene oxide (also known as polyurethane-14), such as those sold as a mixture under the name DynamX® H20 by Akzo Nobel®.

[0068] The hair styling polymer can be a nonionic hair styling polymer or a mixture of nonionic hair styling polymers such as Luviskol VA 64 from BASF and PVP K30 from Ashland. The nonionic hair styling polymer can be a water-soluble natural polymer such as hydroxyalkyl cellulose (e.g., hydroxymethyl-, hydroxyethyl-, or hydroxypropyl cellulose) and starch.

[0069] The hair styling polymer can be an amphoteric hair styling polymer or a mixture of amphoteric hair styling polymers such as Diaformer® Z 731 N from Clariant®.

[0070] Some non-limiting examples of hair styling polymers can be found in co-pending U.S. Patent Application No. 17 / 874,600 (Brown et al., filed July 27, 2022).

[0071] The hairspray composition can be substantially free of water-insoluble and / or water-immiscible polymers and / or alcohol-insoluble polymers. High molecular weight (e.g., greater than 200,000 g / mol) polymers can be avoided or used only at very low levels so that the hairspray composition does not exceed the desired viscosity. The hairspray composition can be substantially free of polymers containing at least two long hydrophobic grafts (e.g., linear fatty chains of 10 or more carbons). Such polymers with such grafts can provide associative interactions in the hairspray composition, which can increase the viscosity without contributing to the strength of the film delivered to the hair.

[0072] Ethanol-based hairspray Ethanol-based hairspray compositions may include an alcohol solvent present at 50% to 99.9% alcohol by weight of the hairspray composition (e.g., 60% to 97%, 70% to 95%, or 80% to 95% ethanol, isopropanol). Some non-limiting examples of alcohol solvents include ethanol, n-propanol, isopropanol, and combinations thereof. The hairspray polymer used in the composition should generally, but not necessarily, be soluble in the alcohol solvent.

[0073] The hairspray composition may further comprise other additional solvents, including water, provided that such additional solvents are chemically and physically compatible with the components of the composition and do not substantially and unduly impair product performance. Some non-limiting formulation examples and additional ingredients that can be used in ethanol-based hairsprays can be found in WO 1998 / 05379.

[0074] Ethanol-free hairspray Some consumers may prefer alcohol / ethanol-free or very low alcohol / ethanol hairsprays because they may have a purer fragrance (considering the absence of alcohol odor), less observed hair drying, and reduced brittleness on hair, and consumers may perceive them as more environmentally friendly and / or healthier to use. The ethanol-free hairspray compositions herein contain less than 2% alcohol / ethanol by weight of the hairspray composition (e.g., less than 1%, less than 0.5%, or even less than 0.25% alcohol / ethanol). In some embodiments, the hairspray composition contains 0% ethanol or alcohol. The hairspray polymers used in the composition should generally, but need not necessarily, be water-soluble.

[0075] The hairspray composition may comprise 30% to 99% water (e.g., 60% to 98% water, 70% to 97% water, 80% to 96%, or 85% to 96% water) by weight of the hairspray composition. Water may provide a solvent for the hair styling polymer and other ingredients in the hairspray composition. It may be desirable to use ingredients for the hairspray composition that are water-soluble.

[0076] compressed gas propellant Compressed gas propellants can include gases such as nitrogen, air, carbon dioxide, nitrous oxide, and other inert gases.

[0077] Optional Ingredients The hairspray composition may contain a panthenol compound and / or a silicone compound. The panthenol compound may be selected from the group consisting of panthenol, pantothenic acid derivatives, and mixtures thereof. The panthenol compound may be selected from the group consisting of D-panthenol ([R]-2,4-dihydroxy-N-[3-15-(hydroxypropyl)]-3,3-dimethylbutamide), D / L-panthenol, pantothenic acid and its salts, panthenyl triacetate, royal jelly, pantethine, pantotheine, panthenyl ethyl ether, pangamic acid, pantoyl lactose, vitamin B complex, and mixtures thereof. The panthenol compound may be useful in terms of providing the benefits of excellent hair appearance and feel. The hairspray composition may contain 0.1% to 0.6% by weight (e.g., 0.1% to 0.3% by weight) of the panthenol compound by weight of the hairspray composition. The hairspray composition may contain a silicone compound. Silicones can be useful because they give hair a smooth feel and also provide shine. The silicone compound can be a dimethicone compound. The silicone compound can be PEG dimethicone, for example, PEG-12 dimethicone.

[0078] The hairspray composition may further comprise a surfactant present at 1% or less by weight of the hairspray composition (e.g., 0.6% or less, 0.4% or less, or 0.3% or less). The surfactant may be selected from the group consisting of cationic surfactants, nonionic surfactants, anionic surfactants, and mixtures thereof.

[0079] The hairspray composition may contain a neutralizing agent. Suitable neutralizing agents may include potassium hydroxide, sodium hydroxide, triisopropanolamine (TIPA), 2-aminobutanol, 2-aminomethylpropanol (AMP), aminoethylpropanediol, dimethylstearamine (Armeen 18 D), sodium silicate, tetrahydroxypropylethylenediamine (Neutrol® TE), ammonia (NH3), triethanolamine, trimethylamine (Tris AminoUltra), and aminomethylpropanediol (AMPD). The neutralizing agent may be 2-aminobutanol, ammonia, or 2-aminomethylpropanol.

[0080] The hairspray composition may include at least one preservative, which may be present in an amount of less than 1.5%, or from 0% to 1%, or from 0.01% to 1% by weight of the hairspray composition.

[0081] The hairspray composition may further include a perfume or fragrance. It may be desirable to limit the amount of perfume or fragrance to 0.5% by weight (e.g., 0% to 0.4% or 0.03% to 0.3% by weight) of the hairspray composition.

[0082] The hairspray composition may include vitamins, amino acids, and preservatives.

[0083] Additional information regarding hairspray compositions and aerosol spray dispensers can be found in US Pat. Nos. 9,986,809, 10,131,488, and 10,426,979.

[0084] Test Method spray speed Spray rate can be determined according to ASTM D 3069-94, "Standard Test Method for Delivery Rate of Aerosol Products." In this test, the delivery rate of a product is determined by measuring the mass lost over a given period of time. This correlates to the amount of material expelled through the valve and actuator combination in a given time. In this case, cans are tested at room temperature (21°C) with actuation times ranging from 2 to 10 seconds in duration. The delivery rate is then determined by the following formula: Spray rate (g / s) = mass loss (g) / operating time (s)

[0085] If the spray rate is greater than 0.45 g / s, the drying time on the hair may be too long and unsatisfactory for consumers. This is specific to the ethanol-free hairsprays described herein, compared to conventional ethanol-based hairsprays, which typically have a delivery rate of 0.55 g / s to 0.85 g / s. The delivery rate can typically be adjusted by changing the pressure in the container (increased pressure correlates with faster delivery rates) and / or the nozzle holes, valve holes, and dip tube inner diameter of the spray device.

[0086] Particle size distribution (Dv50) Dv50 is the largest particle size that less than 50% of the sample volume has. Dv50 is sometimes called the median particle size by volume. Dv90 is the largest particle size that less than 90% of the sample volume has.

[0087] Droplet size throughout the life of the can can be important because it affects the dry feel, dry time, and hold performance of a hairspray. Smaller droplets dry faster. More small droplets feel less wet than fewer large droplets. For hold, more small droplets provide greater surface area coverage and even coating of hair fusing points. If droplets are too small, they do not bridge and hold hairs together at the fusing point. This can be important for alcohol-free hairsprays, which do not have the advantage of the fast evaporative drying of ethanol formulations. Ethanol hairsprays have a much wider working droplet size range, e.g., 30-130 μm. Ethanol-free hairsprays with a Dv50 below 40 μm may have hold issues. Ethanol-free hairsprays with a Dv50 above 80 μm may have significantly slower dry times and an initial wet hair feel. Dv90, although much smaller, represents the largest droplet size in a spray. Dv90 values ​​above 180 μm, which grow up to 400 μm over the life of the can, can result in a visually uneven-looking spray with larger, sputtering droplets. These large droplets make the spray less misty and uniform. This can lead to clumping of hair where the large droplets land. These clumps can make the final finished hair result feel unnatural and difficult to run your fingers or brush through.

[0088] The mean particle size distribution (Dv50) can be important in terms of the drying time of the dispensed composition, which must be acceptable to consumers.In fact, a small mean particle size distribution (Dv50) can be useful in that the more particles there are, the higher the surface area to volume ratio, which means faster drying time.On the other hand, if the mean particle size distribution (Dv50) is too low, it may mean that not enough hair styling polymer is provided to hair to provide spot fusion.

[0089] Particle size distribution is measured using a Malvern Spraytec™ instrument. The Malvern Spraytec™ instrument uses the technique of laser diffraction to measure the size of spray particles. The intensity of light scattered as a laser beam passes through the spray is measured. This data is then analyzed to calculate the size of the particle that produced the scattering pattern. The Malvern Spraytec™ 2000 is used according to the manufacturer's instructions. The test sample has a temperature of 20°C to 22°C.

[0090] Spray Diameter The spray pattern over the life of the can can be important because it affects the dry feel, drying time, and hold performance of the hairspray. A smaller spray diameter, or a more localized spray, can make hair feel wetter, take longer to dry, and provide more hold due to more and larger fusion points between hairs. A larger spray diameter, or a more misty spray, can result in areas where the droplets do not bridge and hold the hairs together at the fusion points, which can be undesirable. Considering the typical size of a human head and the distance the container can be comfortably held from the head, a spray diameter of 2 inches to 6 inches is desirable.

[0091] The spray diameter is measured using thermal paper mounted on a rigid test stand. The test sample is equilibrated to 20-24°C. The test can is positioned perpendicular to the paper at ±10° and 6 inches away. After spraying is complete, the test paper is scanned and analyzed with imaging software. The outer diameter of the spray is then measured. diameter=2 * It is calculated as ("area" / 3.141593)^0.5. where "area" is the cell location in the imaging software including the outer diameter area

[0092] viscosity Kinematic viscosity can be measured with an Ubbelohde tube viscometer. Kinematic viscosity is a measure of a fluid's resistance to flow and is equal to its absolute viscosity divided by its density. The SI unit of kinematic viscosity is m 2 ·s-1 The physical unit of kinematic viscosity in cgs (centimeters per gram per second) is the stoke (St), which can be expressed in centistokes (cSt). 1 cSt = 1 mm 2 ·s -1 =10 -6 m 2 ·s -1 Water at 20°C has a kinematic viscosity of 1 cSt. The Ubbelohde tube is a viscometer for measuring the kinematic viscosity of transparent Newtonian liquids by the suspended level principle, as described in ASTM D 445 and D 446, and ISO 3104 and 3105. For Ubbelohde tube measurements, the results are independent of temperature; for other kinematic viscometers, temperatures outside the specified test range may affect the results. Herein, measurements were performed at a temperature of 20°C ±0.1°C. This method can be used to measure viscosities from 0.6 cSt to 100 cSt. See ASTM D 445 for instructions for using an Ubbelohde viscometer. For viscosities from 0.6 to 3 cSt at 20°C ±0.1°C, use Ubbelohde tube size 0. For viscosities from 2 to 10 cSt at 20°C ±0.1°C, use Ubbelohde tube size 1. ASTM D445 is the "Standard Test Method for Kinematic Viscosity of Transparent and Opaque Liquids." ASTM D446 is the "Specification and Operating Instructions for Glass Capillary Kinematic Viscometers." [Example]

[0093] Aerosol dispensers were filled with either ethanol-free hairspray (i.e., water-based hairspray) or ethanol-based hairspray and 60% nitrogen propellant. Each experimental aerosol dispenser had an aerosol assembly containing one of four Salvalco Eco-Valves®, identified by the color of the insert (pink, green, red, blue, clear, or yellow). Each Salvalco Eco-Valve® appears to have a different configuration, which may include varying the thickness and diameter of the exit hole and / or varying the number, height, and width of the passages tangential to the hole. Without being limited by theory, it is believed that different atomizer configurations affect spray characteristics.

[0094] The spray characteristics (e.g., spray rate (g / sec) and droplet size (μm)) of an aerosol dispenser with Salvalco Eco-Valves® were compared to a control (Pantene® Pro-V Airspray Flexible Hold Hairspray) throughout the life of the dispenser. Cans were filled to 40-60% nitrogen at 135 PSIG. Cans were tested from 100% product (can full) to when 25% of the product remained in the can. An initial value was obtained when the container was full (i.e., when 100% of the composition was present), and a final value was obtained when approximately 25% of the hairspray composition remained. Test results for ethanol-based hairspray compositions are summarized in Table 2A. Test results for ethanol-free hairspray compositions are summarized in Table 2B.

[0095] [Table 2]

[0096] [Table 3]

[0097] In the examples in Tables 3 and 4 below, aerosol containers were filled with nitrogen gas and hair spray compositions. The aerosol containers contained a Salavaco Eco-Valve with a green insert. The hair spray in Table 3 contains twice the concentration of actives and a higher viscosity compared to the paired examples in Table 4.

[0098] The examples in Tables 3 and 4 were tested to determine whether they met the properties set forth in Table 1 herein. Spray properties were maintained if the initial spray rate and Dv50 changed by less than 10% and 20 microns, respectively, compared to the spray rate and Dv50 when 25% of the hairspray composition remained in the container.

[0099] [Table 4]

[0100] None of the Examples tested in Table 3 met all of the success criteria outlined herein. For the ethanol-based hairsprays combined with 40% and 60% nitrogen propellant (Examples JJ in Table 7 below), the spray rate was acceptable to consumers, but the Dv50 average particle size was too large to result in a consumer-acceptable hairspray product.

[0101] For the ethanol-free hairspray (Example AA in Table 5 below), spray rates were acceptable to consumers for the examples containing 40% and 60% nitrogen propellant. However, the particle size for these examples fell outside the success criteria. For the 40% nitrogen propellant, the particle size was too large, and for the 60% nitrogen propellant, it was too large at both test points. For the 20% nitrogen propellant, the initial particle size was acceptable to consumers, but when 25% of the composition remained, the average particle size was too large and not acceptable to consumers.

[0102] Examples AA and JJ tested in Table 3 had similar active concentrations to current products using hydrocarbon propellants. Because nitrogen propellants do not liquefy like hydrocarbon propellants, it was found that lower concentrations of hairspray compositions could be used while still providing excellent styling results. Furthermore, since the Dv50 particle size at 40% nitrogen loading was too high for both the ethanol-based and ethanol-free hairsprays, and the Dv50 particle size at 60% was closer to the preferred range for both the initial and remaining 25% of the product, it was decided that 60% nitrogen would be used in the lower concentration formulation.

[0103] [Table 5]

[0104] Examples J (Table 7 below) and A (Table 5 below) tested in Table 4 have half the activity level compared to Examples JJ and AA tested in Table 3. Both the ethanol-based hairspray (Example J) and the ethanol-free hairspray (Example A) have consumer-acceptable spray rates and Dv50 average particle sizes upon initial spray and when 25% of the hairspray composition remains in the can.

[0105] The examples in Tables 5, 6, and 7 can be made using conventional methods of making hairspray compositions and products.

[0106] [Table 6] KEY: 1 =Balance® CR polymer; 2 =DynamX H20; 3 =Acudyne 1000; 4 =Amphomer; 5 =Luviskol VA64; 6 =Luviquat FC550; 7 =Hydagen® HCMF; 8 =Celquat L-200.

[0107] [Table 7] KEY: 1 =Balance® CR polymer; 2 =DynamX H20; 3 =Acudyne 1000; 4 =Amphomer; 5 =Luviskol VA64; 6 =Luviquat FC550; 7 =Hydagen® HCMF; 8 =Celquat L-200.

[0108] [Table 8] KEY: 1 =Resyn 28-2930; 2 =Amphomer; 3 =Balance 47;

[0109] Dimensions and values ​​disclosed herein should not be understood as being strictly limited to the exact numerical values ​​recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."

[0110] All documents cited herein, including any cross-referenced or related patents or patent applications, and any patent applications or patents to which this application claims priority or benefit, are incorporated herein by reference in their entirety, unless expressly stated to the contrary. The citation of any document shall not be deemed to be prior art to any invention disclosed or claimed herein, or to teach, suggest, or disclose any such invention, either alone or in combination with any other reference or references. Furthermore, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall control.

[0111] While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

[0112] Examples / Combinations 1. An aerosol hair spray product comprising: a) a pressurizable container comprising a container wall enclosing a reservoir for storing a compressed gas propellant and a hairspray composition, the hairspray composition comprising: i) 30% to 98.5% by weight of the hairspray composition of a solvent; ii) a pressurizable container containing 1.5% to 8% by weight of the hair spray composition of a hair styling polymer, wherein the hair styling polymer is soluble in a solvent; b) a spray device clamped onto the container for dispensing the hairspray composition from a reservoir of the container, the spray device comprising: i) a valve assembly including a housing having an interior wall defining a valve chamber, the valve chamber including a liquid inlet in fluid communication with a hairspray composition in a reservoir and a gas inlet in fluid communication with a compressed gas propellant in the reservoir; ii) a valve stem including a proximal end and a distal end, the proximal end being received within the valve chamber and the distal end protruding through a sealed opening in the valve chamber, the valve stem further including an outlet flow conduit having an outlet opening at the distal end, a first stem inlet for receiving a liquid, and a second stem inlet for receiving a gas; the housing includes a lip around the periphery of the valve stem to form a seal around the periphery of the valve stem; a valve chamber liquid inlet at the proximal end of the rim and a valve chamber gas inlet at the distal end of the rim; The valve stem is a closed position, wherein the first stem inlet is at a distal end of the rim and the second stem inlet is at a distal end of the sealed opening of the valve chamber, such that the first stem inlet is not in fluid communication with the valve chamber liquid inlet and the second stem inlet is not in fluid communication with the valve chamber gas inlet; an open position, wherein a first stem inlet is at a proximal end of the rim and in fluid communication with the valve chamber liquid inlet, and a second stem inlet is at a proximal end of the sealed opening of the valve chamber and at least partially distal to the rim and in fluid communication with the valve chamber gas inlet, such that a bubble-containing flow is generated in the outlet flow conduit; a spray device that is movable between c) an actuator coupled to the spray device; d) An aerosol hair spray product comprising an actuator and an overcap that covers the top of the container. 2. The aerosol hair spray product of paragraph 1, wherein the actuator includes an outlet orifice having an outlet orifice area, and the valve stem includes an orifice having a valve stem orifice area, and wherein the ratio of the valve stem orifice area to the actuator outlet orifice area is less than 10, preferably less than 8, and more preferably less than 5. 3. The aerosol hairspray product of paragraph 1 or 2, wherein the valve assembly is vertically oriented and the actuator is seated in the vertically oriented valve system. 4. The aerosol hairspray product of any preceding paragraph, wherein the solvent is water and the hairspray composition is alcohol-free. 5. The aerosol hairspray product of any preceding paragraph in which the compressed gas propellant includes nitrogen. 6. The aerosol hairspray product of any preceding paragraph, further comprising 5.5% to 8% of an anionic hair styling polymer comprising a hair styling polymer derived from acrylic acid, preferably selected from acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymer, acrylate / hydroxyester acrylate copolymer of butyl acrylate, methyl methacrylate, methacrylic acid, ethyl acrylate, and hydroxyethyl methacrylate, polyurethane-14 / AMP-acrylate copolymer blend, octylacrylamide / acrylate / butylaminoethyl / methacrylate copolymer, methacrylic acid / ester acrylate / ester methacrylate copolymer, acrylate / hydroxyethyl methacrylate copolymer, methacrylic acid / hydroxyethyl methacrylate / acrylate ester copolymer; N-butyl methacrylate / methacrylic acid / ethyl acrylate copolymer, and combinations thereof. 7. The aerosol hair spray product of any preceding paragraph, further comprising 5.5% to 8% of an anionic hair styling polymer, including anionic hair styling polymers derived from crotonic acid, preferably vinyl acetate / vinyl tertbutyl benzoate / crotonic acid terpolymer, crotonic acid / vinyl acetate / vinyl neododecanoate terpolymer, and combinations thereof. 8. The aerosol hair spray product of any preceding paragraph, wherein the hair spray product has a spray rate of 0.3 g / sec to 1.0 g / sec, preferably 0.3 g / sec to 0.8 g / sec, and more preferably 0.3 to 0.6 g / sec, according to a spray rate test. 9. The aerosol hairspray product of paragraph 8, wherein the spray rate of the hairspray product changes by no more than 30%, preferably no more than 20%, and more preferably no more than 10% when the container contains 100% of the hairspray composition compared to when the container contains 25% of the hairspray composition. 10. The aerosol hair spray product of any preceding paragraph, wherein the hair spray product has a Dv50 of 40 μm to 90 μm according to a particle size distribution test. 11. The aerosol hair spray product of paragraph 10, wherein the Dv50 changes by no more than 20 μm when the container contains 100% of the hair spray composition compared to when the container contains 25% of the hair spray composition. 12. The aerosol hairspray product of paragraph 1, wherein the hairspray product has a spray diameter of between 5 cm and 15.25 cm. 13. The aerosol hairspray product of paragraph 12, wherein the spray diameter changes by no more than 30%, preferably no more than 20%, and more preferably no more than 10% when the container contains 100% of the hairspray composition and when the container contains 25% of the hairspray composition. 14. The aerosol hairspray product of any preceding paragraph, wherein at least one of the container, the spraying device, the actuator, and the overcap contains 10% or more of a material selected from recycled materials, bio-based plastics, and combinations thereof. 15. A method of styling hair, comprising: a), providing an aerosol hair spray product of any preceding paragraph; b) applying the hairspray composition to the target portion of the hair where the styling effect is desired.

Claims

1. 1. An aerosol hair spray product comprising: a) a pressurizable container comprising a container wall enclosing a reservoir for storing a compressed gas propellant and a hairspray composition, said hairspray composition comprising: i) 30% to 98.5% by weight of the hairspray composition of a solvent; ii) a pressurizable container containing 1.5% to 8% by weight of the hairspray composition of a hair styling polymer, wherein the hair styling polymer is soluble in the solvent; b) a spray device clamped onto the container for dispensing the hairspray composition from the reservoir of the container, the spray device comprising: i) a valve assembly including a housing having an interior wall defining a valve chamber, the valve chamber including a liquid inlet in fluid communication with the hairspray composition in the reservoir and a gas inlet in fluid communication with the compressed gas propellant in the reservoir; ii) a valve stem including a proximal end and a distal end, the proximal end being received within the valve chamber and the distal end projecting through a sealed opening in the valve chamber, the valve stem further including an outlet flow conduit having an outlet opening at the distal end, a first stem inlet for receiving a liquid, and a second stem inlet for receiving a gas; the housing includes a lip around the periphery of the valve stem to form a seal around the periphery of the valve stem; the valve chamber liquid inlet is at a proximal end of the rim and the valve chamber gas inlet is at a distal end of the rim; The valve stem is a closed position, wherein the first stem inlet is at a distal end of the rim and the second stem inlet is at a distal end of the sealed opening of the valve chamber, such that the first stem inlet is not in fluid communication with the valve chamber liquid inlet and the second stem inlet is not in fluid communication with the valve chamber gas inlet; an open position, wherein the first stem inlet is proximal to the rim and in fluid communication with the valve chamber liquid inlet, and the second stem inlet is proximal to the sealed opening of the valve chamber and at least partially distal to the rim and in fluid communication with the valve chamber gas inlet, such that a bubble-laden flow is generated in the outlet flow conduit; a spray device that is movable between c) an actuator coupled to the spray device; d) An aerosol hairspray product comprising the actuator and an overcap covering the top of the container.

2. 10. The aerosol hairspray product of claim 1, wherein the actuator comprises an outlet orifice having an outlet orifice area, the valve stem comprises an orifice having a valve stem orifice area, and the ratio of the valve stem orifice area to the actuator outlet orifice area is less than 10, preferably less than 8, and more preferably less than 5.

3. 3. The aerosol hairspray product of claim 1 or 2, wherein the valve assembly is vertically oriented and the actuator is seated in the vertically oriented valve system.

4. 10. The aerosol hairspray product of any one of the preceding claims, wherein the solvent is water and the hairspray composition is alcohol-free.

5. 10. The aerosol hairspray product of any one of the preceding claims, wherein the compressed gas propellant comprises nitrogen.

6. 10. The aerosol hairspray product of any one of the preceding claims, further comprising 5.5% to 8% of an anionic hair styling polymer comprising a hair styling polymer derived from acrylic acid, preferably selected from acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymer, acrylate / hydroxyester acrylate copolymer of butyl acrylate, methyl methacrylate, methacrylic acid, ethyl acrylate and hydroxyethyl methacrylate, polyurethane-14 / AMP-acrylate copolymer blend, octylacrylamide / acrylate / butylaminoethyl / methacrylate copolymer, methacrylic acid / ester acrylate / ester methacrylate copolymer, acrylate / hydroxyethyl methacrylate copolymer, methacrylic acid / hydroxyethyl methacrylate / acrylate ester copolymer; N-butyl methacrylate / methacrylic acid / ethyl acrylate copolymer and combinations thereof.

7. 10. The aerosol hair spray product of any one of the preceding claims, further comprising 5.5% to 8% of an anionic hair styling polymer comprising an anionic hair styling polymer derived from crotonic acid, preferably vinyl acetate / vinyl tertbutyl benzoate / crotonic acid terpolymer, crotonic acid / vinyl acetate / vinyl neododecanoate terpolymer, and combinations thereof.

8. 10. The aerosol hairspray product of any one of the preceding claims, wherein the hairspray product has a spray rate of from 0.3 g / sec to 1.0 g / sec, preferably from 0.3 g / sec to 0.8 g / sec, more preferably from 0.3 to 0.6 g / sec, according to the Spray Rate Test.

9. 9. The aerosol hairspray product of claim 8, wherein the spray rate of the hairspray product changes by no more than 30%, preferably no more than 20%, and more preferably no more than 10% when the container contains 100% of the hairspray composition compared to when the container contains 25% of the hairspray composition.

10. 10. The aerosol hair spray product of any one of the preceding claims, wherein the hair spray product has a Dv50 according to a particle size distribution test of from 40 μm to 90 μm.

11. 11. The aerosol hairspray product of claim 10, wherein the Dv50 changes by no more than 20 μm when the container contains 100% of the hairspray composition and when the container contains 25% of the hairspray composition.

12. 10. The aerosol hairspray product of claim 1, wherein the hairspray product has a spray diameter of from 5 cm to 15.25 cm.

13. 13. The aerosol hairspray product of claim 12, wherein the spray diameter changes by no more than 30%, preferably no more than 20%, and more preferably no more than 10% when the container contains 100% of the hairspray composition and when the container contains 25% of the hairspray composition.

14. 10. The aerosol hairspray product of any one of the preceding claims, wherein at least one of the container, the spraying device, the actuator, and the overcap comprises 10% or more of a material selected from recycled materials, bio-based plastics, and combinations thereof.

15. 1. A method of styling hair, comprising: a) providing an aerosol hair spray product according to any one of the preceding claims; b) applying the hairspray composition to the target portion of the hair where the styling effect is desired.

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