Aerosol dispenser containing hair spray composition and nitrogen propellant

Abstract

An aerosol hair spray product having a spray device and an environmentally friendly pressurizable container. The container includes a container wall that encloses a reservoir for storing a compressed gas propellant and a hair spray composition. Spray characteristics of the product, including spray rate, median droplet size, and spray diameter, are maintained throughout the life of the product.

Description

Technical Field

[0001] An aerosol hair spray product includes an environmentally friendly pressurized container enclosing a reservoir for storing a hair spray composition and a compressed gas propellant. Background Art

[0002] Hair styling products such as hair spray can be used to hold hair in place, protect hair from moisture, and create volume. Hair spray is typically packaged in an aerosol container that is under pressure and includes a release valve for emitting 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 there is enough pressure inside the container to convert the gas into a liquid. As the hair spray product is dispensed, the product level in the container decreases, and more propellant evaporates into the headspace above the product, thereby maintaining a roughly constant pressure. This, in turn, produces consistent spray characteristics, such as spray rate and average particle size distribution.

[0003] While hydrocarbon propellants provide significant benefits, some consumers prefer hair spray 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, it can be difficult to manufacture an aerosol hair spray product that is acceptable to consumers using nitrogen propellants because, unlike liquefied hydrocarbons, nitrogen propellants are always in a vapor state, and therefore the pressure in the container decreases as the product is dispensed, making it difficult to dispense the hair spray composition with a particle size distribution and spray rate acceptable to consumers over the life of the container. As the pressure in the container drops, the average particle size distribution increases, eventually releasing a mass of hair spray that takes too long to dry and can make hair look dull, limp, and stiff. Ultimately, the pressure can be so low that no product is released even if there is product left in the can.

[0005] The relationship between the various mechanical components of a hair spray product (nozzle, valve, stem, dip tube, etc.) and the rheological properties of the hair spray composition can also affect product performance, including clumping, slow spray rates, and undesirable spray patterns. Therefore, it is desirable to provide a hair spray product in which the mechanical and rheological elements of the hair spray product are tailored to provide appropriate product performance.

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

[0007] Therefore, there is a need for an aerosol dispenser containing a hair spray product and a nitrogen propellant that has consistent spray characteristics, such as spray rate and average particle size distribution, over the life of the container.There is also a need to provide the hair spray product in an environmentally friendly container. Summary of the Invention

[0008] Disclosed herein is an aerosol hair spray product comprising an environmentally friendly pressurized container containing a compressed gas propellant and a hair spray composition. The hair spray composition comprises 30% to 98.5% of a carrier and 5% to 8% of a hair styling polymer. The hair spray product also includes a spray device riveted to the container. The spray device includes a valve assembly and a nozzle. The valve assembly includes a housing having an inner wall defining a valve chamber. The valve chamber includes a liquid inlet in fluid communication with the hair spray composition and a gas inlet in fluid communication with the compressed gas propellant. The spray device also includes a valve stem. A proximal end of the valve stem is received in the valve chamber, and a distal end of the valve stem protrudes through a sealed opening in the valve chamber. The valve stem also includes an outlet flow conduit having an outlet orifice at its distal end, a first stem inlet for liquid, and a second stem inlet for gas. The housing includes a lip projecting inwardly 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 distal to the lip and the second stem inlet is distal to the sealed opening in the valve chamber, such that neither the first stem inlet nor the second stem inlet is in fluid communication with its corresponding liquid inlet or gas inlet. In the open position, the first stem inlet is proximate the lip and in fluid communication with the valve chamber liquid inlet, and the second stem inlet is proximate the sealed opening in the valve chamber and in fluid communication with the valve chamber gas inlet. When in the open position, a gas-laden flow of the hair spray composition is generated in the outlet flow conduit. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] Figure 1 An exploded view of the spray device is shown.

[0010] Figure 2 Shown is a spray device riveted to a container.

[0011] Figure 3A and Figure 3B The spray device is shown schematically in a respective closed and open position.

[0012] Figure 3C yes Figure 3B Detailed view of a portion of the rod showing the relative positions of the annular lip and the rod gas inlet.

[0013] Figure 4A and Figure 4B is a perspective view of the cover portion of the valve housing showing the gas flow conduit.

[0014] Figure 5A is a perspective view of a wand forming part of the spray device.

[0015] Figure 5B It passes through Figure 5A The cross section of the rod.

[0016] Figure 6 is a cross-sectional view of a hair spray product having an actuator

[0017] Figure 7 A plan view of a hair spray product having a top cover. DETAILED DESCRIPTION

[0018] Many consumers would be interested in aerosol hair spray 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 may be preferred.

[0019] Hydrocarbon propellants are commonly used in aerosol hair spray products. These propellants exist in both a gaseous and liquid phases (in aerosol spray devices) that are miscible with the liquid hair spray composition. Examples of hydrocarbon propellants may include butane, propane, dimethyl ether, isobutane, 1,1-difluoroethane, or mixtures thereof. Upon discharge, the gaseous propellant "propels" the liquid in the container (including the dissolved liquid propellant) through the nozzle.

[0020] One reason hydrocarbon propellants are popular is because they are able to produce finer sprays than compressed gas aerosols because during discharge of the liquid from the aerosol spray device, most of the liquefied gas "flashes" and this rapid expansion produces a fine spray. These fine sprays are difficult to obtain using compressed air.

[0021] It has been discovered that aerosol hair spray products having an aerosol dispenser with a valve assembly, as described herein, in combination with ethanol-based and / or ethanol-free hair spray compositions and a compressed air propellant, such as nitrogen, can exhibit consumer-preferred spray characteristics (such as spray rate, particle size, and spray diameter) throughout the product's life, up to the point where the container contains 25% or less by weight of the hair spray composition. Providing an appropriate spray rate and Dv50 droplet size delivers enough hair spray composition to hold the hair in place, provide the desired hold, and / or create volume, while also providing a non-sticky and natural hair look and feel. Because ethanol-free hair sprays typically contain a high content of water (e.g., 30%-60%), as opposed to the volatile ethanol that flashes off, too much hair spray composition can be delivered to the hair, causing it to become over-wet. Over-wet hair not only takes longer to dry (which is undesirable), but the hair spray composition can also disrupt the hair's internal ionic interactions, causing it to loosen and lose its desired style. Dispensing issues can be exacerbated as the propellant drains from the canister over the product's life.

[0022] The hair spray products described herein are aerosol hair spray products and do not include mousse products or any pump spray products. Aerosol hair spray products may include ethanol-based hair spray compositions or non-ethanol-containing (eg, water-based) hair spray compositions.

[0023] Table 1 below shows the desired spray characteristics for ethanol-based and ethanol-free hair spray products. Specifically, these characteristics are desired upon initial spraying, both when the container is full and when 25% or less of the hair spray composition remains in the container. Thus, the spray characteristics in Table 1 should collectively or individually 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 aspects, 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 their respective test methods, described in more detail below.

[0024] Table 1: Spray characteristics

[0025]

[0026] "About" modifies a particular value by referring to a range of plus or minus 20% or less (eg, plus or minus 15% or less, 10% or less, or even 5% or less) of the stated value.

[0027] "Hair" means mammalian hair, including scalp hair, facial hair, and body hair, more preferably hair on the human head and scalp. "Hair shaft" refers to an individual hair strand and is used interchangeably with the term "hair."

[0028] "Life of the product" means the time from when the container contains 100% of the hair spray composition initially placed in the container to when the container contains 25% or less of the hair spray composition initially placed in the container.

[0029] Unless otherwise indicated, "molecular weight" or "M.Wt." refers to weight average molecular weight. Molecular weight can be determined according to the industry standard method of gel permeation chromatography ("GPC").

[0030] "Substantially free" means about 2% or less (eg, 1% or less, 0.5% or less, or 0.1% or less) of the recited ingredient. "Free" means no detectable amount of the recited ingredient or substance.

[0031] "Water-soluble" means that the material is sufficiently soluble in water to form a single-phase solution in water at a concentration of 0.1% by weight of the material at 25°C to the naked eye. It may be necessary to adjust the pH of the mixture or to fully neutralize the mixture after the material is added to the water to achieve water solubility. These methods are known, for example, in the water-soluble hair styling polymer application industry and are generally guided by the use of supplied material samples. 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 the pH adjusted / neutralized as necessary. This is stirred vigorously for 30 minutes on a magnetic stirrer set at 600 rpm. The solution is then allowed to settle for 1 hour and the number of phases observed by the naked eye. For example, if any solid material can be seen in an otherwise single-phase solution, then this is considered to be two-phase.

[0032] Unless otherwise indicated, all percentages are by weight of the total composition. Unless otherwise indicated, all ratios are by weight. All ranges are inclusive and combinable. The number of significant figures does not express a limitation on the amount shown nor on the accuracy of the measurements. All numerical values ​​are understood to be modified by the word "about" unless otherwise indicated.

[0033] Unless otherwise specified, all measurements are understood to be at 25° C. and ambient conditions, wherein “ambient conditions” means conditions at one atmosphere of pressure and 50% relative humidity. Unless otherwise specified, 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.

[0034] 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 will include 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 falling within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.

[0035] Pressurized container

[0036] Aerosol hair spray products include pressurized containers. The type of container is not particularly limited and may include cans, bottles, or other suitable container types known for use with hair spray products. The container may be formed of any suitable material, including metal, plastic, paper pulp, glass, and combinations thereof. The pressure within the reservoir may be measured using a pressure gauge (GCAS#60001439). Internal compressed gas (e.g., nitrogen) pressure may be determined based on DOT 2Q regulations for aerosol cans. In some embodiments, the pressure within the container may be 100 PSIG to 159 PSIG (e.g., 110 PSIG to 150 PSIG, 120 PSIG to 140 PSIG, or even 130 PSIG to 135 PSIG) at 70°F.

[0037] Spray device

[0038] Figure 1 is an exploded view of an exemplary spray device for dispensing a hair spray composition, and Figure 2 A spray device is shown riveted to a container. The aerosol hair spray product includes a spray device attached to container 118 for dispensing the hair spray composition from reservoir 204 of container 118. The spray device includes a valve assembly 205 and a nozzle. Valve assembly 205 includes valve housing 109, stem 107, and spring 108. Housing 109 includes a lower cup portion 306 and an upper cover portion 308. In this example, valve assembly 205 is in fluid communication with the hair spray composition in reservoir 204.

[0039] The valve housing 109 can have a valve tail piece 115, and wherein the valve tail piece 115 has an orifice that receives a dip tube 116 that can be in fluid communication with the hair spray in the reservoir 204. The valve tail piece 115 orifice (which 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).

[0040] The stem 107 has a stem orifice 105 that serves as an outlet for the container contents (ie, the hair spray composition and the propellant). The stem orifice 105 may have an inner diameter of 0.127 mm to 0.635 mm (eg, 0.203 mm to 0.340 mm, or 0.279 mm to 0.356 mm).

[0041] The valve assembly 205 can include a stem washer 104 that seals against a stem washer seat on the stem 107 and optionally covers a side hole in the stem that leads to the stem aperture 105. In some embodiments, the stem washer 104 can be preassembled to the stem 107. The stem 107 and the valve housing 109 can be made of polyphenylene sulfone.

[0042] The spring 108 can be pre-assembled to the base of the stem molding. The spring can be made of a material that is resistant to corrosion or oxidation (e.g., plastic or stainless steel). The mounting cup 102 can be pre-assembled with the cup gasket 103 to form an airtight seal against the container bead 117 when the assembled valve is riveted to the container. The above subassemblies are crimped together using a base crimping tool to produce the fully assembled valve assembly 205. The stem gasket 104 is compressed approximately 50% in thickness by the crimping process, and the base of the mounting cup 102 is deformed during crimping to engage and retain the surface of the valve housing 109. The dip tube 116 (e.g., made of polyethylene) is pushed into sealing engagement with the tailpiece 115 to complete the valve assembly 205.

[0043] The hair spray composition and compressed gas propellant are placed in the container 118 before the valve assembly 205 and the dip tube 116 are riveted to the container bead 117 using conventional riveting equipment to form an airtight seal between the valve assembly 205 and the container 118. The container 118 is then pressurized to the desired operating pressure by inflating through the stem orifice 105. When the stem 107 is depressed by applying an external force (e.g., to an actuator coupled to the stem) exceeding about 1 mm, the stem washer 104 deforms away from the side hole in the area of ​​the stem washer seat 106, thereby opening a path between the container 118 and the external environment. When the external force is released, the spring 108 returns the valve stem to its fully closed position.

[0044] like Figure 2As shown, after being filled with the hair spray composition, the valve assembly 205 is riveted to the top of the container 118. The stem orifice 105 is the outlet for the stem 107. The container wall 201 defines a reservoir 204 for storing the hair spray composition and a compressed gas propellant. Actuation of the valve assembly 205 is achieved by applying an external force to depress the engaged stem 107, thereby releasing the hair spray 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 the propellant gas from the reservoir 204 to enter the flow of hair spray composition, which rises along the dip tube 116 when the valve assembly 205 is opened.

[0045] Figure 3A and Figure 3B Another example of a valve assembly is shown. Figure 3C yes Figure 3B Magnified view of component C. Figure 3A and Figure 3B The valve assembly 200 shown in FIG. 1 may be incorporated into Figure 1 and Figure 2 The valve assembly 200 includes a housing 202 having an inner wall defining a valve chamber 304 and a valve stem 220. The housing 202 is formed of two parts: a lower cup portion 206; and an upper cover portion 208. The valve assembly 200 can be placed in a container (e.g., Figure 1 and Figure 2 118) is crimped into place at the top of the container 118 in the container, with the distal portion of the valve stem 220 protruding from the top of the container for connection to the actuator.

[0046] The cup portion 206 has a lower wall 210 with an aperture 212 therethrough. A tubular spigot 214 extends from the lower wall 210. A dip tube (not shown) can be connected to the tubular spigot 214, typically via an enlarged lower end, with the dip tube extending to the base of the container to which the valve assembly 200 is assembled. It should be understood that the lower region of the container to which the valve assembly 200 is assembled is in fluid communication with the valve chamber 304 via the dip tube, the spigot 214, and the aperture 212 (which provides liquid access to the valve chamber).

[0047] like Figure 3C As shown, the stem gas inlet 286 is moved to a position where it is slightly offset distally from the lip 226, i.e., the central axis 287 of the stem gas inlet 286 is just above the centerline 227 of the lip 226. This allows not only gas to enter the stem gas inlet 286 from the valve chamber gas inlet 234a, but also allows a small amount of liquid to enter from the valve chamber liquid inlet 212.

[0048] In some embodiments, the stem gas inlet 286 is stepped, with the diameter of the outer portion 286a (opening to the stem surface 272) being larger than the diameter of the inner portion 286b (opening to the outlet conduit 280). Alternatively, the stem gas inlet 286 may have a conical cross-section, tapering from a larger outer portion to a smaller inner portion. In the configuration of the valve assembly 200, the total cross-sectional area of ​​the bleed passages 240, 238, 234, 286 should not be too large to prevent excessive gas from being vented into the outlet conduit 280, causing the container to be depleted of pressurized propellant before all the hair spray composition is discharged. The total cross-sectional area of ​​the bleed passages may be equivalent to the total cross-sectional area of ​​a single circular cross-section inlet having a diameter of 0.15 mm to 0.8 mm.

[0049] Figure 4A Shown from Figure 3A and Figure 3B An example of the cover portion 208. Figure 4A As shown, the cover portion 208 has a generally cylindrical inner wall 224 with a lip 226 projecting inwardly from the inner wall at its upper end. The lower end 228 of the cover portion has a narrower outer diameter to provide an interference fit with the interior of the cup portion 206. At the upper end of the cover portion 208, an annular rim 230 and an upper surface 232 together define a shelf within which an annular sealing gasket 260 is seated.

[0050] Figure 4B A plurality of radial grooves 234 are shown defined between corresponding radial ribs 236 on the upper surface 232. The inner ends 234a of the grooves 234 open into the upper end of the valve chamber above the lip 226. The outer ends 234b of the grooves 234 open into a circumferential groove 238 that surrounds the upper surface 232 just inside the rim 230. The lower and side surfaces of the respective grooves 234, 238 are formed by the cup portion itself, while their upper surfaces are formed by the lower surface 262 of the gasket 260.

[0051] A conduit 240 is formed through the cover portion 208, with its upper end opening into the circumferential groove 238 via an aperture 242 and its lower end exiting the side of the cup portion 206 via an aperture 244 in the outer surface of the cup portion. It will be appreciated that the headspace of the container to which the valve assembly 200 is assembled communicates with the valve chamber 304 via the conduit 240, the circumferential groove 238, and the radial groove 234 (which together provide a gas inlet to the valve chamber).

[0052] The valve stem 220 is generally cylindrical, having an outer surface 272 having a diameter equal to the inner diameter of the lip 226, such that the lip 226 forms a seal around the periphery of the valve stem 220. A proximal end 274 of the valve stem is received in the valve chamber 304, and a distal end 276 protrudes through the center 264 of the annular sealing gasket 260, which is sized to seal against the outer surface 272 of the valve stem 220. The lower surface 262 of the gasket 260 defines the top of the valve chamber 304.

[0053] Figure 5A and Figure 5B An exemplary valve stem 320 for use in the present hair spray product is shown. The valve stem 320 includes an outlet flow conduit 280 having an orifice 282 at the 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 middle of the valve stem, with the gas inlet 286 slightly distal to the liquid inlet 284. It should be understood that alternative arrangements are contemplated. For example, there may be multiple liquid inlets 284 and / or multiple gas inlets 286; the inlets 284, 286 may be positioned more proximally or distally than shown; and the axial spacing between the respective liquid and gas inlets may be greater than shown.

[0054] like Figure 5A and Figure 5B As shown, toward the proximal end 274 of the valve stem 220, an enlarged shoulder portion 290 projects radially from the cylindrical 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 portion 290. Four conduits 294 extend radially from the center to the exterior within the shoulder portion 290, where they open into the bore 292. At the outer ends, the radial conduits 294 open into corresponding axial grooves 296 in the outer surface of the shoulder 290, which extend parallel to the bore 292 and parallel to the outlet conduit 280.

[0055] As shown, the valve stem 220 is biased upwardly to the valve assembly (and hence the aerosol device) by a coil spring 222. The lower end of the coil spring 222 is positioned around the aperture 212 in the cup portion 206 of the housing 202. In the closed valve position, as shown Figure 3AAs shown, shoulder 290 abuts lip 226 under the force of spring 222, and the flow passage defined by bore 292, radial conduit 294, and axial groove 296 is blocked because the top of axial groove 296 abuts the underside of lip 226. In addition, liquid inlet 284 is further away than sealing gasket 260. Therefore, there is no fluid communication between the valve chamber liquid inlet 212 and outlet conduit 280. There is also no fluid communication between the valve chamber gas inlet 234a and outlet conduit 280 because gas inlet 286 is also further away than sealing gasket 260, which hermetically seals against the outer surface 272 of the valve stem.

[0056] The abutment of the shoulder 290 against the lip 226 acts as an upper limit stop, preventing the valve stem 220 from being pushed further out of the valve housing 202 .

[0057] When the valve stem moves to the open position, Figure 3B As shown, the stem liquid inlet 284 is moved below (i.e., proximal to) the lip 226 so as to be in fluid communication with the valve chamber liquid inlet 212 via a flow passage defined by the bore 292, radial conduit 294, and axial groove 296 extending through the stem shoulder portion 290. Furthermore, the stem gas inlet 286 is moved below (i.e., proximal to) the sealing gasket 260 to a position at the upper end of the valve chamber 304 so as to be in fluid communication with the valve chamber gas inlet 234a. At least a portion of the stem gas inlet 286 must open into the upper portion of the valve chamber 304 (i.e., the portion above the lip 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 limit stop.

[0058] Thus, to operate 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. Consequently, the liquid stem inlet 284 and the gas stem inlet 286 are displaced past the gasket 260 and into fluid communication with the liquid hair spray composition from the container 2 and the compressed gas from the headspace, respectively.

[0059] Compressed gas may now flow into outlet conduit 240 by passing through aperture 244 in the outer surface of cover portion 208 , conduit 280 , aperture 242 , circumferential groove 238 , and radial groove 234 , and through stem gas inlet 286 .

[0060] The hair spray composition can now flow into the upper portion of the valve chamber 304 by passing upward along the dip tube 20 through the inlet 212, the bore 292, the radial conduit 294, and the axial groove 296. The hair spray composition introduced into the upper portion of the valve chamber 304 is transferred to the flow conduit 280 via the stem liquid inlet 284, where it mixes with the compressed gas released through the stem gas inlet 286. A uniform stream of bubbles having similar diameters (Dv50) and no significant coalescence or stratification is formed in the outlet flow conduit 280. This stream of bubbles can then flow, preferably undisturbed, through the stem orifice and the actuator.

[0061] A non-limiting example of a spray device suitable for use with the spray product of the present invention is provided by Salvalco, York, GB. Such a valve is disclosed in U.S. Patent No. 10,071,849.

[0062] actuator

[0063] Figure 6 An exemplary hair spray product 600 is shown, which includes a container 601, a spray device 605 and a spray actuator 610. Figure 6 As shown, container wall 608 encloses a reservoir 618 containing a compressed gas propellant 620 and a hair spray composition 606. Spray device 605 can be one of the spray devices described herein. A dip tube 619 extends into reservoir 618 and provides fluid communication between the reservoir and the valve assembly of spray device 605. The valve assembly and valve stem of spray device 605 are configured to provide fluid communication between the dip tube and spray actuator 610. When sufficient force is applied to spray actuator 610, hair spray composition 606 travels upward through dip tube orifice 615 and dip tube 619 and out actuator outlet orifice 612.

[0064] In some embodiments, it may be desirable to use a button-type actuator to provide a short flow path for the hair spray 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 function with (e.g., seat on) a valve assembly and / or valve stem that is vertically configured, such as Figure 1 and Figure 2 In this configuration, the valve is actuated by applying a downward actuation force rather than a lateral force as used, for example, in a tilt valve configuration.

[0065] In some cases, 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 discovered that the ability of the valve assembly and actuator nozzle to atomize the hair spray composition can differ significantly. Without wishing to be bound by any theory, it is believed that by keeping the area of ​​the actuator outlet orifice closer to that of the valve stem orifice, the hair spray composition is prevented from rushing past the actuator and becoming a "bottleneck" at the outlet. If the hair spray composition forms a bottleneck at the outlet orifice, it loses the energy required for atomization. The so-called valve stem orifice refers to the orifice through which the hair spray composition passes. Some spray devices may have a second orifice through which only compressed gas passes.

[0066] Top cover

[0067] Figure 7 An example of a hair spray product 700 is shown having a top cap 750 to prevent accidental discharge of the hair spray composition, provide tamper resistance or serve as a tamper-evident seal, protect the actuator from damage, and / or coordinate the aesthetic appeal of the hair spray product. The top cap 750 covers the top portion of the hair spray product 700 (e.g., the spray actuator 710, the valve stem, and the valve assembly). The top cap 750 can be releasably attached to the container 701 or the container neck 705 by an outwardly protruding ridge that surrounds the inner lower edge of the top cap and interacts with the curling or seam surrounding the top portion of the container 701. When the top cap 750 is placed onto the top portion of the container 701, downward pressure can be applied to the top cap 750 so that the ridge spans the outer edge of the seam and locks under the flange defined by the lower surface of the seam. As desired, the top cap 750 can be transparent, translucent, opaque, colored, or colorless. Figure 7 As shown, the top cover 750 is colorless and transparent so that the actuator outlet orifice 712 is generally visible to the user.

[0068] Container, spray device, actuator and / or top cap can be made of any suitable desired material.The particularly suitable material for making these features comprises recyclable, reclaimed and / or the material in sustainable source.For example, one or more in container, spray device, actuator and / or top cap can be made of the material that comprises 10% to 100% (for example, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or even 100%) recyclable, reclaimed or the material in sustainable source.Some non-limiting examples of recyclable material comprise metal, glass, plastic and paper.Some non-limiting examples of recycled material comprise the plastic made of (PCR) resin, recycled aluminum and recycled glass after consumption.Some non-limiting examples of the container material in sustainable source comprise bio-based plastics, which is the polymeric material made of renewable carbon raw material such as plant (for example, soybean, 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. Additional examples and descriptions of bio-based plastics and modern carbon percentage values ​​can be found in U.S. Patent Nos. 11,433,158 and 10,166,312.

[0069] Hair spray composition and compressed gas propellant

[0070] The aerosol hair spray product herein comprises a hair spray composition and a compressed gas propellant stored in a reservoir of a container. The compressed gas propellant and the hair spray composition may be stored in the same or separate compartments. The reservoir may contain 50% to 65% by volume of the hair spray composition (e.g., 55% to 60%). The reservoir may contain 35% to 70% by volume (e.g., 40% to 60%, 45% to 55%, or 45% to 50%) of the propellant. As used herein, unless otherwise indicated, details of the hair spray composition and propellant refer to the composition before it is placed in the can.

[0071] The hair spray composition is dispensed as a plurality of 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 an ethanol-based hair spray may be

[0072] The ethanol-free hair spray may have a spray delivery rate of 0.2 g / s to 0.9 g / s (e.g., 0.25 g / s to 0.8 g / s, 0.28 g / s to 0.75 g / s, or 0.3 g / s to 0.7 g / s), as determined by the Delivery Rate Test Method. The ethanol-free hair spray may have a spray delivery rate of 0.2 g / s to 0.6 g / s (e.g., 0.25 g / s to 0.55 g / s or 0.3 g / s to 0.5 g / s), as determined by the Delivery Rate Test Method.

[0073] The kinematic viscosity of the ethanol-free hair spray compositions herein without propellant may be from 0.5 cSt to 5.5 cSt (e.g., from 1 cSt to 5 cSt, from 1.25 cSt to 4.5 cSt, from 1.5 cSt to 4.0 cSt, from 1.75 cSt to 3.5 cSt, from 1.8 cSt to 3 cSt, or even from 2.0 cSt to 2.5 cSt). The kinematic viscosity of the ethanol-based hair spray compositions herein without propellant may be from 1 cSt to 20 cSt (e.g., from 3 cSt to 18 cSt, or from 5 cSt to 15 cSt).

[0074] The hair spray composition may include 1.5% to 10% of a hair fixative polymer, by weight of the hair spray composition. The amount of hair fixative polymer is important for balancing hold performance and moisturization on the hair. The amount of hair fixative polymer drives hold performance but is limited by the maximum sprayable viscosity. The hair spray composition may include 2% to 8% (e.g., 3% to 7% or 3.5% to 6%) of a hair fixative polymer, by weight of the hair spray composition. These amounts may be the total amount of hair fixative polymer in the hair spray composition.

[0075] 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 provides a viscosity of 6 cSt or less as measured before the addition of the propellant. The hair spray composition containing the soluble hair styling polymer is then pressurized in a can with a gaseous propellant. In some examples, the user can shake the can prior to dispensing to mix the hair spray composition with the hair styling polymer and the propellant.

[0076] The hair styling polymer may be any water-soluble or alcohol-soluble film-forming polymer or mixture of such polymers. This includes homopolymers or copolymers of natural or synthetic origin having functional groups such as hydroxyl, amine, amide or carboxyl groups which render the polymer water-soluble.

[0077] When diluted within the claimed range, soluble hair-fixing polymers form transparent or translucent stable solutions. Depending on the specific polymer type, 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-fixing polymers can be divided into two types, (completely) synthetic polymers and natural products, along with their chemically modified derivatives, and can be further grouped under three main headings: naturally occurring polymers, semi-synthetic polymers, and completely synthetic polymers. The hair-fixing polymer can be selected from the group consisting of cationic hair-fixing polymers, anionic hair-fixing polymers, nonionic hair-fixing polymers, and amphoteric hair-fixing polymers. The molecular weight of the hair-fixing polymer should be such that the propellant-free hair spray composition meets the specified viscosity requirements. The hair-fixing polymer can be linear or branched.

[0078] 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: a quaternized acrylate or methacrylate; a quaternary homopolymer or copolymer of vinylimidazole; a homopolymer or copolymer comprising dimethyldiallylammonium chloride; a non-cellulosic cationic polysaccharide; a cationic cellulose derivative; chitosan and its derivatives; and mixtures thereof.

[0079] The hair-fixing polymer may be an anionic hair-fixing polymer or a mixture of anionic hair-fixing polymers. The anionic hair-fixing polymer may be selected from those comprising groups derived from carboxylic or sulphonic acids. The copolymers containing acid units are generally used in their partially or fully neutralised form, more preferably in fully neutralised form. The anionic hair styling polymer may comprise: (a) at least one monomer derived from a carboxylic acid such as acrylic acid, or methacrylic acid, or crotonic acid or their salts, or a C4-C8 monounsaturated polycarboxylic acid or anhydride (e.g. maleic acid, fumaric acid, itaconic acid and their anhydrides), and (b) one or more monomers selected from the group consisting of: esters of acrylic acid and / or methacrylic acid (e.g. C1-C4 alkyl acrylates, methyl acrylate, ethyl acrylate, tert-butyl acrylate and methacrylate derivatives of these); acrylates grafted onto polyalkylene glycols such as polyethylene glycol (e.g. poly(ethylene glycol) acrylate); hydroxy acrylates (e.g. hydroxyethyl methacrylate); acrylamide, methacrylamide, which may or may not be substituted on nitrogen by a lower alkyl group (C1-C4); N- Alkylated acrylamides (e.g., N-tert-butyl acrylamide); hydroxyalkylated acrylamides; aminoalkylated acrylamides (e.g., dimethylaminopropyl methacrylamide); alkyl acrylamides (e.g., tert-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate); alkyl ether acrylates (e.g., 2-ethoxyethyl acrylate); monoolefinic monomers such as ethylene, styrene; vinyl esters (e.g., vinyl acetate or vinyl propionate, vinyl tert-butylbenzoate); vinyl esters grafted onto polyalkylene glycols such as polyethylene glycol; vinyl ethers; vinyl halides; phenyl vinyl derivatives; allyl esters or methallyl esters; vinyl lactams such as vinyl pyrrolidone or vinyl caprolactam; alkyl maleimides, hydroxyalkyl maleimides (e.g., ethyl / ethanol maleimide). When present, the anhydride functional groups of these polymers may optionally be monoesterified or monoamidated. The anionic hair styling polymers may comprise monomers derived from sulfonic acids.The anionic polymer may comprise: (a) at least one monomer derived from a sulfonic acid, such as vinylsulfonic acid, styrenesulfonic acid, naphthalenesulfonic acid, acrylylalkylsulfonic acid, acrylamidoalkylsulfonic acid or salts thereof, and (b) one or more monomers selected from the group consisting of: esters of acrylic acid and / or methacrylic acid (e.g., C1-C4 alkyl acrylates, methyl acrylate, ethyl acrylate, tert-butyl acrylate and methacrylate derivatives of these); acrylates grafted onto polyalkylene glycols such as polyethylene glycol (e.g., poly(ethylene glycol) acrylate); hydroxy acrylates (e.g., hydroxyethyl methacrylate); acrylamide, methacrylamide, which may or may not be substituted on nitrogen by lower alkyl groups (C1-C4); N-alkylated acrylamides (e.g., N- tert-butylacrylamide); hydroxyalkylated acrylamide; aminoalkylated acrylamide (e.g., dimethylaminopropyl methacrylamide); alkyl acrylamide (e.g., tert-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate); alkyl ether acrylate (e.g., 2-ethoxyethyl acrylate); monoolefin monomers such as ethylene, styrene; vinyl esters (e.g., vinyl acetate or vinyl propionate, vinyl tert-butylbenzoate); vinyl esters grafted to polyalkylene glycols such as polyethylene glycol; vinyl ethers; vinyl halides; phenyl vinyl derivatives; allyl esters or methallyl esters; vinyl lactams such as vinyl pyrrolidone or vinyl caprolactam; alkyl maleimides, hydroxyalkyl maleimides (e.g., ethyl / ethanol maleimide). When present, the anhydride functional groups of these polymers may optionally be monoesterified or monoamidated.

[0080] Anionic hair styling polymers may be selected from: copolymers derived from acrylic acid, such as acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers, such as those derived from that sold as Ultrahold 8; octylacrylamide / acrylates / butylaminoethyl / methacrylate copolymer, such as that sold by Akzo As Methacrylate / acrylate / methacrylate, such as that sold by Akzo As Octyl acrylamide / acrylates / butylaminoethyl methacrylate copolymer, such as that sold by Akzo As 47 sold that; methacrylic acid / hydroxyethyl methacrylate / various acrylates, such as by Chemical sells it as Acudyne TM 1000; acrylates / hydroxyethyl methacrylates, such as Chemical as AcudyneTM 180 sold that; methacrylic acid / hydroxyethyl methacrylate / various acrylates, such as by Chemical as Acudyne TM that sold by DHR; n-butyl methacrylate / methacrylic acid / ethyl acrylate copolymers, such as those made from As that sold as Fix A-1000; copolymers derived from crotonic acid, such as vinyl acetate / vinyl tert-butylbenzoate / crotonic acid terpolymers and crotonic acid / vinyl acetate / vinyl neododecanoate terpolymers, such as those sold by Akzo As Resyn TM Hair styling polymers derived from sulfonic acids may include those sold by Ashland TM As Sulfopolyester (also known as polyester-5), such as that sold by Eastman as Eastman AQ 48; Sulfopolyester (also known as polyester-5), such as that sold by Eastman as Eastman AQ S38; Sulfopolyester (also known as polyester-5), such as that sold by Eastman as Eastman AQ 55. Anionic hair styling polymers may be selected from: copolymers derived from acrylic acid, such as acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers, such as those sold by Eastman as As 8; octylacrylamide / acrylates / butylaminoethyl / methacrylate copolymers, such as those sold as Amphomer; methacrylic acid / acrylates / methacrylates, such as those sold by Akzo As Octyl acrylamide / acrylates / butylaminoethyl methacrylate copolymer, such as that sold by Akzo As 47 sold that; methacrylic acid / hydroxyethyl methacrylate / various acrylates, such as by Chemical sales are called 1000; acrylates / hydroxyethyl methacrylates, such as Chemical as 180 sold that; methacrylic acid / hydroxyethyl methacrylate / various acrylates, such as by Chemical as that sold by DHR; n-butyl methacrylate / methacrylic acid / ethyl acrylate copolymers, such as those made from As that sold as Fix A-1000; copolymers derived from crotonic acid, such as vinyl acetate / vinyl tert-butylbenzoate / crotonic acid terpolymers and crotonic acid / vinyl acetate / vinyl neododecanoate terpolymers, such as those sold by Akzo As Resyn TM 282930. Hair styling polymers derived from styrene sulfonic acid may include those sold by Ashland TM As 130; sulfopolyester (also known as polyester-5), such as that sold by Eastman as Eastman AQ 48; sulfopolyester (also known as polyester-5), such as that sold by Eastman as Eastman AQ S38; sulfopolyester (also known as polyester-5), such as that sold by Eastman as Eastman AQ55.

[0081] The hair styling polymer may be an anionic hair styling polymer, and wherein the anionic hair styling polymer is selected from: copolymers derived from acrylic acid, such as acrylic acid / ethyl acrylate N-tert-butylacrylamide terpolymer; octylacrylamide / acrylates / butylaminoethyl / methacrylate copolymer; methacrylic acid / acrylates / methacrylates; octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer; methacrylic acid / hydroxyethyl methacrylate / various acrylates; acrylates / hydroxyethyl methacrylate; methacrylic acid / hydroxyethyl methacrylate / various acrylates; n-butyl methacrylate / methacrylic acid / ethyl acrylate copolymer; copolymers derived from crotonic acid, such as vinyl acetate / tert-butylbenzoate / crotonic acid terpolymer; and crotonic acid / vinyl acetate / neododecanoate terpolymer; and mixtures thereof.

[0082] The hair styling polymer may be a polyurethane dispersed or dissolved in a solvent (e.g., water, ethanol, or another alcohol). Such polyurethanes may include those such as adipic acid, 1-6 hexanediol, neopentyl glycol, isophorone diisocyanate, isophorone diamine, N-(2-aminoethyl)-3-aminoethanesulfonic acid, sodium salt (also known as polyurethane-48), such as those prepared from As C 1008; and polyurethanes such as isophorone diisocyanate, dimethylolpropionic acid, 4,4-isopropylidene diphenol / propylene oxide / ethylene oxide (also known as polyurethane-14), such as those sold by Akzo by H20 is the name of the kind sold as a mixture.

[0083] The hair styling polymer may be a nonionic hair styling polymer or a mixture of nonionic hair styling polymers (such as from of VA 64 and PVP K30 from Ashland). The nonionic hair styling polymers may be water-soluble natural polymers such as hydroxyalkylcelluloses (eg hydroxymethylcellulose, hydroxyethylcellulose or hydroxypropylcellulose) and starch.

[0084] The hair styling polymer may be an amphoteric hair styling polymer or a mixture of amphoteric hair styling polymers, such as those from of Z 731N.

[0085] Some non-limiting examples of styling polymers can be found in co-pending U.S. Patent Serial No. 17 / 874,600, filed on July 27, 2022 by Brown et al.

[0086] The hair spray composition can be substantially free of water-insoluble and / or water-immiscible polymers and / or alcohol-insoluble polymers. High molecular weight (e.g., >200,000 g / mol) polymers can be avoided or used only at very low levels so that the hair spray composition does not exceed the desired viscosity. The hair spray 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 lead to associative interactions in the hair spray composition, which can drive up viscosity without contributing to the strength of the film delivered to the hair.

[0087] Alcohol-based hair spray

[0088] An ethanol-based hair spray composition can include an alcohol solvent present in an amount of 50% to 99.9% alcohol (e.g., 60% to 97%, 70% to 95%, or 80% to 95% ethanol, isopropyl alcohol, etc.), based on the weight of the hair spray composition. Some non-limiting examples of alcohol solvents include ethanol, n-propanol, isopropyl alcohol, and combinations thereof. The hair spray polymer used in the composition should generally be soluble in the alcohol solvent, but this is not necessarily the case.

[0089] The hair spray composition may also contain other additional solvents, including water, provided that such additional solvents are chemically and physically compatible with the ingredients of the composition and that they do not significantly and unduly impair product performance. Some non-limiting examples of formulations and additional ingredients that can be used in ethanol-based hair sprays can be found in WO 1998 / 05379.

[0090] Alcohol-free hair spray

[0091] Some consumers may prefer alcohol-free or very low alcohol-free hair sprays because they may have a purer fragrance (given the absence of alcohol odor), less observed hair drying and reduced brittleness, and may be perceived by consumers as more environmentally friendly and / or healthier to use. The alcohol-free hair spray compositions herein contain less than 2% alcohol / ethanol (e.g., less than 1%, 0.5%, or even less than 0.25% alcohol / ethanol) by weight of the hair spray composition. In some embodiments, the hair spray composition contains 0% ethanol or alcohol. The hair spray polymer used in the composition should generally be water-soluble, but not necessarily so.

[0092] The hair spray composition can include from 30% to 99% water (e.g., from 60% to 98% water, from 70% to 97% water, from 80% to 96% or from 85% to 96%) by weight of the hair spray composition. The water can provide a solvent for the hair styling polymer and other ingredients in the hair spray composition. It may be desirable to use ingredients of the hair spray composition that are water-soluble.

[0093] Compressed gas propellant

[0094] Compressed gas propellants may include gases such as nitrogen, air, carbon dioxide, nitrous oxide, and other inert gases.

[0095] Optional ingredients

[0096] The hair spray composition may include a panthenol compound and / or an organosilicon 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-dimethylbutanamide), D / L-panthenol, pantothenic acid and its salts, panthenol triacetate, royal jelly, pantethine, panthenylthiothionine, panthenyl ethyl ether, panthenic acid, pantothenyllactose, vitamin B complexes, and mixtures thereof. Panthenol compounds may be useful in providing excellent hair appearance and feel benefits. The hair spray composition may include 0.1% to 0.6% (e.g., 0.1% to 0.3%) of the panthenol compound by weight of the hair spray composition. The hair spray composition may include an organosilicon compound. Organosilicon may be useful because it imparts a smoother feel and shine to the hair. The organosilicon compound may be a polydimethylsiloxane compound. The silicone compound may be PEG dimethicone, such as PEG-12 dimethicone.

[0097] The hair spray composition may further include a surfactant present at 1% or less (e.g., 0.6% or less, 0.4% or less, or 0.3% or less) by weight of the hair spray composition. The surfactant may be selected from the group consisting of a cationic surfactant, a nonionic surfactant, an anionic surfactant, and mixtures thereof.

[0098] The hair spray composition may include a neutralizing agent. Suitable neutralizing agents may include potassium hydroxide, sodium hydroxide, triisopropanolamine (TIPA), 2-aminobutanol, 2-aminomethylpropanol (AMP), aminoethylpropylene glycol, dimethyloctadecylamine (Armeen 18D), sodium silicate, tetrahydroxypropylethylenediamine ( TE), ammonia (NH3), triethanolamine, trimethylamine (TrisAminoUltra), aminomethylpropylene glycol (AMPD). The neutralizing agent can be 2-aminobutanol, ammonia or 2-aminomethylpropanol.

[0099] The hair spray composition may include at least one preservative.The preservative 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 hair spray composition.

[0100] The hair spray composition may also include a fragrance or perfume.It may be desirable to limit the amount of fragrance or perfume to 0.5% (eg, 0% to 0.4% or 0.03% to 0.3%) by weight of the hair spray composition.

[0101] Hair spray compositions may include vitamins, amino acids, and preservatives.

[0102] Additional information regarding hair spray compositions and aerosol spray dispensers can be found in U.S. Patent Nos. 9,986,809, 10,131,488, and 10,426,979.

[0103] Test Method

[0104] Spray rate

[0105] The 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 loss over a given time period. This is related to the amount of material discharged through the valve and actuator combination over a given time period. In this case, the can is tested at room temperature (at 21°C) and with an actuation duration of 2 seconds to 10 seconds. The delivery rate is then determined by the following equation:

[0106] Spray rate (g / s) = mass loss (g) / actuation time (s)

[0107] If the spray rate is greater than 0.45 g / s, the drying time on the hair may be too long to satisfy the consumer. This is unique for the ethanol-free hair sprays described herein, as compared to conventional ethanol-based hair sprays, which typically contain volatile alcohols and have delivery rates between 0.55 g / s and 0.85 g / s. The delivery rate can generally be adjusted by varying the pressure inside the container (increased pressure is associated with faster delivery rates) and / or the orifice in the spray device (such as an orifice in the nozzle, an orifice in the valve) and the inner diameter of the dip tube.

[0108] Particle size distribution (Dv50)

[0109] Dv50 is the maximum particle size diameter below which 50% of the sample volume has a maximum particle size diameter. Dv50 is sometimes referred to as the median particle size by volume. Dv90 is the maximum particle size diameter below which 90% of the sample volume has a maximum particle size diameter.

[0110] Droplet size can be important throughout the life of the can because it affects the dry feel, drying time, and hold of the hair spray. Smaller droplets dry faster. More small droplets feel less wet than fewer large droplets. For hold, a larger number of smaller droplets provides greater surface area coverage to provide an even coating of hair welds. If the droplets are too small, they will not bridge the hair together at the weld point and will not hold. This can be important for non-alcoholic hair sprays, which do not have the fast evaporation drying advantage of ethanolic formulas. Alcoholic hair sprays have a much wider working droplet size range, for example, 30um-130um. Non-alcoholic hair sprays with a Dv50 below 40um may have hold issues. Non-alcoholic hair sprays with a Dv50 above 80um may have a significantly slower drying time and an initial wet feel. Dv90 represents the largest droplets in the spray, although there are far fewer of them. Dv90 values ​​exceeding 180 μm, which grow larger over the life of the canister, reaching as high as 400 μm, can cause the spray to appear visually uneven, with larger, more splattered droplets. These large droplets make the spray less misty and more uniform. This can cause hair to clump where these large droplets land. These hair clumps can give the finished hair an unnatural feel that makes it difficult to run fingers or a brush through.

[0111] The average particle size distribution (Dv50) can be important in view of the drying time of the spray composition, which must be acceptable to the consumer. In fact, a smaller average particle size distribution (Dv50) can be useful because more particles have a higher surface area to volume ratio, which means faster drying time. On the other hand, too low an average particle size distribution (Dv50) may mean that not enough hair styling polymer is provided to the hair to provide spot welding.

[0112] Malvem Spraytec TM Instrument used to measure particle size distribution. Malvern Spraytec TM The instrument uses laser diffraction technology to measure the size of spray particles. It measures the intensity of light scattered when a laser beam passes through the spray. This data is then analyzed to calculate the size of the particles that form the scattered pattern. Use the Malvern Spraytec according to the manufacturer's instructions. TM 2000. The test sample has a temperature between 20°C and 22°C.

[0113] Spray diameter

[0114] The spray pattern can be important throughout the life of the can because it affects the dry feel, drying time, and hold properties of the hair spray. A smaller spray diameter or a more localized spray can make the hair feel wetter, take longer to dry, and provide more hold due to more and larger welds between the hairs. A larger spray diameter or a more misty spray can result in areas where the droplets do not bridge the hairs together in the weld points and will not hold, which can be undesirable. Given the typical size of a human head and the distance a person can comfortably hold the container from their head, a spray diameter of 2 inches to 6 inches is desirable.

[0115] The spray diameter is measured using thermal paper mounted on a rigid test stand. The test sample is equilibrated to 20°C to 24°C. The test can is placed perpendicular to the paper at a distance of 6 inches + / - 10°. After the spray is completed, the test paper is scanned and analyzed using imaging software. The outer diameter of the spray is calculated by the following formula

[0116] Diameter = 2*("area" / 3.141593)^0.5

[0117] Where "area" is the location of the cell containing the outer diameter area in the imaging software.

[0118] Viscosity

[0119] Kinematic viscosity can be measured using an Ubbelohde 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 for kinematic viscosity is m 2 ·s. The physical unit of kinematic viscosity is stokes (St), which can be expressed in centistokes (cSt). 1 cSt = 1 mm 2 ·s -1 =10 -6 m 2 ·s -1. The kinematic viscosity of water at 20°C is 1 cSt. The Ubbelohde tube is a viscometer used to measure the kinematic viscosity of transparent Newtonian liquids by the principle of suspended level as described in ASTM D445 and D 446 and ISO 3104 and 3105. For Ubbelohde tube measurements, there is no temperature effect on the results, for other kinematic viscometers, temperatures different from the specified test range may affect the results. In this article, the measurements are carried out at a temperature of 20°C + / - 0.1°C. This method can be used to measure 0.6 cSt to 100 cSt. For instructions for use of the Ubbelohde viscometer, see ASTM D 445. For viscosities of 0.6 cSt to 3 cSt at 20°C + / - 0.1°C, use Ubbelohde tube No. 0. For viscosities of 2 cSt to 10 cSt at 20°C + / - 0.1°C, use Ubbelohde tube No. 1. ASTM D445 is "Standard Test Method for Kinematic Viscosity of Transparent and Opaque Liquids". ASTM D446 is "Specifications and Operating Instructions for Glass Capillary Viscometers."

[0120] Example

[0121] The aerosol dispensers were filled with either ethanol-free hair spray (i.e., water-based hair spray) or ethanol-based hair spray and 60% nitrogen propellant. Each experimental aerosol dispenser had an aerosol assembly that included four Salvalco Eco- Each Salvalco Eco- There appear to be different configurations which may include varying the thickness and diameter of the outlet orifice and / or varying the number, height and width of channels tangential to the orifice. Without being limited by theory, it is believed that different spray device configurations affect the spray characteristics.

[0122] Throughout the life of the dispenser, it will have the Salvalco Eco- The spray characteristics (e.g., spray rate (g / s) and droplet size (μm)) of the aerosol dispenser were compared with those of the control ( The cans were filled with 40% to 60% nitrogen at 135 PSIG. The cans were tested from 100% product (full can) to when 25% of the product remained in the can. Initial values ​​were obtained when the container was full (i.e., when 100% of the composition was present), and final values ​​were obtained when approximately 25% of the hair spray composition remained. The test results for the ethanol-based hair spray compositions are summarized in Table 2A. The test results for the non-ethanol-based hair spray compositions are summarized in Table 2B.

[0123] Table 2A

[0124]

[0125] Table 2B

[0126]

[0127] In the examples in Tables 3 and 4 below, an aerosol container was filled with nitrogen and a hair spray composition. The aerosol container comprised a Salavaco Eco-Valve with a green insert. Compared to the paired examples in Table 4, the hair spray in Table 3 contained twice the concentration of active ingredient and a higher viscosity.

[0128] The examples in Tables 3 and 4 were tested to see if they met the properties described herein in Table 1. Spray properties are maintained if the initial spray rate and Dv50 vary by less than 10% and no more than 20 microns, respectively, from the spray rate and Dv50 when 25% of the hair spray composition remains in the container.

[0129] Table 3: Spray rate and Dv50 of compositions with high concentration of active substance

[0130]

[0131] None of the examples tested in Table 3 met all of the success criteria outlined herein. For the ethanol-based hair sprays combined with 40% and 60% nitrogen propellants (Examples JJ in Table 7 below), the spray rate was acceptable to consumers, however the Dv50 average particle size was too large to be a consumer acceptable hair spray product.

[0132] For the ethanol-free hair spray (Example AA in Table 5 below), the spray rate was acceptable to consumers for the examples with 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, this was true at both test points. For the 20% nitrogen propellant, the initial particle size was acceptable to consumers, but by the remaining 25% of the composition, the average particle size was too large to be acceptable to consumers.

[0133] Examples AA and JJ tested in Table 3 have similar active concentrations to current products using hydrocarbon propellants. It was discovered that because nitrogen propellants do not liquefy like hydrocarbon propellants, lower concentrations of hair spray compositions can be used while still providing excellent styling benefits. Additionally, since the Dv50 particle size for 40% nitrogen fill was too high for both ethanol-based and ethanol-free hair sprays, and a Dv50 particle size of 60% was closer to the preferred range for both the initial and 25% remaining products, it was determined that 60% nitrogen would be used for the lower concentration formulations.

[0134] Table 4: Spray rate and Dv50 of hair sprays with lower concentrations of active substances

[0135]

[0136] Examples J (Table 7 below) and A (Table 5 below) tested in Table 4 had half the active level compared to Examples JJ and AA tested in Table 3. Both the ethanol-based hair spray (Example J) and the ethanol-free hair spray (Example A) had consumer acceptable spray rates and Dv50 average particle sizes upon initial spraying and when 25% of the hair spray composition remained in the can.

[0137] The examples in Tables 5, 6 and 7 can be prepared using conventional methods for making hair spray compositions and products.

[0138] Table 5: Alcohol-free hair spray compositions of Examples AD (active substance level %)

[0139]

[0140] key: CR polymer; 2 =DynamX H20; 3 =Acudyne 1000; 4 =Amphomer; 5 =Luviskol VA64; 6 =Luviquat FC550; HCMF; 8 =Celquat L-200.

[0141] Table 6: Example EI hair spray composition without ethanol (active substance level %)

[0142]

[0143] key: CR polymer; 2 =DynamX H20; 3 =Acudyne 1000; 4 =Amphomer; 5 =Luviskol VA64; 6 =Luviquat FC550; HCMF; 8 =Celquat L-200.

[0144] Table 7: Example JK Ethanol-Based Finishing Gel

[0145]

[0146]

[0147] key: 1=Resyn 28-2930; 2 =Amphomer; 3 =Balance 47;

[0148] The dimensions and values ​​disclosed herein should not be understood as being strictly limited to the exact numerical values ​​recited. Instead, unless otherwise indicated, each such dimension is intended to mean both the recited value and a functionally equivalent range encompassing that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."

[0149] Unless expressly excluded or otherwise limited, each document cited herein, including any cross-referenced or related patent or patent application and any patent application or patent to which this application claims priority or the benefit of, is hereby incorporated by reference in its entirety. The citation of any document is not an admission that it is prior art to any of the present inventions disclosed or claimed herein, or an admission that it, by itself or in combination with any one or more references, proposes, suggests, or discloses any such invention. Further, 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 govern.

[0150] Although specific embodiments of the present invention have been illustrated and described, it will be apparent to those skilled in the art that various other changes and modifications may be made without departing from the spirit and scope of the invention. It is therefore intended that all such changes and modifications within the scope of the invention be encompassed in the appended claims.

[0151] Examples / Combinations

[0152] 1. An aerosol hair spray product, comprising:

[0153] a) a pressurizable container comprising a container wall enclosing a reservoir for storing a compressed gas propellant and a hair spray composition comprising:

[0154] i) 30% to 98.5% by weight of the hair spray composition of a solvent, and

[0155] ii) from 1.5% to 8% by weight of the hair spray composition of a hair styling polymer,

[0156] wherein the hair styling polymer is soluble in the solvent;

[0157] b) a spray device riveted to the container for dispensing the hair spray composition from the reservoir of the container, wherein the spray device comprises:

[0158] i) a valve assembly comprising a housing having an inner wall defining a valve chamber, wherein the valve chamber comprises a liquid inlet in fluid communication with the hair spray composition in the reservoir, and a gas inlet in fluid communication with the compressed gas propellant in the reservoir,

[0159] ii) a valve stem comprising a proximal end and a distal end, wherein the proximal end is received in the valve chamber and the distal end protrudes through a sealed opening in the valve chamber, the valve stem further comprising an outlet flow conduit having an outlet aperture at the distal end, a first stem inlet for receiving liquid, and a second stem inlet for receiving gas,

[0160] wherein the housing includes a lip around a periphery of the valve stem to form a seal around the periphery of the valve stem,

[0161] wherein the valve chamber liquid inlet is proximal to the lip, and the valve chamber gas inlet is distal to the lip, and

[0162] The valve stem is capable of moving between the following positions:

[0163] a closed position wherein the first stem inlet is distal to the lip and the second stem inlet is distal to the sealed opening in 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, and

[0164] an open position wherein the first stem inlet is proximal to the lip and in fluid communication with the valve chamber liquid inlet, and the second stem inlet is proximal to the sealed opening in the valve chamber and at least partially distal to the lip and in fluid communication with the valve chamber gas inlet, thereby generating a gas carrier gas flow in the outlet flow conduit;

[0165] c) an actuator coupled to the spray device; and

[0166] d) a top cover covering the actuator and a top portion of the container.

[0167] 2. The aerosol hair spray product of paragraph 1, wherein the actuator comprises an outlet orifice having an outlet orifice area, and the valve stem comprises 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.

[0168] 3. The aerosol hair spray product of paragraphs 1 or 2, wherein the valve assembly is vertically oriented and the actuator is seated on the vertically oriented valve system.

[0169] 4. An aerosol hair spray product according to any preceding paragraph, wherein the solvent is water and the hair spray composition is free of alcohol.

[0170] 5. An aerosol hair spray product according to any preceding paragraph, wherein the compressed gas propellant comprises nitrogen.

[0171] 6. An aerosol hair spray product according to any preceding paragraph, further comprising 5.5% to 8% of an anionic hair fixative polymer, the anionic hair fixative polymer comprising a hair fixative polymer derived from acrylic acid, preferably selected from acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymer, acrylates / hydroxyacrylate copolymers of butyl acrylate, methyl methacrylate, methacrylic acid, ethyl acrylate and hydroxyethyl methacrylate, polyurethane-14 / AMP-acrylates copolymer blend, octylacrylamide / acrylates / butylaminoethyl / methacrylate copolymer, methacrylic acid / acrylates / methacrylate copolymer, acrylates / hydroxyethyl methacrylate copolymer, methacrylic acid / hydroxyethyl methacrylate / acrylates copolymer; n-butyl methacrylate / methacrylic acid / ethyl acrylate copolymer and combinations thereof.

[0172] 7. An aerosol hair spray product according to any preceding paragraph, further comprising 5.5% to 8% of an anionic hair styling polymer, said anionic hair styling polymer comprising an anionic hair styling polymer derived from crotonic acid, preferably vinyl acetate / vinyl t-butylbenzoate / crotonic acid terpolymer, crotonic acid / vinyl acetate / vinyl neododecanoate terpolymer, and combinations thereof.

[0173] 8. An aerosol hair spray product according to any preceding paragraph, wherein the hair spray product has a spray rate of 0.3 g / s to 1.0 g / s, preferably 0.3 g / s to 0.8 g / s, and more preferably 0.3 g / s to 0.6 g / s, according to the Spray Rate Test.

[0174] 9. The aerosol hair spray product of paragraph 8, wherein the spray rate of the hair spray product varies by no more than 30%, preferably no more than 20%, and more preferably no more than 10% from when the container holds 100% of the hair spray composition to when the container holds 25% of the hair spray composition.

[0175] 10. The aerosol hair spray product of any preceding paragraph, wherein the hair spray product has a Dv50 of 40 μm to 90 μm, as tested by Particle Size Distribution.

[0176] 11. The aerosol hair spray product of paragraph 10, wherein the Dv50 does not change by more than 20 μm from when the container is 100% filled with the hair spray composition to when the container is 25% filled with the hair spray composition.

[0177] 12. The aerosol hair spray product according to paragraph 1, wherein the hair spray product has a spray diameter of 5 cm to 15.25 cm.

[0178] 13. The aerosol hair spray product of paragraph 12, wherein the spray diameter does not vary by more than 30%, preferably by more than 20%, and more preferably by more than 10% from when the container contains 100% of the hair spray composition to when the container contains 25% of the hair spray composition.

[0179] 14. The aerosol hair spray product of any preceding paragraph, wherein at least one of the container, the spray device, the actuator, and the cap comprises 10% or more of a material selected from recycled materials, bio-based plastics, and combinations thereof.

[0180] 15. A method for styling hair, the method comprising:

[0181] a) providing an aerosol hair spray product according to any preceding paragraph; and

[0182] b) applying the hair spray composition to target portions of the hair where styling benefits are desired.

Claims

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 hair spray composition comprising: i) 30% to 98.5% by weight of the hair spray composition of a solvent, and ii) from 1.5% to 8% by weight of the hair spray composition of a hair styling polymer, wherein the hair styling polymer is soluble in the solvent; b) a spray device riveted to the container for dispensing the hair spray composition from the reservoir of the container, wherein the spray device comprises: i) a valve assembly comprising a housing having an inner wall defining a valve chamber, wherein the valve chamber comprises a liquid inlet in fluid communication with the hair spray composition in the reservoir, and a gas inlet in fluid communication with the compressed gas propellant in the reservoir, ii) a valve stem comprising a proximal end and a distal end, wherein the proximal end is received in the valve chamber and the distal end protrudes through a sealed opening in the valve chamber, the valve stem further comprising an outlet flow conduit having an outlet aperture at the distal end, a first stem inlet for receiving liquid, and a second stem inlet for receiving gas, wherein the housing includes a lip around a periphery of the valve stem to form a seal around the periphery of the valve stem, wherein the valve chamber liquid inlet is proximal to the lip, and the valve chamber gas inlet is distal to the lip, and The valve stem is capable of moving between the following positions: a closed position wherein the first stem inlet is distal to the lip and the second stem inlet is distal to the sealed opening in 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, and an open position wherein the first stem inlet is proximal to the lip and in fluid communication with the valve chamber liquid inlet, and the second stem inlet is proximal to the sealed opening in the valve chamber and at least partially distal to the lip and in fluid communication with the valve chamber gas inlet, thereby generating a gas carrier gas flow in the outlet flow conduit; c) an actuator coupled to the spray device; and d) a top cover covering the actuator and a top portion of the container.

2. The aerosol hair spray product of claim 1 , wherein the actuator comprises an outlet orifice having an outlet orifice area, and the valve stem comprises 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. An aerosol hair spray product according to claim 1 or 2, wherein the valve assembly is vertically oriented and the actuator is seated on the vertically oriented valve system.

4. An aerosol hair spray product according to any preceding claim, wherein the solvent is water and the hair spray composition is free of alcohol.

5. An aerosol hair spray product according to any preceding claim, wherein the compressed gas propellant comprises nitrogen.

6. An aerosol hair spray product according to any preceding claim, further comprising 5.5% to 8% of an anionic hair fixative polymer comprising a hair fixative polymer derived from acrylic acid, preferably selected from acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymer, acrylates / hydroxyacrylate copolymers of butyl acrylate, methyl methacrylate, methacrylic acid, ethyl acrylate and hydroxyethyl methacrylate, polyurethane-14 / AMP-acrylates copolymer blend, octylacrylamide / acrylates / butylaminoethyl / methacrylate copolymer, methacrylic acid / acrylates / methacrylate copolymer, acrylates / hydroxyethyl methacrylate copolymer, methacrylic acid / hydroxyethyl methacrylate / acrylate copolymer; n-butyl methacrylate / methacrylic acid / ethyl acrylate copolymer and combinations thereof.

7. An aerosol hair spray product according to any preceding claim, 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 t-butylbenzoate / crotonic acid terpolymer, crotonic acid / vinyl acetate / vinyl neododecanoate terpolymer and combinations thereof.

8. An aerosol hair spray product according to any preceding claim, wherein the hair spray product has a spray rate of 0.3 g / s to 1.0 g / s, preferably 0.3 g / s to 0.8 g / s, and more preferably 0.3 g / s to 0.6 g / s, according to the Spray Rate Test.

9. The aerosol hair spray product of claim 8, wherein the spray rate of the hair spray product varies by no more than 30%, preferably no more than 20%, and more preferably no more than 10% from when the container holds 100% of the hair spray composition to when the container holds 25% of the hair spray composition.

10. An aerosol hair spray product according to any preceding claim, wherein the hair spray product has a Dv50 of from 40 μm to 90 μm, as measured by the Particle Size Distribution Test.

11. The aerosol hair spray product of claim 10, wherein the Dv50 does not change by more than 20 μm from when the container is 100% filled with the hair spray composition to when the container is 25% filled with the hair spray composition.

12. The aerosol hair spray product according to claim 1, wherein the spray diameter of the hair spray product is 5 cm to 15.25 cm.

13. The aerosol hair spray product of claim 12, wherein the spray diameter does not vary by more than 30%, preferably by more than 20%, and more preferably by more than 10% from when the container is 100% filled with the hair spray composition to when the container is 25% filled with the hair spray composition.

14. An aerosol hair spray product according to any preceding claim, wherein at least one of the container, the spray device, the actuator and the cap comprises 10% or more of a material selected from recycled materials, bio-based plastics and combinations thereof.

15. A method for styling hair, the method comprising: a) providing an aerosol hair spray product according to any preceding claim; as well as b) applying the hair spray composition to target portions of the hair where styling benefits are desired.

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