Patent Application
20240299610
The invention relates to air freshener aerosol sprays, methods of generating such aerosol sprays, and systems for dispensing such aerosol sprays.
Aerosol sprays are used to provide many consumer products, including air fresheners, deodorizers, disinfectants, insecticides, and cleaners. To provide such aerosol sprays, different types of dispensing systems have been developed. Some aerosol spray dispensing systems have or are connected to a power source causing the system to automatically dispense the sprays. Other types of aerosol dispensing systems are provided in containers that are actuated by a user on demand.
Even with the wide variety of dispensing systems and dispensing system configurations, for some products it can be difficult to generate an aerosol spray having desired properties. For example, in the case of air freshening products, the goal is for the system to provide the product such that a sufficient amount of fragrance experience is achieved soon after the dispensing, but also such that there is longevity in the fragrance experience. To achieve this, it is often important that the size of the particles in the aerosol spray be in a certain range, and that the particles do not greatly deviate from certain sizes. It is also often important that particles in an air freshening spray do not fall to the ground too quickly after the spray is dispensed and that the particles are discharged a sufficient distance from the dispensing system.
Many aerosol dispensing systems include a container that holds a product with liquid and gas parts. The gas included with the liquid product acts as a propellant to discharge the liquid product from the container when the system is actuated. The propellant pressurizes the container holding the liquid composition, and provides a force to expel the liquid composition from the container when the system is actuated. For such systems, there are two main types of propellants: (1) liquefied gas propellants (LPGs), such as hydrocarbon and hydrofluorocarbon (HFC) propellants, and (2) compressed gas propellants (CGAs), such as carbon dioxide and nitrogen. Generally speaking, as compared to CGA propellant systems, aerosol dispensing systems that use LPG propellants are able to produce smaller, more consistent sized particles in sprays. Thus, from a performance standpoint, systems using LPG propellants are often superior to systems using CGAs as propellants. But, LPG propellants include a high amount of volatile organic compounds (VOCs), thereby making their use subject to various regulations.
According to one aspect, our invention provides an air freshener aerosol spray dispensing system. The system includes a non-pressurized container that contains an air freshening formulation. The system also includes a spray nozzle in fluid communication with the container, the spray nozzle including a membrane having micropores through which the product passes as the product is dispensed from the system. The system further includes a pump configured to provide a force causing the air freshening formulation to move from the container and through the spray nozzle such that the air freshening formulation is discharged from the system as an aerosol spray. Particles in the spray have a Dv(50) size of about 30 μm to about 70 μm.
Optionally, the aerosol spray may emanate from the micropores of the membrane in the spray nozzle in Rayleigh jets that subsequently break up into particles of the aerosol spray.
Optionally, the nozzle may include 40 to 125 micropores, and the micropores may range in diameter from about 5 μm to about 10 μm.
Optionally, the micropores may range in diameter from about 5 μm to about 8 μm.
Optionally, a total open area on the surface of the membrane provided by the pores may be from about 1100 μm2 to about 6150 μm2.
Optionally, a total open area on the surface of the membrane provided by the pores may be from about 1100 μm2 to about 3200 μm2.
Optionally, the aerosol spray may include at least one air freshening composition including (i) fragrance oil and (ii) water or a solvent.
Optionally, the pump may be a positive displacement pump.
According to another aspect, our invention provides a method of generating an air freshener aerosol spray. The method includes steps of forcing an air freshener composition out of a non-pressurized container, and passing the composition through micropores on a membrane such that Rayleigh jets are produced, with the Rayleigh jets subsequently breaking up into particles of the aerosol spray. The composition includes (i) fragrance oil and (ii) water or a solvent.
The micropores may range in diameter from about 5 μm to about 10 μm and, optionally, from about 5 μm to about 8 μm.
Optionally, the aerosol spray may have a spray experience factor with a (negative) spray efficacy of up to about −3300 and a (negative) span factor of about up to about −1.25.
Optionally, the aerosol spray may have a particle quality factor with a (negative) Dv(90) particle size of up to about −90 μm and a (negative) span factor of up to about −1.25.
Optionally, a total open area on the surface of the membrane provided by the pores may be from about 1100 μm2 to about 6150 μm2.
Optionally, a total open area on the surface of the membrane provided by the pores may be from about 1100 μm2 to about 3200 μm2.
According to yet another aspect, our invention provides an air freshener aerosol spray with particles of an air freshener composition that includes a fragrance oil. The particles have a Dv(50) particle size of about 30 μm to about 70 μm, and the aerosol spray has a spray experience factor with a (negative) spray efficacy of about up to about −3300 and a (negative) span factor of up to about −1.25.
Optionally, the particles may have a Dv(50) particle size of about 35 μm to about 45 μm.
Optionally, the composition may include water, and the aerosol spray may have a spray experience factor with a (negative) spray efficacy of about 0 to about −400 and a (negative) span factor of about −0.75 to about −1.0.
Optionally, the composition may include solvent, and the aerosol spray may have a spray experience factor with a (negative) spray efficacy of about −950 to about −3300 and a (negative) span factor of about −0.8 to about −1.1.
According to a further aspect, our invention provides an air freshener aerosol spray with particles of a composition that includes a fragrance oil. The particles have a Dv(50) particle size of about 30 μm to about 70 μm, and the aerosol spray has a particle quality factor with a (negative) Dv(90) particle size of up to about −90 μm and a (negative) span factor of up to about −1.25.
Optionally, the particles may have a Dv(50) particle size of about 35 μm to about 45 μm.
Optionally, the composition may include water, and, the aerosol spray may have a particle quality factor with a (negative) Dv(90) particle size of about −50 μm to about −65 μm and a (negative) span factor of −0.75 to about −1.0.
Optionally, the composition may include a solvent, and the aerosol spray may have a particle quality factor with a (negative) Dv(90) particle size of about −40 μm to about −65 μm and a (negative) span factor of −0.8 to about −1.1.
The present invention relates to air freshener aerosol sprays, methods of generating such aerosol sprays, and systems for dispensing air freshener aerosol sprays. An aerosol spray is a suspension of particles (solid or liquid) in air or a gas. In many aerosol sprays, the spray is dispensed from a system with the use of a propellant gas. As discussed below, sprays according to embodiments of the invention are not formed using propellant gases. Thus, as used herein, an aerosol spray may mean a collection of particles suspended in normal air without a further propellant gas.
In some embodiments of the invention, the aerosol spray includes a fragrance compound(s) to provide an air freshening product.
Particular properties of the aerosol sprays described herein make the sprays useful for air freshening products. One such property is the size of the particles in the spray. The particle size may be characterized by the Dv(50) of the particles, which is the diameter for which 50% of the total spray volume is made up of droplets of equal or lesser diameter. In some embodiments of the invention wherein the aerosol spray is an air freshening product, the particles range in Dv(50) size from about 30 μm to about 70 μm. In more preferred embodiments of the invention, the particles range in Dv(50) size from about 35 μm to about 45 μm. The sizes of particles in aerosol sprays generated by the methods and systems described herein will be further described below and compared to sprays generated by other types of systems.
Another advantageous property of aerosol sprays according to embodiments of the invention is the distribution of the sizes of the particles in the sprays. The size distribution can be quantified as the span factor, which is defined by the following equation:
where Dv(10) is the diameter for which 10% of the total spray volume is made of droplets of equal or lesser diameter, Dv(50) is the diameter for which 50% of the total spray volume is made of droplets of equal or lesser diameter, and Dv(90) is the diameter for which 90% of the total spray volume is made of droplets of equal or lesser diameter. In embodiments of the invention, the span factor may range from about 0.75 to about 1.25. In particular embodiments of the invention using air freshening compounds with a water formulation, the span factor for the particles may range from about 0.75 to about 1.0. In other particular embodiments of the invention using air freshening compounds in a solvent-based formulation, the span factor for the particles in the aerosol spray may range from about 0.80 to about 1.1.
Still other advantageous properties of aerosol sprays according to embodiments of the invention are the distance spray particles travel from the dispensing system, the low amount of fallout of the particles from the spray in the air onto the ground, and the longevity of spray particles in the air over time. Methods for determining these properties will be described in conjunction with the comparative experiments described below.
Also described below are combinations of the properties of the aerosol sprays, such as a spray experience factor. As used herein, the spray experience factor is defined herein by the combination of spray efficacy and the negative of the span factor of the particles, where spray efficacy is defined as the negative of the product of the percent fallout and spray distance. Those skilled in the art will appreciate that the spray experience factor is indicative of the performance of an aerosol spray in a product such as an air freshener. In embodiments of the invention providing air freshening sprays, the spray experience factor has a (negative) spray efficacy of about 0 up to about −3300 and a (negative) span factor of up to about −1.25. In particular embodiments of the invention providing air freshening sprays with a water-based formulation, the spray experience factor has a spray efficacy of about 0 to about −400 and a (negative) span factor of about −0.75 to about −1.0. In other particular embodiments of the invention providing air freshening sprays with a solvent-based formulation, the spray experience factor has a spray efficacy of about −950 to about −3300 and a (negative) span factor of about −0.80 to about −1.1. The comparative data discussed below demonstrates that fragrant sprays dispensed from prior art systems do not have spray experience factors falling in the range of the spray experience factors of aerosol sprays according to embodiments of the invention.
Another combination of properties of sprays according to embodiments of the invention that is indicative of performance is a particle quality factor, which is defined herein by the negative Dv(90) particle size for the spray and the negative of the span factor for the spray particles. As will be appreciated by those skilled in the art, Dv(90) particle size is indicative of the amount of larger size particles in a spray, e.g., a lower Dv(90) indicates a lower amount of large particles. And, a lower number of large particles usually equates to less fallout of the spray. In embodiments of the invention, the particle quality factor has a (negative) Dv(90) of up to about −90 μm and a (negative) span factor of up to about −1.25. In particular embodiments of the invention providing air freshening sprays with a water-based formulation, the particle quality factor has a (negative) Dv(90) of about −50 μm to about −65 μm and a (negative) span factor of about −0.75 to about −1.0. In other particular embodiments of the invention providing air freshening sprays with a solvent-based formulation, the particle quality factor has a (negative) Dv(90) of about −40 μm to about −65 μm and a (negative) span factor of about −0.8 to about −1.1. The comparative data discussed below demonstrates that fragrant sprays dispensed from prior art systems do not have particle quality factors falling in the range of the particle quality factors of aerosol sprays according to embodiments of the invention.
Aerosol sprays as described herein may be generated using an aerosol dispensing system that includes a spray nozzle through which the product forming the aerosol spray passes. A spray nozzle 100 according to embodiments of the invention is shown in
It should be noted that nozzles according to embodiments of the invention are not limited to the configuration of the spray nozzle 100 depicted in
In particular embodiments of the invention, the membranes used with the nozzles are silicon wafer chips that are created using well-known manufacturing techniques that are often used to produce semiconductors. Examples of such silicon wafer chips and their manufacture can be seen in U.S. Pat. Nos. 8,936,160, 8,814,059, 9,566,398, and 10,632,265, which are hereby incorporated by reference their entirety.
The layout and number of the micropores in the membranes in spray nozzles according to embodiments of the invention is not limited to the configuration shown in
One design parameter for nozzles according to embodiments of the invention is the total number of micropores in the membrane used in the nozzle, i.e., the number of micropores in the nozzle. In some embodiments of the invention, the number of micropores for a spray nozzle range from 40 to 125. Other design parameters of the spray nozzles are the diameter of the micropores in the membrane and the cone angle of the spray emanating from the micropores. In some embodiments of the invention, the diameters of the pores range from about 5 μm to about 10 μm. In more preferred embodiments of the invention, the diameters of the pores range from about 5 μm to about 8 μm. In most preferred embodiment of the invention, the diameters of the pores range from about 5 μm to about 7 μm. Regarding, cone angle, this is defined as the angle of the spray jet produced by a micropore relative to the axis of that micropore. For example, as shown in the spray nozzle 300 depicted in
Another manner of designing the parameters of spray nozzles according to embodiments of the invention is by looking to the open area in the membrane that is provided by the pores, i.e., the cross-sectional area of a pore on the surface of the membrane multiplied by the number of pores. For example, a membrane in a spray nozzle according to an embodiment of the invention has eighty-two pores having diameters of 6 μm, for a total open area of about 2318 μm2. In embodiments of the invention, the total open area on the surface of the membrane provided by the pores the membranes is from about 1100 μm2 to about 6150 μm2. In preferred embodiments of the invention, the total open area on the surface of the membrane provided by the pores is from about 1100 μm2 to about 3200 μm2. Those skilled in the art will appreciate that the open area for the nozzle will be related to operating conditions for the dispensing systems, particularly the means for generating the force that pushes the formulated product through the membrane. For example, in embodiments of the invention that use a pump mechanism (as will be discussed below), the open area provided by the pores of the membrane will be correlated to the pressure force that the pump generates to cause the formulated product to move through the membrane.
Configurations of nozzles according to specific embodiments of the invention are shown in TABLE 1. The layout of the micropores and membranes for the nozzles shown in TABLE 1 is as shown in
The spray nozzles described herein may be used in conjunction with many different types of dispensing systems. Two types of systems that are well known in the art are automatic aerosol dispensers and base-container aerosol dispensers. A specific example of an automatic aerosol dispensing system is sold under the name GLADE® Automatic Spray by S.C. Johnson & Son, Inc. of Racine, Wisconsin (the assignee of the subject application), and a specific example of a base-container aerosol dispensing system is sold under the name GLADE® Air Freshener by S.C. Johnson & Son, Inc. Example configurations of automatic aerosol dispensers and base-container aerosol dispensers will now be described.
Unlike prior art automatic aerosol dispensing systems, systems according to embodiments of the invention do not use a propellant gas to pressurize the container as a means for effecting discharge of the product from the container; the product in the container remains at standard atmospheric pressure. Rather than using a propellant gas, in embodiments of the invention the actuating mechanism 410 is a pump. More specifically, the actuating mechanism 410 may be in the form of a positive displacement pump, such as a reciprocating pump or a rotary pump. For example, as a reciprocating pump, the pump can include a piston, plunger, diaphragm, or other structure that functions to provide the force that drives the product out of the container 404. In the case of rotary pumps, the pump may include gears, lobes, screws, vanes, and/or cams to generate the force to discharge the product from the container. In particular embodiments of the invention, the pump can use a precompression valve that functions to provide a highly linear delivery of pressure, which results in a consistent flow of product out of the system.
It should be noted that automatic aerosol dispensing systems according to embodiments of the invention are not limited to the specific configuration shown in
Because the automatic aerosol dispensing systems according to embodiments of the invention do not use a propellant gas, the systems will not be subject to the regulations associated with systems using VOC-containing propellant gases, such as LPGs. However, as will be demonstrated by the comparison results below, the systems according to the invention may still provide product sprays having equivalent or better properties to sprays generated in LPG systems. Moreover, the sprays from inventive systems are often superior to sprays generated from other types of systems that do not use VOC-containing propellant gases, such as CGAs.
Base-container aerosol dispensing systems according to embodiments of the invention are not limited to the specific configuration shown in
In embodiments of the invention, a propellant gas is used to effect the discharge of the aerosol product from the base-container dispensing system. For example, the containers in automatic and base-container aerosol dispensing systems as described above may be pressurized with a propellant gas. As discussed above, in many prior art systems, the propellant gas contains a significant amount of volatile organic compounds (VOCs). Propellants can be categorized by being low VOC, no VOC, and VOC exempt. Low VOC propellants, such as dimethyl ether, have a low vapor pressure and are used to reduce the VOC level in products. Dimethyl Ether can be blended with water. Non-VOC propellants include HFC 152a, HFC 134, and Ethane. LPGs such as propane, butane and isobutane are considered VOCs. The propellant HFO 1234ze sold by Honeywell International Inc., of Charlotte, North Carolina, is part of a new generation of VOC exempt propellants. With this, low VOC could be a combination of a VOC propellant with either a VOC-free propellant or solvent or VOC exempt propellant. Base-container aerosol systems according to embodiments of the invention may use low VOC, no VOC, and VOC exempt propellants.
No propellant gas is used in still other embodiments of base-container aerosol systems according to the invention. Instead, in these embodiments a pumping mechanism generates the pressure force to discharge the product through the spray nozzle. Examples of such pumping mechanisms include hand-actuated trigger systems, such as those that are commonly found in consumer products. Specific examples can be seen in U.S. Pat. Nos. 5,474,215, 6,189,739, and 6,708,852, which are hereby incorporated by reference in their entirety. As is the case with the non-propellant automatic aerosol dispensing systems discussed above, the base-container aerosol systems according to the invention do not include VOC-containing LPGs but provide aerosol sprays with desirable properties.
Different formulations are used in a myriad of commercial products to deliver fragrance in the air. Single phase base-container CGA aerosol dispensing systems tend to have water-based formulations that typically include water, emulsifier and fragrance. At other times, water-based formulations are used in conjunction with an LPG to create a dual phase formulation. In such cases, the product is shaken to disperse the LPG within the water formulations. Automatic aerosol dispensing systems often rely on the LPG propellant as a co-solvent for the fragrance. In such automatic devices the fragrance is dissolved in an organic solvent and is blended with the LPG to create a single-phase formulation. Diffusing systems use fragrance oil that usually consist of aroma chemicals mixed with various solvents.
In one embodiment of present invention, the air freshener composition may be a water-based formulation comprising water, emulsifier, and fragrance oil, as follows:
In other embodiments of the invention, the air freshening compound may be a solvent-based formulation having a co-solvent, such as an alcohol, to facilitate the solubilization of the ingredients. Preferably, the co-solvent is a low molecular weight monohydric C alcohol, such as ethanol, propanol, isopropanol, butanol or isobutanol. Other co-solvents, such as acetone, may also be included in the aerosol composition. In a general embodiment, an emulsifier may be present as set forth above. If the co-solvent is present in the composition in an amount that is insufficient to form an emulsion without the presence of the emulsifier, the emulsifier can be present in such instance in an amount ranging from about 0.4 to about 4 wt. %. Additional adjuvants, such as fragrances, corrosion inhibitors, pH adjustors, antimicrobials, preservatives, and the like, may also be included. Preferred individual ranges for the above-listed adjuvants are from 0 to about 5 wt. %, more preferably from 0 to about 2 wt. %.
In another embodiment, the aerosol composition could consist of just the fragrance oils that are developed by Givaudan Company of Vernier, Switzerland, Takasago International Corporation of Tokyo, Japan, and Surmise AG of Holzminden, Germany. Such products are typically used in plug in scented oils or diffusers. Additionally, the fragrance oil could be added to a solvent such as low vapor pressure solvent such as DPMA (dipropylene glycol ether acetate), Isopar™ M (by ExxonMobil Chemical Company of Irving, Texas), DPM (dipropylene glycol monomethyl ether), ethanol, and combinations thereof, can be used to add vapor pressure to enhance the fragrance experience and less fallout. Additionally, low-VOC formulations could be created using low-VOC solvents. For low-VOC formulations, a class of materials includes acetone, dimethyl carbonate, methyl acetate, parachlorobenzotrifluoride (sold under the brand name OXSOL® 100 by Mana of New York, New York), tert-butyl acetate, and propylene carbonate. For solvent-based formulations, the air freshening composition may be as follows:
In order to demonstrate the unique properties of aerosol sprays according to embodiments of the invention, experiments were conducted to compare the properties of the sprays to sprays dispensed from commercially available aerosol dispensing systems.
To model systems according to embodiments of the invention, inventive systems were created using spray nozzles as described above. In particular, spray nozzles having the configurations of design numbers 1-9 in TABLE 1 above were used in the inventive systems. The spray nozzles were attached to a testing apparatus that simulates the automatic aerosol dispensing systems with pump actuating mechanisms described above. The testing apparatus included a stepper motor driving an actuating plate to generate the force to move the composition out of a container and through a spray nozzle according to embodiments of the invention. The force was comparable to the force that is used to discharge formulated product out of automatic dispensing systems. Both a water-based formulation and a solvent-based formulation (as described above) were tested with the spray nozzles.
The air freshening aerosol sprays dispensed from the testing apparatus were compared to air freshening sprays dispensed from commercially available automatic aerosol spray dispensing systems, base-container aerosol dispensing systems, and other types of aerosol dispensing systems. Five different automatic aerosol dispensing systems were tested. The automatic aerosol dispensing systems used solvent-based formulations. Three of the automatic systems had a configuration as generally found in the automatic systems described above, with the automatic systems using propellant gases to generate the aerosol spray. The other two automatic aerosol systems were wick diffuser systems (hereafter “diffusers”), as are well known in the art. Five different base container aerosol systems having water-based formulations and liquified gas propellants (LPG), and eight different base aerosol systems having water-based formulation and compressed gases (CGA) as propellants were tested. Also tested were two base-container aerosol systems having a bag-on-valve configuration. Such bag-on-valve systems are well-known in the art, and examples of such systems can be seen, for example, in U.S. Pat. No. 9,902,552. Further tested were three trigger-based dispensing systems with water-based formulations, with these dispensing systems having a hand-operated trigger that operates a pump to generate the aerosol spray, as described above.
The aerosol sprays as dispensed from the inventive and comparison systems were evaluated at ambient indoor conditions, i.e., 70° F. and ordinary humidity. The systems were stored for at least twenty-four hours before the tests. The spray rates were determined through weight change during a ten second spray, were reported as grams per second, and are averaged over two sprays during the first forty seconds of sample life. The automatic aerosol dispensing systems were actuated five times for each trial. The actuator for the base-container aerosol systems (i.e., the LPG, CPG, and bag-on-valve systems) were completely depressed for five seconds for each trial, and the systems were shaken appropriately before spraying, allowing up to two to four seconds between shaking and spraying. The trigger-based dispensing systems were actuated five times for each trial. Multiple trials were conducted for each of the systems.
The particle size as mass median diameter, Dv(50), in microns (micrometers, μm) was determined from a Malvern laser diffraction particle size analyzer equipped with a 300 mm lens. The base-container aerosol systems and trigger systems were sprayed at a distance of six inches from the beam. The automatic systems were sprayed one to two inches from the lens. All products were sprayed to ensure no products were not on the lenses. A cutoff was applied at 301.7 μm to eliminate ghost peaks caused by “beam steering.” The span factor was determined based on the measurements from the diffraction particle size analyzer and calculated according to the equation described above.
The fallout and product spray distance were tested in a low current room to minimize drifts from air current. Each system was placed on a lab jack and sprayed horizontally on 3 ft×100 in craft paper. Spray height was adjusted to be about eighteen inches from the floor. Each of the systems were sprayed for five seconds or actuated ten times to get reproducible amount of product on the craft paper. The fallout was determined through weight change of the craft paper before and after spraying the product. The weight of the product (package and refill) were determined before and after testing. The amount of product on the paper was determined gravimetrically. The fallout was determined by the quotient of amount of product that accumulated on the craft paper and the amount of product that were sprayed in the air times one hundred:
The spray distance was determined by visual inspection of the majority of droplets on the paper or in the air. The spray distance was measured (in inched) as the distance from the tip of the product to the end of the plume.
The longevity of the aerosol sprays was measured by monitoring total particle concentration in a twenty-four cubic foot mixed chamber. Equal dosages of the sprays were dispensed into the chamber from the inventive and comparison systems and concentrations were measured using a TSI 3321 aerodynamic particle sizer in twenty second intervals over the course of twenty-five minutes. The inventive and comparison systems were placed upright at the bottom center of the chamber that is mixed and has no air exchanges. The sampling was done via a one-half inch port approximately two feet above the plume. The longevity was determined as the time to teach a 5% particle concentration.
Results of the experiments are shown in TABLE 2. For the inventive systems listed in the table, “SN” designates the spray nozzle number (per the configurations described above), “WB” indicates that a water-based formulation was used, and “SB” indicates that a solvent-based formulation was used. A discussion of the results follows.
Fallout is a significant factor in the evaluation of aerosol sprays because too much fallout is undesirable from a consumer satisfaction standpoint. The data shown in
The results of the longevity tests for an inventive system and comparison systems are shown in TABLE 4 and
The longevity of the aerosol spray from the inventive systems was greater than the longevity of the aerosol sprays from the automatic and diffuser systems, greater than most of the CGA propellant systems, and comparable to the LPG propellant system.
As described herein, the present invention provides aerosol sprays, methods of generating aerosol sprays, and systems for generating aerosol sprays that are not found in the prior art. The inventive aerosol sprays have properties and combinations of properties that make the sprays ideal for many applications, particularly as air freshening products.
While various embodiments of the invention have been described above, it should be understood that they have been presented by way of example, and not limitation. It is apparent to persons skilled in the relevant arts that various changes in form and detail can be made therein. Thus, the invention should not be limited by any of the above-described embodiments, but should be defined only in accordance with the following claims and their equivalents.
The invention described herein can be used in the commercial production of aerosol dispensing systems. Such aerosol dispensing systems have a wide variety of uses, for example, in the market of air freshening products.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/050925 | 1/17/2022 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 63138505 | Jan 2021 | US |
