Classifications

• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
  • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
  • A01N25/10—Macromolecular compounds
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
  • A01N25/28—Microcapsules or nanocapsules
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/04—Dispersions; Emulsions
  • A61K8/044—Suspensions
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/11—Encapsulated compositions
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin

Definitions

• the present invention relates to an aqueous slurry that contains oily medium-filled microcapsules dispersed in an aqueous medium.
• the microcapsules have an ionic acrylate copolymer that can provide for beneficial leak resistance of the oily-medium and yet can release the oily medium upon drying/removal of the aqueous medium.
• the aqueous slurry is useful in a broad range of applications including agriculture and cosmetics.
• Microcapsules have been used in a variety of fields. Most commonly, microcapsules found commercial utility in carbonless paper and pressure-sensitive adhesives. These microcapsules need to be durable and to rupture upon sufficient pressure. Such microcapsules have been formed from a variety of polymers including a urea-formaldehyde or a urea-melamine copolymer. Such microcapsules can be formed by interfacial polymerization wherein one monomer is in the oil phase and the other is in the aqueous phase. One phase is dispersed a droplets in the other and then polymerization proceeds at the oil-water interface to form a shell wall around the droplet. But sometimes it is advantageous have a core without the need to include a monomer.
• U.S. Pat. No. 5,073,296 relates to in-situ polymerization wherein the monomers are contained in a continuous aqueous phase.
• the polymerization forms a micrapsule wall or shell around the dispersed oil microdroplets.
• the monomer is a water-soluble vinyl monomer, such as vinylpyrrolidone, and optionally a comonomer.
• the intended result is a stable homogenous dispersion of oil microdroplets in an aqueous medium.
• Such an aqueous medium can be used in cosmetics wherein the microdroplets rupture upon slight pressure to release the oil, such as a skin aid.
• U.S. Pat. No. 5,711,951 also relates to in-situ polymerization using water-soluble monomer to encapsulate a dispersed oil phase.
• the stability of the dispersion is increased by the further inclusion of a thickening agent.
• These suspensions are also useful in cosmetic and shampoo products.
• microcapsule suspension product is disclosed in U.S. Pat. No. 7,915,215.
• the shell of the microcapsule is formed from polyvinyl alcohol crosslinked by boron or persulfate ions.
• the microcapsules contain an oil phase such as a fragrance or cleaning product. Once the water phase is removed, however, the microcapsules break down and release the oil material.
• One example shows that coating the aqueous suspension onto paper and allowing it to dry resulted in the paper being oil saturated after one hour. Thus, upon removal of water, the microcapsules disintegrated and released the oil core material without the need for pressure.
• the crosslinked polyvinyl alcohol microcapsule suspension of the U.S. Pat. No. 7,915,215 is quite useful. It has been discovered, however, that the storage stability of the suspension could be improved. Specifically, while in the aqueous suspension, the microcapsules sometimes leak some of the oil core, which is undesirable. It would be useful to develop an alternative aqueous microcapsule suspension. It would further be advantageous to have an alternative suspension that also begins release of the oil phase from the microcapsule upon drying without the need for pressure/force to rupture the microcapsule. It would also be useful to have a suspension that resists leaking of the oil phase core material while in the aqueous suspension but can still provide automatic release of the oil upon drying.
• the present invention relates to an aqueous suspension or slurry having oil-filled microcapsules therein.
• a first aspect of the invention relates to a composition, comprising an aqueous medium having dispersed therein oily medium-containing microcapsules, wherein the oily medium-containing microcapsules comprise an ionic acrylate copolymer shell encapsulating said oily medium.
• the ionic acrylate copolymer can contain anionic or cationic groups pendent to an acrylate monomer.
• the copolymer typically is formed from a mono-functional acrylate having an ionic group and a poly-functional acrylate, though other monomers can also be present.
• Another aspect of the invention relates to a process of making an aqueous slurry composition, which comprises: (a) combining an oily medium, which contains an oil-soluble polymerization initiator, with an aqueous medium, which contains a water-soluble polymerization initiator, a water-soluble mono-functional acrylate monomer having an ionic group, a water-soluble multi-functional acrylate monomer, and/or water-soluble polymerizates thereof, to form an emulsion wherein the oily medium is the dispersed phase in the form of droplets and the aqueous medium is the continuous phase; and (b) subjecting the emulsion to sufficient temperature and duration to deposit and/or polymerize an ionic acrylate copolymer shell around substantially every droplet to thereby encapsulate said oily medium and form said aqueous slurry.
• a further aspect of the invention relates to the use of the aqueous slurry composition to deliver the oily medium to a substrate.
• a process which comprises applying the aqueous slurry to a substrate and drying the slurry to thereby release the oily medium onto the substrate.
• the oily medium can contain an effective agent for cosmetics, cleaners, or agriculture, but is not limited thereto.
• the substrate can include skin, hair, soil, or vegetation such as plants, but is not limited thereto.
• the present invention is based on the discovery that in an aqueous slurry containing microcapsules, an ionic acrylate copolymer can form a useful microcapsule wall or shell around an oily medium.
• the aqueous slurry comprises an aqueous medium having dispersed therein oily medium-containing microcapsules.
• the dispersion need not be a homogenous suspension of the microcapsules, i.e., the microcapsules can settle in the aqueous medium, though such a uniform suspension can be advantageous in some embodiments.
• the aqueous medium comprises water and optionally other water-soluble compounds to form a solution. Additional compounds can include water-soluble or water-swellable polymers, thickeners, surfactants, and/or colorants, as well as pH adjusting agents (acid or base). The polymerization initiators or their by-products from the microcapsule formation can also be present.
• the aqueous medium can also comprise water-miscible solvents such as alcohols, though their presence is usually limited, if present at all, to less than 10% of the aqueous medium. Generally, water is the majority component of the aqueous medium and typically comprises at least 50%, and more typically at least 75% and often at least 90% of the aqueous medium.
• microcapsules Dispersed within the aqueous medium are microcapsules. These microcapsules contain an oily medium.
• the oily medium comprises one or more oils, optionally with oil-soluble compound(s) dissolved therein.
• An “oil” as used herein means a substance that is substantially immiscible in water and will provide a separate phase when mixed with water.
• the oil and the oily medium are not particularly limited as a variety of organic or hydrophobic substances can be advantageous dispersed in an aqueous medium for convenient application or storage via the microcapsules of the present invention.
• the oily medium can contain hydrocarbons, halogenated hydrocarbons, silicone oil, etc., but is not limited thereto.
• the oily medium comprises an effective agent optionally mixed with a carrier.
• Effective benefit agents are substances that provide a beneficial effect for an intended use or purpose.
• the effective agents most commonly used in the aqueous slurry of the invention are cosmetic effective agents and agricultural effective agents.
• Cosmetic effective benefit agents are useful for improving the look, feel, or smell of a substrate to which it is applied. Skin and hair are typical substrates, but other substrates may include wood (cabinets, flooring, etc.) tile, and leather.
• Examples of cosmetic effective benefit agents include a fragrance, a UV-absorber, a moisturizer, especially a skin or hair moisturizer, etc. Two or more agents can be used in the oily medium.
• Agricultural effective agents are useful for improving or protecting the health or growth of animals or plants.
• the agricultural effective agents are used on plants and include such agents as a pesticide, a herbicide, and/or a plant fertilizer.
• the effective agent such as a cosmetic effective agent or an agricultural effective agent, may be used per se as an oil or can be combined with an oil carrier such as an alkane, an aromatic, etc.
• additional compounds can be present in the oily medium in dissolved or dispersed form.
• the polymerization initiators or their by-products from the microcapsule formation can also be present.
• the oily medium is contained in microcapsules that are dispersed in the aqueous medium.
• the microcapsules generally have a size in the range of 1 to 50 microns, and often 5 to 25 microns, but it not particularly limited.
• the microcapsule shell that is the wall that surrounds the oily medium, comprises an ionic acrylate copolymer.
• an ionic acrylate copolymer means a polymer of two or more monomers where at least one monomer is a mono-functional acrylate having an ionic group.
• the ionic group can be anionic such as a carboxylic acid, a sulfonic acid, etc., or cationic such as an ammonium group.
• the ester moiety of the mono-functional acrylate contains 1 to 6 carbon atoms, more typically 1 to 4 carbon atoms.
• the ionic group is generally a substituent on one of the carbon atoms of the ester moiety.
• 2-carboxyethyl acrylate is a suitable anionic mono-functional acrylate monomer
• trimethylammoniumchloride ethyl methacrylate is a suitable cationic mono-functional acrylate monomer.
• the ionic mono-functional acrylate should be water-soluble.
• the copolymer contains another monomer.
• this additional monomer is multi-functional so as to allow for crosslinking and is usually an acrylate as well; i.e., a biacrylate or triacrylate monomer.
• the commoner is also water-soluble.
• a water-soluble ethoxylated trimethylolpropane triacrylate is a suitable comonomer for forming an ionic acrylate copolymer of the present invention.
• Additional comonomers can also be present including non-acrylate monomers.
• Preferably all monomers used to form the ionic acrylate copolymer are water-soluble.
• the monomers are partially polymerized to form a polymerizate, also known as a prepolymer, and it is preferred that such polymerizates are also water-soluble.
• the weight ratio of mono-functional acrylate to multi-functional acrylate is not particularly limited, especially if the monomers and any polymerizates remain water-soluble.
• the weight ratio of mono-functional acrylate to multi-functional acrylate is within the range of 30:70 to 70:30, respectively; more typically 35:65 to 65:35; and often 40:60 to 60:40.
• Higher amounts of the multi-functional acrylate tend to reduce leakage of the oily medium from the microcapsule while in the aqueous slurry. But too high a ratio may cause microcapsule shell formation to be difficult; e.g., the polymerizates may become water-insoluble.
• the weight ratio of mono-functional to multi-functional is about 35:65 to 60:40.
• the microcapsule shell generally comprises 5 to 25% and more typically 10 to 20%, by weight, of the microcapsule.
• the microcapsules are intended to contain the oily medium within them while the microcapsule remains dispersed in the aqueous medium of the slurry composition. Removal of the aqueous medium, however, should trigger the breakdown of the microcapsules and release of the oily medium.
• the release of the oily medium while the microcapsule is still in the slurry, e.g., leaking, is typically less than 10%, more typically less than 5%, preferably less than 2%, more preferably less than 1%, and often less than 0.5% when the slurry is stored for four weeks.
• the removal of the aqueous medium can result in release of the oily medium over various time periods, depending on the ionic acrylate copolymer shell material, size, and amount, but often achieves release of 50%, or over 50%, of 80-100%, or even of 95-100% of the oily medium, in some embodiments within 6 hours after the aqueous medium is removed, or in other embodiments within 24 hours, or even within 48 hours after the aqueous medium is removed.
• the release does not require pressure to rupture the microcapsules but instead begins spontaneously during or after the removal of the aqueous medium.
• the slurry composition according to the invention is conveniently made by a process that deposits the ionic acrylate copolymer only from the aqueous phase to form a shell around the dispersed oily medium.
• the process comprises combining an oily medium, which contains an oil-soluble polymerization initiator, with an aqueous medium, which contains a water-soluble polymerization initiator, a water-soluble mono-functional acrylate monomer having an ionic group, a water-soluble multi-functional acrylate monomer, and/or water-soluble polymerizates thereof, to form an emulsion.
• the emulsion is an oil-in-water emulsion wherein the oily medium is the dispersed phase in the form of droplets and the aqueous medium is the continuous phase.
• the emulsion is subjected to sufficient temperature and duration to deposit and/or polymerize an ionic acrylate copolymer shell around substantially every droplet to thereby encapsulate the oily medium and form the aqueous slurry of the invention.
• the system is usually subject to mixing in order to form and maintain the emulsion state.
• the monomers used to form the ionic acrylate copolymer can be partially polymerized in the aqueous medium. Generally at least one monomer species remains and often two or more species remain along with the newly formed polymerizates. The type of monomers, the ratios, and the amount of reaction should be controlled so that the polymerizates and any remaining monomers are water-soluble. Additional monomers of the same or different species as the mono- and multi-functional acrylate monomers can be added before, during, and/or after the polymerizates are formed.
• the polymerization and/or deposition of the ionic acrylate copolymer can begin.
• the conditions used to form the shell wall correspond to polymerization conditions.
• the phrase “polymerization and/or deposition” is used to include polymerization from only monomers as well as polymerization involving a polymerizate from a prior partial polymerization; e.g., a prepolymer may deposit onto the droplet and react with other prepolymers and/or monomers in forming the shell.
• the aqueous medium may contain additional monomers of the same or different species as the mono- and multi-functional acrylate monomers, which additional monomers can be added before and/or during the polymerization and deposition step.
• the aqueous medium contains a pH adjusting agent such as an inorganic acid or base.
• the reaction usually takes place between 50° C. to 100° C., such as around 75° C. to 95° C.
• the reaction is run for sufficient time that substantially all of the droplets are encapsulated.
• the aqueous medium contains a small amount of non-encapsulated oily medium, such that the amount of free oil in the aqueous medium is less than 5%, more typically less than 1%, and usually less than 0.5%, by weight.
• Suitable initiators and/or catalysts are well known in the art. Typically azo initiators are used as both water-soluble and oil-soluble forms are commercially available. Other initiator types include sodium persulfate and ammonium persulfate. The initiators are energy activated generating free radicals when subjected to heat or other energy input. In certain embodiments initiators can include peroxy initiators, azo initiators, peroxides, and compounds such as 2,2′-azobismethylbutyronitrile, dibenzoyl peroxide.
• the free radical initiator can be selected from the group of initiators comprising an azo or peroxy initiator, such as peroxide, dialkyl peroxide, alkyl peroxide, peroxyester, peroxycarbonate, peroxyketone and peroxydicarbonate, 2,2′-azobis (isobutylnitrile), 2,2′-azobis(2,4-dimethylpentanenitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis(2-methylpropanenitrile), 2,2′-azobis (methylbutyronitrile), 1,1′-azobis (cyclohexanecarbonitrile), 1,1′-azobis(cyanocyclohexane), benzoyl peroxide, decanoyl peroxide; lauroyl peroxide; benzoyl peroxide, di(n-propyl) peroxydicarbonate, di(sec-butyl) peroxydicarbonate, di(
• the aqueous slurry of the present invention can be used in a variety of applications.
• the process comprises applying the aqueous slurry to a substrate and drying the slurry to thereby release the oily medium onto said substrate.
• the substrate can be skin or hair, such as in a cosmetic for humans, soil or plants, such as for agriculture, wood, tile, or leather, but is not limited thereto.
• the oily medium can contain an appropriate effective benefit agent for the intended application.
• the oily medium can contain a fragrance, such as an aromatic compound(s), and provide a somewhat sustained release of the fragrance after drying.
• Benefit agents can include fragrances, perfumes, silicones, waxes, flavors, vitamins, fabric softening agents, pharmaceuticals, lubricants, cleaners, and/or biocontrol agents including biocides, herbicides, insecticides, mildewcides, and the like.
• the objective of such treatment is generally to leave deposited on the surfaces of substrates enough benefit agent so that there is a residual benefit imparted to the substrate surface after treatment of the substrate is completed. This feature can be useful in a cosmetic as well as a cleaner.
• the slurry can be applied to soil and the oily medium can contain a herbicide.
• the aqueous medium Upon applying the slurry of the invention, such as by spraying, onto a substrate such as plants and/or soil, the aqueous medium will dry and the microcapsules will release the benefit agent such as herbicide over a somewhat delayed and/or sustained time frame. In further embodiments the microcapsules will release upon drying, releasing the benefit agent.
• Benefit agents that are herbicides can include sulfonylurea herbicides, urea herbicides, imidazolinone herbicides, diphenyl ether herbicides, hydroxybenzonitrile herbicides, 2-(4-aryloxyphenoxy)alkanoic acid herbicides and oxime herbicides; carbamate and thiocarbamate herbicides, quaternary ammonium salt herbicides, triazole herbicides; phytohormone herbicides, including aryloxyalkanoic acid herbicides, arenecarboxylic acid herbicides, pyridinecarboxylic acid herbicides, and pyridyloxyacetic acid herbicides; 2,6-dinitroaniline herbicides, amide herbicides, and anilide herbicides, isoproturon, chlortoluron, metoxuron, linuron, monolinuron, dimefuron, diuron; imidazolinone herbicides such as im
• Isoxaben anilide herbicides such as diflufenican, mefenacet and monalide; phenoxyalkanoic acid herbicides such as 2,4-dichlorophenoxy acetic acid (2,4-D); 2-methyl-4-chlorophenoxy acetic acid (MCPA); and 2-(4-chloro-2-methylphenoxy) propionic acid (mecoprop); salts, esters of N-(phosphonomethyl)glycine (glyphosate); bipyridyl herbicides, e.g.
• Benefit agents can also include agrochemicals such as fungicides, e.g., dodine; and plant growth regulators such as chlormequat, ethephon and maleic hydrazide. and mixtures of one or more of any of the foregoing.
• Water phase 1 containing water and water phase initiator, is placed in a jacketed steel reactor at 40° C. with mixing at 1000 rpm with a 4-tip flat mill, and a nitrogen blanket at 100 cc/min. The batch is heated from 40 to 75° C. in 45 minutes and held at 75° C. for 45 minutes. A second water phase (containing a water-soluble multifunctional acrylate, a charged mono-functional acrylate, acid or base solution for pH adjustment (optionally), and water, and pre-heated to 60° C.) is added, and the combined water phases held at 75° C. for another 60 minutes before cooling to 60° C. in 75 minutes.
• a second water phase containing a water-soluble multifunctional acrylate, a charged mono-functional acrylate, acid or base solution for pH adjustment (optionally), and water, and pre-heated to 60° C.
• An oil phase solution containing the core oil and oil phase initiators (pre-heated to 60° C.) is added and mixing rpm increased to about 3000 for milling. After 30 minutes, batch temperature is increased to 75° C. in 30 minutes, increased from 75 to 95° C. in 7 hours, and held at 95° C. for 6 hours. To maintain emulsion stability during the acrylate wall deposition and cross-linking, milling is continued throughout the curing cycle.
• the water phase initiator used was Wako V-50.
• the oil phase initiators were both Vazo-67 and Vazo-88.
• An anionic wall polymer was created using SR415 (30 ⁇ ethoxylated trimethylolpropane triacrylate) and CD9055 (2-carboxyethyl acrylate). In this case pH adjustment of the water phase was done with 21.5% NaOH solution.
• a cationic version of the polymer was also prepared, using SR415 and TMACEMA (trimethylammoniumchloride ethyl methacrylate—a quaternary ammonium methacrylate)
• a series of anionic wall capsule batches was prepared and evaluated.
• the variables evaluated in this series include wall composition (ratio of SR415/CD9055), wall level, and V-50 initiator level. Test results for batches made with different wall compositions are shown in Table 1.

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• Public Health (AREA)
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• Animal Behavior & Ethology (AREA)
• Birds (AREA)
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• 2016
  • 2016-09-01 WO PCT/US2016/049861 patent/WO2017040759A1/fr active Application Filing
  • 2016-09-01 CA CA2980193A patent/CA2980193C/fr active Active
  • 2016-09-01 EP EP16842968.6A patent/EP3344382A4/fr active Pending
  • 2016-09-01 AU AU2016317844A patent/AU2016317844B2/en active Active
  • 2016-09-01 CN CN201680023919.XA patent/CN107530672B/zh active Active
  • 2016-09-02 US US15/255,986 patent/US20170064945A1/en not_active Abandoned
• 2019
  • 2019-10-17 US US16/656,436 patent/US11889831B2/en active Active

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