JP2022100123A - Aerosol composition, aerosol product and unmanned flying body - Google Patents

Abstract

To provide an aerosol composition that has high pigment dispersion stability to offer good visibility, and can be sprayed to a target site with high accuracy and from a long distance.SOLUTION: An aerosol composition contains a pigment, clay mineral A, a polymer thickener and water. In the aerosol composition, the content of the clay mineral A is 0.8 mass%-12.0 mass% and the content of the polymer thickener is 0.03 mass%-0.9 mass%. The water dispersion of the clay mineral A has thixotropy.SELECTED DRAWING: None

Description

The present disclosure relates to an aerosol composition used as a marking agent and the like, and an aerosol product and an unmanned air vehicle using the aerosol composition.

In recent years, against the backdrop of the declining birthrate and aging population and the aging of infrastructure, the use of remotely controllable unmanned aerial vehicles such as drones and multicopters has been actively promoted in the civil engineering and construction fields. For example, at the infrastructure inspection site, it is necessary to mark the parts that need repair at the time of inspection, but by mounting the aerosol on an unmanned aerial vehicle such as a drone, even for bridges and structures that require scaffolding. , Easy, efficient and safe marking.
For example, in Patent Document 1, it is considered to eject a liquid from an aerosol container provided in an unmanned flying object to perform marking.

Japanese Unexamined Patent Publication No. 2020-175683

Assuming marking by spraying aerosol from an unmanned aerial vehicle such as a drone, the function as an aerosol is important, for example, long-distance spraying of 3 m or more and stable spraying from various angles are possible. I've come to understand. However, at present, there is no aerosol composition that can meet such needs.
In view of such problems, the present disclosure discloses an aerosol composition having high pigment dispersion stability, good visibility, high elasticity collection and long-distance spraying, and an aerosol product and unmanned flight using the aerosol composition. Provide the body.

The present disclosure is an aerosol composition.
The aerosol composition contains a pigment, clay mineral A, polymer thickener and water.
The content of the clay mineral A in the aerosol composition is 0.8% by mass to 12.0% by mass.
The content of the polymer thickener in the aerosol composition is 0.03% by mass to 0.9% by mass.
The clay mineral A relates to an aerosol composition in which the aqueous dispersion has thixotropic properties.

According to the present disclosure, an aerosol composition having high pigment dispersion stability, good visibility, high elasticity, and long-distance spraying, and an aerosol product and an unmanned air vehicle using the aerosol composition are provided. Can be done.

Unless otherwise specified, the description of "XX or more and YY or less" or "XX to YY" indicating a numerical range means a numerical range including a lower limit and an upper limit which are end points.
When numerical ranges are described step by step, the upper and lower limits of each numerical range can be arbitrarily combined.

Hereinafter, each component used in the above aerosol composition will be described.
The aerosol composition contains a pigment. The pigment is not particularly limited, and known pigments such as inorganic pigments and organic pigments can be adopted. By using a pigment, the visibility required as a marking agent can be imparted to the aerosol composition. The pigment preferably contains an inorganic pigment.

Inorganic pigments are, for example, white pigments such as titanium oxide, zinc oxide, lead white, calcium carbonate, magnesium carbonate and silica; black pigments such as carbon black, titanium black and iron black; red pigments such as red iron oxide and cadmium red; yellow. Yellow pigments such as lead, ocher, and cadmium yellow; blue pigments such as navy blue, azure, and cobalt blue; and the like.
Examples of the organic pigment include alkaline blue, lysole red, carmine 6B, disazoero, phthalocyanine blue, quinacridone red, and isoindolenone yellow.

Among them, from the viewpoint of visibility, the pigment preferably contains at least one selected from the group consisting of white pigments, and more preferably contains titanium oxide.
If necessary, in addition to the white pigment, at least one selected from the group consisting of red pigment, yellow pigment and blue pigment may be mixed from the viewpoint of visibility. Further, from the viewpoint of visibility, in addition to the pigment, at least one selected from the group consisting of a red dye, a yellow dye and a blue dye may be used in combination.

The content of the pigment in the aerosol composition may be appropriately changed according to the required visibility and is not particularly limited, but is preferably 1.0% by mass to 10.0% by mass, and more preferably 1. It is 00% by mass to 10.00% by mass, more preferably 2.0% by mass to 5.0% by mass, and even more preferably 2.00% by mass to 5.00% by mass.
When the inorganic pigment is fine particles such as titanium oxide, the number average particle size of the primary particles is preferably 10 nm to 30 μm, more preferably 50 nm to 1000 nm, and further preferably 100 nm to 500 nm.

The aerosol composition contains clay mineral A. The aqueous dispersion of the viscous mineral A needs to have thixotropic properties.
"The aqueous dispersion has thixotropic properties" means that the viscosity decreases when a shear stress is applied to the aqueous dispersion, and the viscosity gradually returns to the original when the stress is removed. For example, when the 1% by mass aqueous dispersion of clay mineral has thixotropic property, the clay mineral can be determined to be clay mineral A.
Since the aqueous dispersion of the viscous mineral A has thixotropic properties, the viscosity of the aqueous dispersion decreases when pressure is applied to the aqueous dispersion, such as when an aerosol is injected. As a result, the flight distance of the aerosol composition is greatly improved, and long-distance injection becomes possible. Further, since the aerosol composition contains a clay mineral such as clay mineral A, the viscosity of the aerosol composition is improved and it is difficult to diffuse at the time of spraying, so that the flight distance of the aerosol composition is improved.

The viscous mineral A is not particularly limited as long as it can impart thixotropic properties to the aerosol composition, and known clay minerals can be used. Further, the viscous mineral A contributes to the dispersion stability of the pigment.
The clay mineral A is preferably at least one selected from the group consisting of smectite-based clay minerals, mica-based clay minerals, kaolinite-based clay minerals and formite-based clay minerals, and is preferably selected from the group consisting of smectite-based clay minerals. It is more preferable that it is at least one.
The clay mineral A is preferably a clay mineral that forms a curd house structure in the aqueous dispersion (for example, in 1% by mass of the clay mineral). The card house structure is a structure in which plate-like particles are intricately laminated without being oriented. For example, a negatively charged layer surface and a positively charged end surface attract each other to form a three-dimensional association structure of a layer surface-end surface bond. When shearing force is applied, the cardhouse structure is destroyed and the viscosity of the dispersion is reduced.

Examples of smectite-based clay minerals include saponite, montmorillonite, bentonite, byderite, hectorite, nontronite, saponite, and stibnsite. More preferably, the aerosol composition comprises saponite.

The content of clay mineral A in the aerosol composition is 0.8% by mass to 12.0% by mass. If it is less than the above lower limit, the pigment dispersion stability is lowered and a good flight distance cannot be obtained. On the other hand, if the above upper limit is exceeded, a sufficient flight distance cannot be obtained.
The content of the clay mineral A in the aerosol composition is preferably 0.80% by mass to 12.00% by mass, more preferably 1.0% by mass to 10.0% by mass, and even more preferably 1. It is 0.00% by mass to 10.00% by mass, more preferably 1.8% by mass to 7.0% by mass, and particularly preferably 1.80% by mass to 7.00% by mass.

The average thickness of the primary particles of the clay mineral A is preferably 0.2 nm to 10.0 nm, and more preferably 0.5 nm to 3.0 nm.
The average value of the major axis of the primary particles of the clay mineral A is preferably 10 nm to 1000 nm, more preferably 20 nm to 600 nm, and further preferably 50 nm to 150 nm.

For the clay mineral A, for example, the viscosity of the 4% by mass aqueous dispersion is preferably 100 mPa · s to 10000 mPa · s, more preferably 200 mPa · s to 7000 mPa · s, and further preferably 2000 mPa · s to 6000 mPa · s.・ S. The viscosity here was determined by using a BM type viscometer immediately after adjusting the 4% by mass aqueous dispersion of clay mineral, and using the rotor No. It is a value measured under the conditions of 60 rpm, 60 sec, and 25 ° C. in 4.

The aerosol composition comprises a polymeric thickener. The polymer thickener improves the collection of elasticity. Further, the improved shot grouping makes it difficult to diffuse, so that the flight distance of the aerosol composition is improved. Further, the polymer thickener makes it easy to control the injection amount of the aerosol composition to be constant.
The polymer thickener is not particularly limited, and known ones can be used. For example, the following can be mentioned.

Cellulose-based thickeners such as cellulose gum, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydrophobic hydroxypropylmethyl cellulose, sodium cellulose sulfate, and cellulose powder;
Plant-based thickeners such as gum arabic, locust bean gum, tara gum, guar gum, glucomannan, xanthan gum, pectin, and agar.
Starches such as starch, carboxymethyl starch, and methylhydroxypropyl starch.
Alginate-based polymers such as sodium alginate and propylene glycol alginate;
In addition, vinyl thickeners such as carboxyvinyl polymers, acrylic acid / alkyl methacrylate copolymers, acrylic acid / alkyl acrylate cross polymers, and sodium polyacrylate;
Polymerized polymers such as highly polymerized polyethylene glycol (highly polymerized PEG, preferably an average degree of polymerization 2000-150,000), (PEG-240 / decyltetradeceth-20 / HDI) copolymers, polyurethanes and the like.

Among the above, at least one selected from the group consisting of a cellulosic thickener, a plant-based thickener, and a vinyl-based thickener is preferable, and it is selected from the group consisting of a cellulosic thickener and a plant-based thickener. At least one is more preferable.
Further, at least one selected from the group consisting of hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose, hydrophobic hydroxypropylmethyl cellulose, xanthan gum and sodium polyacrylic acid is more preferable. Even more preferably, it is at least one selected from the group consisting of xanthan gum, hydroxyethyl cellulose and sodium polyacrylate, and particularly preferably at least one selected from the group consisting of xanthan gum and hydroxyethyl cellulose.

The content of the polymer thickener in the aerosol composition is 0.03% by mass to 0.9% by mass. If it is less than the above lower limit, sufficient shot grouping cannot be obtained. On the other hand, if the above upper limit is exceeded, a sufficient flight distance may not be obtained, and nozzle clogging may occur.
The content of the polymer thickener is preferably 0.03% by mass to 0.90% by mass, more preferably 0.05% by mass to 0.8% by mass, and further preferably 0.05% by mass. % To 0.80% by mass, still more preferably 0.18% by mass to 0.6% by mass, and particularly preferably 0.18% by mass to 0.60% by mass.

The aerosol composition comprises water. The combination of water and the clay mineral A can impart thixotropic properties suitable for the aerosol composition, and improve the flight distance of the aerosol composition. In addition, assuming that an aerosol is mounted on an unmanned aerial vehicle such as a drone or a multicopter, dangerous substances such as organic solvents cannot be used, so it is necessary to use water as a base.
The content of water in the aerosol composition is preferably 50.0% by mass to 90.0% by mass, more preferably 50.00% by mass to 90.00% by mass, still more preferably 60.0% by mass. It is 85.0% by mass, still more preferably 60.00% by mass to 85.00% by mass, particularly preferably 65.0% by mass to 80.0% by mass, and particularly preferably 65. It is 0.00% by mass to 80.00% by mass.

The aerosol composition preferably contains alcohols. When the aerosol composition is used as a marking agent, it is preferable that the pigment has high detergency so that the pigment can be quickly washed off by water, rain, or the like after the marking function is completed. Detergency is improved by containing alcohols in the aerosol composition.
The present inventors consider that the reason why the detergency of the pigment is improved by the alcohol is that the alcohol acts as a wetting agent such as forming a film on the surface of the pigment and has improved compatibility with water. There is.

Further, in order to improve the flight distance of the aerosol composition, it is preferable that the nozzle attached to the aerosol container is long to some extent. At that time, alcohols having improved detergency are effective from the viewpoint of preventing nozzle clogging.
In particular, assuming that the aerosol is mounted on an unmanned aircraft, the aerosol container is heavy and should be installed as close to the center as possible. Further, in order to reduce the influence of the wind caused by the propeller or the like on the discharged aerosol composition, it is necessary to lengthen the nozzle to some extent. In such a case, in order to prevent the nozzle from being clogged, the aerosol composition preferably contains alcohols having improved detergency.

The alcohols may be aliphatic alcohols or aromatic alcohols. For example, ethanol, propanol, isopropanol, butylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, isopentyldiol, 1,3-pentanediol, pentylene glycol, 1,3-propanediol, glycerin, phenoxyethanol. And so on.

Among them, at least one selected from the group consisting of aliphatic diols (preferably 1 to 6 carbon atoms, more preferably 2 to 4 carbon atoms) is preferable from the viewpoint of wettability and compatibility with water. .. For example, at least one selected from the group consisting of butylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, isopentyldiol, 1,3-pentanediol, pentylene glycol, and 1,3-propanediol. preferable. From the viewpoint of detergency and prevention of nozzle clogging, the aerosol composition more preferably contains propylene glycol.

The content of alcohols in the aerosol composition is preferably about 3.0% by mass to 40.0% by mass, more preferably about 3.00% by mass to 40.00% by mass, and even more preferably. It is about 10.0% by mass to 30.0% by mass, more preferably about 10.00% by mass to 30.00% by mass, and particularly preferably about 15.0% by mass to 25.0% by mass. It is particularly preferably about 15.00% by mass to 25.00% by mass.

The aerosol composition may contain other known additives to the extent that the effect of the aerosol composition is not impaired.
For example, thickeners, surfactants, colorants, fluorescent materials and the like other than the above can be added. The aerosol composition is preferably for marking.

Next, the aerosol product will be described.
Aerosol products
The inner container filled with the aerosol composition is stored in the outer container provided with the discharge mechanism, and the propellant is filled in the space formed between the inside of the outer container and the inner container.
The discharge mechanism and the container are not particularly limited, and known ones may be adopted. The container may be any container as long as it can withstand the pressure of the propellant, and a known resin or metal container can be used.

The aerosol product has, for example, an inner container, which is a foldable flexible bag, sealed in an opening inside the outer container in the discharge mechanism. A space is formed between the outer container and the inner container, and the space is filled with a propellant for discharging the aerosol composition from the discharge mechanism. The discharge mechanism has a discharge port for discharging the aerosol composition filled in the inner container, and when the valve is operated, a flow path to the outside of the inner container is generated. The pressure from the propellant arranged between the inner container and the outer container causes pressure on the inner container, and the filled aerosol composition is discharged to the outside of the outer container.
Such aerosol products are commonly referred to as bag-on-valves or bag-in-cans. An aerosol product using a bag-on-valve can similarly discharge the contents of the bag from any angle, and can discharge 95% of the contents.

The propellant is not particularly limited, and a liquefied gas may be used or a compressed gas may be used. Assuming that an aerosol is mounted on an unmanned aircraft, hazardous materials cannot be used, so aerosol products preferably contain compressed gas. It is preferable not to contain a flammable propellant.
The compressed gas is not particularly limited, and known ones that can be used for aerosol products can be used. The compressed gas is preferably at least one selected from the group consisting of carbon dioxide gas, nitrogen gas, sulfite nitrogen gas, argon, helium, compressed air and the like, and more preferably selected from the group consisting of carbon dioxide gas and nitrogen gas. At least one.

The compressed gas is preferably filled so that the pressure (gauge pressure) in the container when filled in the aerosol container is 0.4 MPa to 1.0 MPa at 25 ° C., and 0.6 MPa to 0. It is more preferable to fill the mixture so that the pressure is 8 MPa.

The method for producing the aerosol composition is not particularly limited. For example, the following method can be mentioned.
The aerosol composition can be obtained by mixing water, a pigment, a clay mineral A and a polymer thickener, and if necessary, alcohols and other components in an arbitrary ratio.

Aerosol products are preferably mounted on unmanned aerial vehicles such as drones and multicopters. That is, an unmanned air vehicle equipped with the above aerosol product is a preferred embodiment. The unmanned aircraft is not particularly limited, and known ones may be adopted.
For example, a multicopter in which a plurality of rotor blades are provided on the airframe can be mentioned. Various known multicopters can be used, such as a tricopter with three rotors, a quadcopter with four rotors, and a hexacopter with six rotors.

The means for mounting the aerosol product on the multicopter is not particularly limited, and a known method can be adopted. For example, it may be mounted horizontally on the machine body, or it may be mounted with the discharge mechanism facing downward. It is preferable that the unmanned aircraft is provided with an opening / closing mechanism that can open / close the ejection mechanism of the aerosol product by remote control.
The shape of the nozzle of the aerosol product is not particularly limited, and may be appropriately changed according to the purpose. When marking on the wall surface, a horizontal nozzle may be used, and when marking on the ground, a nozzle bent 90 ° downward from the horizontally mounted aerosol product may be used.

Hereinafter, the present disclosure will be specifically described with reference to Examples. However, the present disclosure is not limited to the following embodiments.

<Examples 1 to 11 and Comparative Examples 1 to 4>
The raw materials were mixed according to the formulations (% by mass) shown in Table 1 to prepare the aerosol compositions of Examples 1 to 11 and the aerosol compositions of Comparative Examples 1 to 4.

In Table 1, the materials used are as follows.
Smekton SA: Saponite (Kunimine Industries, Ltd.)
TITANIX JR-806: Titanium Oxide (Tayca Corporation)
Echo Gum T: Xanthan Gum (DSP Gokyo Food & Chemical Co., Ltd.)
HEC SE600: Hydroxyethyl Cellulose (Daicel FineChem Co., Ltd.)
AH-105X: Na polyacrylic acid (Toagosei Co., Ltd.)
Industrial Propylene Glycol: Propylene Glycol (ADEKA CORPORATION)
Fluorescent water for snow Magenta: Legal dye (Shin Roihi Co., Ltd.)

Then, each of the obtained aerosol compositions was filled in a bag-on-valve type aerosol container to obtain an aerosol product. Nitrogen was used as the propellant, and the pressure (gauge pressure) in the container was 0.7 MPa.

The following evaluation was performed using the obtained aerosol composition. The results are shown in Table 1.
(1. Pigment dispersion stability)
The undiluted solution was collected in a 50 ml vial and stored in a constant temperature bath at 45 ° C. for 3 months as an accelerated test to confirm the sedimentation state of the pigment in the undiluted solution.
A: No pigment settling B: A small amount of pigment settling C: Pigment settling

The following evaluation was performed using the obtained aerosol product. The results are shown in Table 1.
(Flying distance and shot grouping)
After immersing the aerosol product in a constant temperature water bath at 25 ° C. for 30 minutes, a nozzle having an inner diameter of 1.0 mm, an outer diameter of 2.6 mm, and a length of 5 mm was attached to the tip of a nozzle having a length of 20 cm and an inner diameter of 3 mm. Using this nozzle, the flight distance and shot grouping of aerosol products were evaluated.
A3 paper was placed horizontally 3 m away from the aerosol product, and the contents were sprayed for 0.5 seconds to evaluate the flight distance and shot grouping according to the following criteria.
(2. Flying distance)
A: 90% or more (mass standard) of the discharged contents is reached B: 50% or more and less than 80% of the discharged contents is reached C: Less than 50% of the discharged contents is reached (3. Collection) Elastic)
A: The diameter of the spray pattern is less than 11 cm B: The diameter of the spray pattern is 11 cm or more and less than 17 cm C: The diameter of the spray pattern is 17 cm or more

(Cleanability)
After immersing the aerosol product in a constant temperature water tank at 25 ° C for 30 minutes, the aerosol product equipped with a button with a nozzle diameter of φ0.5 mm was placed on a table with a height of 1.5 m and placed on a wall made of mortar 1.5 m away. It was sprayed toward it for 1 second. After leaving it at room temperature (20 ° C to 30 ° C) for 1 week, the detergency of the contents adhering to the wall was confirmed.
A: Adhesives fall off just by running water for 30 seconds B: After running water for 30 seconds, deposits fall off by scrubbing with a water-soaked turtle scrubbing brush (10 times) C: 30 seconds After running water, scrubbing with a turtle scrubbing brush soaked in water (10 times) does not remove the deposits.

(Clog)
After immersing the aerosol product in a constant temperature water bath at 25 ° C. for 30 minutes, the aerosol product equipped with a button having a nozzle diameter of φ0.5 mm was sprayed for 1 second and then stored in a constant temperature chamber at 25 ° C. for 1 week. After saving, the button was activated to check for clogging.
A: Can be injected with one operation B: Can be injected with 2 to 5 operations although there is initial clogging C: Cannot be injected with 6 or more to 10 operations

Claims (12)

It is an aerosol composition
The aerosol composition contains a pigment, clay mineral A, polymer thickener and water.
The content of the clay mineral A in the aerosol composition is 0.8% by mass to 12.0% by mass.
The content of the polymer thickener in the aerosol composition is 0.03% by mass to 0.9% by mass.
The clay mineral A is an aerosol composition characterized in that its aqueous dispersion has thixotropic properties. The aerosol composition according to claim 1, wherein the clay mineral A is at least one selected from the group consisting of smectite-based clay minerals, mica-based clay minerals, kaolinite-based clay minerals, and formite-based clay minerals. The aerosol composition according to claim 1 or 2, wherein the clay mineral A is a clay mineral that forms a curd house structure in the aqueous dispersion. The aerosol composition according to any one of claims 1 to 3, wherein the content of the clay mineral A in the aerosol composition is 1.0% by mass to 10.0% by mass. The aerosol composition according to any one of claims 1 to 4, wherein the aerosol composition contains alcohols. The aerosol composition according to claim 5, wherein the alcohols are at least one selected from the group consisting of aliphatic diols having 1 to 6 carbon atoms. The aerosol composition according to claim 5 or 6, wherein the content of the alcohols in the aerosol composition is 3.0% by mass to 40.0% by mass. The aerosol composition according to any one of claims 1 to 7, wherein the pigment contains an inorganic pigment. The aerosol composition according to any one of claims 1 to 8, wherein the content of the polymer thickener in the aerosol composition is 0.05% by mass to 0.8% by mass. The aerosol according to any one of claims 1 to 9, wherein the polymer thickener is at least one selected from the group consisting of a cellulosic thickener, a plant thickener and a vinyl thickener. Composition. It ’s an aerosol product,
The inner container filled with the aerosol composition is stored in the outer container provided with the discharge mechanism, and the space formed between the inside of the outer container and the inner container is filled with the propellant.
An aerosol product in which the aerosol composition is the aerosol composition according to any one of claims 1 to 10. An unmanned vehicle equipped with the aerosol product according to claim 11.