Capsule manufacturing method and capsule manufacturing device

Abstract

A cylindrical body (111) is formed in a cylindrical shape surrounding a virtual central line (VL). On an inner surface of the cylindrical body (111), a guide groove (112) having a spiral shape is formed around the virtual central line (VL). A rotation device (120) rotates the cylindrical body (111) around the virtual central line (VL). A dropping device (130) drops, onto the inner surface of the cylindrical body (111), a substance to be encapsulated and a wall material precursor liquid that is a precursor of a wall material that covers the substance to be encapsulated. The droplet dropped by the dropping device (130) rolls along the guide groove (112) of the cylindrical body (111) rotated by the rotation device (120).

Description

[Technical Field]

[0001] The present invention relates to a capsule manufacturing method and a capsule manufacturing apparatus. [Background technology]

[0002] As disclosed in Patent Document 1, capsules having a structure in which an encapsulated substance is covered by a wall material are known. The encapsulated substance is, for example, a desired substance such as a pesticide, ink, or pharmaceutical. The wall material serves to improve the handleability of the encapsulated substance, protect the encapsulated substance from the external environment, and control the release rate of the encapsulated substance.

[0003] Patent Document 1 proposes the following capsule manufacturing method. First, droplets of a raw material liquid containing a monomer liquid or polymer liquid, which is a precursor of the wall material, and an encapsulated substance, are dropped onto the surface of a flat plate. The dropped droplets maintain their spherical shape due to surface tension. Next, the monomer liquid or polymer liquid is solidified to form the wall material. This completes the capsule. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-87479 Summary of the Invention [Problem to be solved by the invention]

[0005] In the conventional capsule manufacturing method described above, when a large number of droplets are placed on a flat plate, coalescence easily occurs, where two or more droplets coalesce into one. This is one of the factors that makes it difficult to efficiently manufacture capsules.

[0006] An object of the present invention is to provide a capsule manufacturing method capable of efficiently manufacturing capsules, and a capsule manufacturing apparatus that can be used to implement the capsule manufacturing method. [Means for solving the problem]

[0007] The capsule manufacturing method according to the present invention comprises: A capsule manufacturing method using a cylindrical body formed in a cylindrical shape surrounding an imaginary center line, the cylindrical body having a spiral or circumferential guide groove formed on an inner surface around the imaginary center line, a dropping step of dropping an encapsulation substance and a wall material precursor liquid, which is a precursor of a wall material that covers the encapsulation substance, onto the inner surface of the cylindrical body; The droplets dropped in the dropping step are guided by the guide groove of the cylindrical body which is rotating around the imaginary center line. While in contact with the inner surface of an encapsulation step in which encapsulation of the encapsulated substance and the wall material precursor liquid proceeds by rolling; a capsule discharging step in which capsules obtained by the encapsulation process are discharged from the cylindrical body; With death, a powder arranging step of arranging powder of solid fine particles smaller than the droplets in advance in the guide groove of the cylindrical body before the dropping step; and In the encapsulation process, the liquid droplets roll along the guide groove of the rotating cylinder together with the solid fine particles, forming liquid marbles with the solid fine particles sprinkled on the surface of the droplets, and the droplets roll along the guide groove in the form of liquid marbles.

[0009] The surface of the guide groove of the cylindrical body may be liquid-repellent to the droplets.

[0010] the amount of the droplet dropped at one time in the dropping step is 15 μL or less; The peripheral speed of the inner surface of the cylindrical body in the dropping step and the encapsulation step may be 0.08 m / s or more and 0.24 m / s or less.

[0011] the wall material precursor liquid has a gelling property, The encapsulation may proceed by the gelation of the wall material precursor liquid.

[0012] the wall material precursor liquid contains a monomer, The encapsulation may proceed by polymerization of the monomer.

[0013] the wall material precursor liquid contains a solvent, The encapsulation may proceed by removal of the solvent.

[0014] The capsule manufacturing apparatus according to the present invention comprises: a cylindrical body formed in a cylindrical shape surrounding an imaginary center line, the cylindrical body having a spiral or circumferential guide groove formed on its inner surface around the imaginary center line; a rotation device that rotates the cylindrical body around the imaginary center line; a dripping device that drips an encapsulation substance and a wall material precursor liquid that is a precursor of a wall material that covers the encapsulation substance onto the inner surface of the cylindrical body; Equipped with a powder of solid fine particles smaller than the droplets dropped by the dropping device is placed in advance in the guide groove of the cylindrical body; The dripping device drips The aforementioned The droplets pass through the guide groove of the cylinder that is being rotated by the rotating device. together with the solid fine particles By rolling, The solid particles are sprinkled on the surface of the droplets to form liquid marbles, and the droplets roll in the guide groove in the form of liquid marbles. The encapsulation of the encapsulated substance and the wall material precursor liquid proceeds.

[0015] The amount of the droplet dispensed by the dispensing device at one time may be 15 μL or less.

[0016] a solidification promoting device that promotes solidification of the wall material precursor liquid in the droplets rolling in the guide groove of the cylindrical body; may further comprise: [Effects of the Invention]

[0017] According to the capsule manufacturing method of the present invention, capsules can be manufactured efficiently. [Brief explanation of the drawings]

[0018] [Figure 1A] FIG. 1 is a conceptual diagram showing an example of a capsule. [Figure 1B] FIG. 10 is a conceptual diagram showing another example of a capsule. [Figure 1C] FIG. 10 is a conceptual diagram showing yet another example of a capsule. [Figure 2] FIG. 1 is a conceptual diagram showing the configuration of a capsule manufacturing device according to a first embodiment. [Figure 3] FIG. 1 is a conceptual diagram showing a main part of a dropping device according to a first embodiment. [Figure 4] 3 is a flowchart of capsule manufacturing according to the first embodiment. [Figure 5] FIG. 3 is an enlarged cross-sectional view showing a guide groove in the cylindrical body according to the first embodiment. [Figure 6A] 1 is a micrograph of a capsule according to Example A1. [Figure 6B] 1 is a micrograph of a capsule according to Example A2. [Figure 6C] Micrograph of capsules according to Example A3. [Figure 6D] Micrograph of capsules according to Example A4. [Figure 6E] Micrograph of capsules according to Example A5. [Figure 6F] Micrograph of capsules according to Example A6. [Figure 7A] Microscopic photograph of a capsule to illustrate the definition of sphericity. [Figure 7B] Micrograph of a capsule to illustrate the definition of wall thickness uniformity. [Figure 8] 1 is a graph showing the relationship between the circumferential speed of the inner surface of a cylindrical body in a capsule manufacturing apparatus and the sphericity, wall thickness uniformity, and success rate of the obtained capsules. [Figure 9] 10 is a micrograph of a capsule according to Example B. [Figure 10] FIG. 10 is an enlarged cross-sectional view showing a guide groove in a cylindrical body according to a second embodiment. [Figure 11] FIG. 10 is a conceptual diagram showing the configuration of a capsule manufacturing device according to a third embodiment. [Figure 12] FIG. 10 is a conceptual diagram showing the configuration of a capsule manufacturing device according to a modified example. DETAILED DESCRIPTION OF THE INVENTION

[0019] Referring to Figures 1A-C, the capsule configuration will be described by way of example.

[0020] 1A shows an example of a capsule 10. This capsule 10 has a structure in which an encapsulated substance 11 is covered with a wall material 12. In this example, the encapsulated substance 11 is present collectively in one continuous region inside the capsule 10. Hereinafter, this form will be referred to as a "mononuclear form."

[0021] The encapsulated substance 11 is a desired substance such as a pesticide, ink, medicine, etc. The wall material 12 serves to improve the handleability of the encapsulated substance 11, to protect the encapsulated substance 11 from the external environment, and to control the release rate of the encapsulated substance 11.

[0022] 1B shows another example of capsule 10. In this example, encapsulated substance 11 is present in a discretely distributed manner in multiple regions inside capsule 10. Hereinafter, this type of form will be referred to as "multinuclear."

[0023] 1C shows yet another example of capsule 10. In this example, the interior of capsule 10 is filled with a single type of composite matrix 13 having a continuous structure. Composite matrix 13 is a mixture of encapsulated substance 11 and wall material 12, as described above, at the molecular level. Even when capsule 10 according to this example is observed under an electron microscope, it is difficult to identify the boundary between encapsulated substance 11 and wall material 12.

[0024] The structure shown in FIG. 1C is also referred to as a "bead." However, in this specification, the concept of a "capsule" also includes "beads." The concept of a "capsule" also includes a structure in which a mononuclear encapsulated substance 11 shown in FIG. 1A or a polynuclear encapsulated substance 11 shown in FIG. 1B is covered with a composite matrix 13 shown in FIG. 1C. The concept of a "capsule" also includes a structure in which a wall material 12 shown in FIG. 1A or FIG. 1B and a composite matrix 13 shown in FIG. 1C coexist.

[0025] The diameter of the capsule 10 described above is typically 10 μm or more and 1 cm or less, more specifically, 100 μm or more and 5 mm or less. The diameter of the capsule 10 can be measured by observation with a stereomicroscope or by a laser diffraction scattering method.

[0026] A capsule manufacturing apparatus for manufacturing the capsules 10 will be described below.

[0027] [First embodiment] As shown in FIG. 2, the capsule manufacturing apparatus 100 according to this embodiment includes a rotating cylinder 110, a rotating device 120 that rotates the rotating cylinder 110, and a dripping device 130 that drops a raw material liquid 20, which is a precursor of the capsules 10, onto the rotating cylinder 110 that is being rotated by the rotating device 120.

[0028] The rotating barrel 110 has a cylindrical body 111 formed in a cylindrical shape surrounding the imaginary center line VL, and a rotating shaft 113 fixed to the cylindrical body 111.

[0029] The rotating shaft 113 is fixed to one end of the cylindrical body 111 in the longitudinal direction parallel to the imaginary center line VL. The rotating shaft 113 extends on the imaginary center line VL. A guide groove 112 is formed on the inner surface of the cylindrical body 111 and extends spirally around the imaginary center line VL. The guide groove 112 is formed from one end to the other end of the cylindrical body 111 in the longitudinal direction.

[0030] The rotating barrel 110 is disposed in a horizontal position with the rotation shaft 113 tilted sideways. Specifically, in this embodiment, the rotating barrel 110 is tilted horizontally, and the length direction of the cylindrical body 111 coincides with the horizontal direction. The rotation device 120 rotates the cylindrical body 111 around the imaginary center line VL via the rotation shaft 113.

[0031] The dripping device 130 is disposed at the end of the cylindrical body 111 opposite to the end to which the rotation shaft 113 is fixed in the longitudinal direction.

[0032] As shown in Fig. 3, the dropping device 130 has an inner tube 131 and an outer tube 132 that concentrically surrounds the outside of the inner tube 131. The inner tube 131 and the outer tube 132 form a double tube. The inner tube 131 discharges the liquid encapsulated substance 11. The outer tube 132 discharges the wall material precursor liquid 21, which is a precursor of the wall material 12 shown in Fig. 1A.

[0033] The discharge of encapsulated substance 11 from inner tube 131 and the discharge of wall material precursor liquid 21 from outer tube 132 are carried out in parallel. As a result, droplets of raw material liquid 20 in which liquid encapsulated substance 11 is covered with wall material precursor liquid 21 are repeatedly dropped from dropping device 130. The diameter of one droplet of raw material liquid 20 is, for example, 0.1 mm or more and 5 mm or less.

[0034] The dropped droplets of the raw material liquid 20 land on the inner surface of the cylindrical body 111 shown in Fig. 2. The distance between the tips of the inner tube 131 and outer tube 132 of the dropping device 130 and the inner surface of the cylindrical body 111 is preferably 5 cm or less, more preferably 2.5 cm or less, and even more preferably 1.5 cm or less. The droplets of the raw material liquid 20 solidify to form the capsule 10 shown in Fig. 1A.

[0035] The capsule manufacturing method according to this embodiment will be specifically described below with reference to the flowchart shown in FIG.

[0036] 2, powder of the solid fine particles 30 is placed on the inner surface of the cylindrical body 111 (powder placing step S1). The powder of the solid fine particles 30 is also placed in the guide grooves 112.

[0037] Next, while the rotating device 120 rotates the cylinder 111, the dropping device 130 drops droplets of the raw material liquid 20 one after another onto the inner surface of the cylinder 111 (dropping step S2). The amount of droplets dropped by the dropping device 130 at one time is, for example, 15 μL or less.

[0038] The behavior of the droplets dropped in dropping step S2 will be described with reference to Fig. 5. Each droplet of raw material liquid 20 rolls together with solid fine particles 30 in guide grooves 112 on the inner surface of rotating cylinder 111. This forms liquid marbles 40 in which the surfaces of the droplets of raw material liquid 20 are coated with solid fine particles 30.

[0039] In the liquid marble 40, the solid fine particles 30 serve to stabilize the shape of the droplets of the raw material liquid 20 into a spherical shape and to prevent a plurality of droplets of the raw material liquid 20 from coalescing into one.

[0040] In this way, the droplets of each liquid material 20 roll in the guide groove 112 in the form of liquid marbles 40. Because the guide groove 112 is spiral, each rolling liquid marble 40 oscillates circumferentially around the cylinder 111 while moving in one direction parallel to the imaginary center line VL shown in Figure 2, specifically, in the direction from the dropping device 130 toward the rotation axis 113. During this movement, encapsulation also progresses (encapsulation step S3).

[0041] Here, "encapsulation" means that the form of the encapsulated substance 11 and the wall material precursor liquid 21 becomes closer to that of a capsule 10. Specifically, in this embodiment, the concept of "encapsulation" includes the solidification of the wall material precursor liquid 21 in the liquid marble 40.

[0042] Then, as the droplets of each raw material liquid 20 are encapsulated, specifically, as the wall material precursor liquid 21 in each liquid marble 40 solidifies, the droplets of raw material liquid 20 become capsules 10, and the capsules 10 are discharged one after another from the cylinder 111 (capsule discharging step S4). For example, capsules 10 with a diameter of approximately 1.0 mm to 3 mm can be obtained from droplets of raw material liquid 20 with a volume of 1 μL or more to 10 μL or less.

[0043] However, solid fine particles 30 adhere to the capsules 10 discharged from the cylindrical body 111. Therefore, if necessary, the solid fine particles 30 adhering to the capsules 10 may be removed after the capsule discharge step S4 (solid fine particle removal step S5).

[0044] As described above, according to this embodiment, the droplets of the liquid raw material 20 move in one direction inside the cylinder 111 while rolling along the guide groove 112 in the form of liquid marbles 40. This prevents the droplets of the liquid raw material 20 from coalescing, allowing for efficient production of a large number of capsules 10.

[0045] Furthermore, the process of sprinkling the solid fine particles 30 onto the droplets of the raw material liquid 20 and the solidification of the wall material precursor liquid 21 can be carried out continuously. This also contributes to the efficient production of a large number of capsules 10.

[0046] Furthermore, since the solidification of the wall material precursor liquid 21 progresses while the liquid marbles 40 roll, it is possible to obtain capsules 10 with high sphericity. Here, sphericity is an evaluation index that indicates how close the shape of the capsule 10 is to a perfect sphere.

[0047] Furthermore, since the solidification of the wall material precursor liquid 21 progresses while the liquid marbles 40 roll, even if the mass densities of the wall material precursor liquid 21 and the encapsulated substance 11 are different, particularly if the mass density of the wall material precursor liquid 21 is greater than the density of the encapsulated substance 11, the position of the encapsulated substance 11 is less likely to become uneven inside the resulting capsule 10.

[0048] In particular, when producing the mono-core capsules 10 shown in Fig. 1A, it is possible to obtain capsules 10 with a uniform thickness of the wall material 12. This also contributes to improving the yield of capsules 10.

[0049] The above-mentioned solid particulates 30 will now be described in detail.

[0050] The solid microparticles 30 have a diameter smaller than the droplets of the raw material liquid 20 dropped from the dropping device 130. Specifically, the diameter of the solid microparticles 30 is small enough to cover the droplets of the raw material liquid 20. More specifically, the diameter of the solid microparticles 30 is, for example, 0.01 μm or more and 500 μm or less, and preferably 1 μm or more and 300 μm or less. In this specification, the diameter of the solid microparticles 30 refers to the number-based average particle size measured by observation with a stereomicroscope or by a laser diffraction / scattering method.

[0051] The solid fine particles 30 preferably have an appropriate liquid repellency with respect to the wall material precursor liquid 21 so as to stably coat the droplets of the raw material liquid 20. Specifically, the solid fine particles 30 preferably exhibit a contact angle with respect to the wall material precursor liquid 21 of 70° or more, preferably 100° or more.

[0052] For example, water-repellent solid particles 30 that exhibit a contact angle with water of 70° or more, preferably 100° or more, can be used. Examples of the water-repellent solid particles 30 include particles of fluororesins such as polytetrafluoroethylene, alkylated silica particles, carbon black, polyvinylidene fluoride, poly[2-(perfluorooctyl)ethyl acrylate], etc.

[0053] Alternatively, the water-repellent solid particles 30 may be silicone monoliths such as aerogels or xerogels having a polysiloxane structure. Silicon monoliths can be obtained, for example, by copolymerizing bifunctional alkoxysilanes and trifunctional or tetrafunctional or higher alkoxysilanes via a sol-gel reaction. Examples of such silicone monoliths include aerogels or xerogels obtained from vinyltrimethoxysilane and methylvinyldimethoxysilane. Such materials are described in a report by Hayase et al. (Angew Chem Int Ed Engl. 2013, 52 (41), 10788-10791).

[0054] Furthermore, solid particles 30 having water and oil repellency can also be used. In this specification, water and oil repellency refers to having both water and oil repellency. For example, solid particles 30 that exhibit a contact angle with water of 70° or more, preferably 100° or more, and a contact angle with n-hexadecane of 70° or more, preferably 100° or more, can be said to have water and oil repellency.

[0055] Examples of the water- and oil-repellent solid particles 30 include a material having a polysiloxane structure and a perfluoroalkyl structure, preferably a silicone monolith such as an aerogel or xerogel having a polysiloxane structure and a perfluoroalkyl structure. One such material is marshmallow gel, a flexible porous material exhibiting water and oil repellency, as described in Hayase et al. (Angew Chem Int Ed Engl. 2013, 52(41), 10788-10791). Other examples of the water- and oil-repellent solid particles 30 include particles of carbon or polyvinylidene fluoride whose surfaces are modified with perfluoroalkyl groups.

[0056] As a combination of the wall material precursor liquid 21 and the solid particles 30, it is preferable that the wall material precursor liquid 21 is hydrophobic and the solid particles 30 are water- and oil-repellent, or that the wall material precursor liquid 21 is hydrophilic and the solid particles 30 are water- and oil-repellent or water-repellent.

[0057] Next, the encapsulation in the above-mentioned encapsulation step S3 will be described.

[0058] In this embodiment, encapsulation, specifically solidification of the wall material precursor liquid 21, can be achieved by, for example, (a) gelling of the wall material precursor liquid 21, (b) polymerization of the wall material precursor liquid 21, (c) removal of the solvent contained in the wall material precursor liquid 21, or a combination of any two or more selected from (a)-(c).

[0059] 2, the capsule manufacturing apparatus 100 may include a solidification accelerator 140 that accelerates the solidification described above. The solidification accelerator 140 accelerates the solidification of the wall material precursor liquid 21 in the liquid marbles 40 moving in one direction inside the cylindrical body 111 in the encapsulation step S3 described above. This will be explained in detail below.

[0060] (a) If the wall material liquid precursor 21 has the property of gelling when subjected to a temperature change, the solidification accelerator 140 applies a temperature change to the liquid marbles 40 moving in one direction inside the cylinder 111. This accelerates the gelation of the wall material liquid precursor 21.

[0061] Specifically, the solidification accelerating device 140 cools or heats the liquid marble 40. Cooling can be achieved by, for example, a Peltier element, a refrigeration cycle, etc. Heating can be achieved by, for example, a Peltier element, an infrared lamp, etc.

[0062] However, if the capsule manufacturing apparatus 100 is placed in a room temperature environment, for example, at a temperature of 15°C or higher and 25°C or lower, and the wall material precursor liquid 21 has been heated in advance to a temperature higher than room temperature, or the wall material precursor liquid 21 has been cooled in advance to a temperature lower than room temperature, gelation of the wall material precursor liquid 21 occurs naturally as the wall material precursor liquid 21 approaches room temperature, the solidification promotion device 140 is not required.

[0063] (b) When the wall material precursor liquid 21 contains a monomer, the solidification promoting device 140 performs a process to promote polymerization of the wall material precursor liquid 21 on the liquid marbles 40 moving in one direction inside the cylinder 111.

[0064] Specifically, in the case of photopolymerization, in which polymerization is accelerated by light, the solidification acceleration device 140 irradiates the liquid marble 40 with light. The light may be emitted from outside the cylinder 111 and transmitted through the cylinder 111 to enter the liquid marble 40. The wavelength of the light is, for example, 380 nm to 780 nm. In the case of thermal polymerization, in which polymerization is accelerated by heat, the solidification acceleration device 140 heats the liquid marble 40. The heating temperature is, for example, 30°C to 80°C.

[0065] However, if the polymerization of the wall material precursor liquid 21, which is a monomer, progresses spontaneously in the environment in which the capsule manufacturing apparatus 100 is placed, the solidification promoting device 140 is not necessary.

[0066] The monomer may be either a hydrophobic monomer or a hydrophilic monomer. In this specification, a hydrophobic monomer refers to a monomer having a solubility of less than 2% by mass in water at 25°C, and a hydrophilic monomer refers to a monomer having a solubility of 2% by mass or more in water at 25°C.

[0067] Examples of hydrophobic monomers include monofunctional acrylates such as isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, decyl acrylate, and dodecyl acrylate; polyfunctional acrylates such as ethylene glycol diacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate, and pentaerythritol tetraacrylate; ethyl methacrylate, propyl methacrylate, and n-butyl acrylate; Examples of suitable hydrophobic monomers include monofunctional methacrylates such as methacrylate, isobutyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, and decyl methacrylate; polyfunctional methacrylates such as ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and pentaerythritol tetramethacrylate; styrene-based monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, and chloromethylstyrene; and divinylbenzene. The hydrophobic monomers may be used alone or in combination. From the viewpoint of the mechanical strength of the wall material 12 of the capsule 10, (meth)acrylate, styrene, and divinylbenzene are preferred as hydrophobic monomers. In this specification, (meth)acrylate refers to monofunctional or polyfunctional acrylate and / or methacrylate.

[0068] Examples of hydrophilic monomers include acrylic acid, methacrylic acid, maleic acid, fumaric acid, vinyl sulfonic acid, styrene sulfonic acid, vinyl alcohol, acrylamide, methacryloxyethyl phosphate, etc. The hydrophilic monomers may be used alone or in combination of two or more.

[0069] The wall material precursor liquid 21 may contain other components besides the monomer, such as a polymerization initiator such as a thermal polymerization initiator or a photopolymerization initiator, a solvent for dissolving or dispersing the monomer, a surfactant, an ultraviolet absorber, a light stabilizer, an antioxidant, a flame retardant, a plasticizer, wax, etc.

[0070] Examples of the thermal polymerization initiator include azo compounds such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis[N-(2-propenyl)2-methylpropionamide], 1-[(1-cyano-1-methylethyl)azo]formamide, 2,2'-azobis(N-butyl-2-methylpropionamide), and 2,2'-azobis(N-cyclohexyl-2-methylpropionamide); and peroxides such as t-butylperoxybenzoate and 2,5-dimethyl-2,5-di(t-butylperoxy)hexane. Among these, azo compounds are preferred, and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) is more preferred.The amount of the thermal polymerization initiator to be added is preferably 0.01 mol % or more and 5 mol % or less based on the monomer.

[0071] Examples of photopolymerization initiators include acetophenone compounds such as diethoxyacetophenone; benzoin compounds such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; acylphosphine oxide compounds such as 2,4,6-trimethylbenzoin diphenylphosphine oxide; benzophenone compounds such as benzophenone and hydroxybenzophenone; thioxanthone compounds such as 2-isopropylthioxanthone and 2,4-dimethylthioxanthone; aminobenzophenone compounds such as 4,4'-diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and camphorquinone. The amount of photopolymerization initiator added is preferably 0.01 mol% or more and 5 mol% or less based on the monomer.

[0072] The photopolymerization initiator may be used in combination with a photopolymerization accelerator in the monomer, if necessary, to more efficiently solidify the monomer.

[0073] Examples of photopolymerization accelerators include benzoic acid compounds such as 4-dimethylaminobenzoic acid, ethyl 4-dimethylaminobenzoate, n-butoxyethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-ethylhexyl 4-dimethylaminobenzoate, and tertiary amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone, and 4,4'-diethylaminobenzophenone. The amount of the photopolymerization accelerator to be added is preferably 0.01 mol% or more and 5 mol% or less based on the monomer.

[0074] (c) When the wall material precursor liquid 21 contains a solvent, the solidification accelerating device 140 applies heat to the liquid marbles 40 moving in one direction inside the cylinder 111 to promote removal of the solvent contained in the wall material precursor liquid 21. However, when the solvent evaporates naturally in the environment in which the capsule manufacturing apparatus 100 is placed, the solidification accelerating device 140 is not necessary.

[0075] The wall material precursor liquid 21 containing a solvent may be a polymer solution in which a polymer is dissolved in an organic solvent.

[0076] Examples of the polymer that can be used include polymers derived from the above-mentioned hydrophobic or hydrophilic monomers, preferably poly(meth)acrylate, polystyrene, and polydivinylbenzene. Also usable are polylactic acid, polyglycolic acid, copolymers of lactic acid and glycolic acid, and polycaprolactone.

[0077] Examples of the organic solvent that can be used include acetone, methanol, ethanol, dimethyl sulfoxide, dichloroethane, dichloromethane, hexane, toluene, xylene, ethyl acetate, chloroform, and diethyl ether.

[0078] The polymer solution may contain components other than the polymer and the solvent, such as a surfactant, an ultraviolet absorber, a light stabilizer, an antioxidant, a flame retardant, a plasticizer, and a wax.

[0079] [Example A] The mono-core capsule 10 shown in FIG. 1A was manufactured using a capsule manufacturing apparatus 100 shown in FIG. 2. The encapsulated substance 11 is made of MCT (Medium Chain Triglyceride), a medium-chain fatty acid. The wall material 12 is made of agarose gel. For the wall material precursor liquid 21, an agarose aqueous solution with a concentration of 3% by mass that was preheated to a temperature higher than room temperature was used. The density of the agarose aqueous solution is greater than that of MCT.

[0080] The amount of raw material liquid 20 dropped by the dropping device 130 at one time was adjusted to be 8 μL or more and 10 μL or less. The dropping device 130 drops 0.5 mL of droplets per minute. 85% to 95% by volume of the droplets of raw material liquid 20 were made of wall material precursor liquid 21, and the remainder was made of encapsulation substance 11. The solid microparticles 30 used were made of fluororesin and had a diameter of about 6±2 μm.

[0081] The droplets of the raw material liquid 20 roll in the guide groove 112 together with the solid fine particles 30 made of fluororesin, so that the droplets of the raw material liquid 20 are covered with the solid fine particles 30 made of fluororesin, and liquid marbles 40 are formed.

[0082] As the liquid marbles 40 roll along the guide grooves 112 and move in one direction, the agarose aqueous solution serving as the wall material precursor liquid 21 cools, causing the agarose aqueous solution to gel. As a result, mononuclear capsules 10 are obtained, each with a wall material 12 made of agarose gel. The capsules 10 are discharged one after another from the end of the cylinder 111.

[0083] Thereafter, in order to further solidify the wall material 12, each of the capsules 10 discharged from the cylindrical body 111 was subjected to a drying treatment to dissipate the moisture contained in the gel-like wall material 12.

[0084] In the above, the circumferential velocity of the inner surface of the cylinder 111 was changed in various ways to investigate the optimal circumferential velocity of the inner surface of the cylinder 111. Example A1 is a case where the circumferential velocity of the inner surface of the cylinder 111 is 0.08 m / s, Example A2 is a case where the circumferential velocity of the inner surface of the cylinder 111 is 0.13 m / s, Example A3 is a case where the circumferential velocity of the inner surface of the cylinder 111 is 0.19 m / s, Example A4 is a case where the circumferential velocity of the inner surface of the cylinder 111 is 0.24 m / s, Example A5 is a case where the circumferential velocity of the inner surface of the cylinder 111 is 0.32 m / s, and Example A6 is a case where the circumferential velocity of the inner surface of the cylinder 111 is 0.42 m / s.

[0085] Then, for the capsules 10 obtained in each of Examples A1 to A6, the sphericity, which indicates how close the shape is to a perfect sphere, the wall thickness uniformity, which indicates the uniformity of the thickness of the wall material 12, the success rate of manufacturing the capsules 10, and the encapsulated substance content, which is the content of the encapsulated substance 11, were measured. The definitions of these evaluation indexes will be specifically explained below.

[0086] The definition of sphericity will be explained with reference to Figure 7A. In a micrograph of the capsule 10 after the drying process, the longest diameter a and the shortest diameter b of the spherical capsule 10 are measured. The sphericity [%] is defined as b / a x 100.

[0087] The definition of wall thickness uniformity will be explained with reference to Figure 7B. In a micrograph of capsule 10 after the drying process, the thickness d of wall material 12 at the thickest part, the radius c of the position including the line segment representing thickness d, the thickness f of wall material 12 at the thinnest part, and the radius e of the position including the line segment representing thickness f are measured. Wall thickness uniformity [%] is defined as (f / e) / (d / c) x 100.

[0088] The success rate [%] is defined as (total number of capsules 10) / (total number of droplets of raw material liquid 20 dropped by dropping device 130) × 100. The success rate was calculated for the stage before the drying process and the stage after the drying process. This is because the wall material 12 may be damaged by the drying process, and if damage to the wall material 12 is found, there is a risk of leakage of the encapsulated substance 11, and it cannot be said that the production of capsules 10 was successful.

[0089] Fig. 8 shows the dependence of the above-mentioned sphericity, wall thickness uniformity, and success rate on the circumferential speed of the inner surface of the cylinder 111. The vertical axis of Fig. 8 represents the sphericity [%], wall thickness uniformity [%], and success rate [%], and the horizontal axis represents the circumferential speed [m / s] of the inner surface of the cylinder 111.

[0090] 8, when the circumferential velocity of the inner surface of the cylinder 111 is 0.08 m / s or more and 0.24 m / s or less, the sphericity [%], wall thickness uniformity [%], and success rate [%] become relatively high. From this, it can be said that when the amount of raw material liquid 20 dropped at one time by the dropping device 130 is 15 μL or less, the circumferential velocity of the inner surface of the cylinder 111 is preferably 0.08 m / s or more and 0.24 m / s or less. The circumferential velocity of the inner surface of the cylinder 111 is more preferably 0.08 m / s or more and 0.19 m / s or less, and most preferably 0.13 m / s.

[0091] In the capsule 10 of Example A2, the sphericity was 98±2% and the wall thickness uniformity was 88±11%, and the success rate before and after the drying process was 100% and 100%, respectively. The encapsulated substance content (%), defined as (mass [g] of encapsulated substance 11) / (mass [g] of capsule 10 before the drying process)×100, was 77%.

[0092] [Example B] Capsules 10 were produced under the same conditions as in Example A, except that edible solid particles 30, specifically soybean wax powder containing linoleic acid as the main component, were used. The diameter of the soybean wax powder used as solid particles 30 was 64±30 μm. Because solid particles 30 are edible, the solid particle removal step S5 shown in FIG. 4 can be omitted even when capsules 10 are intended for consumption. The peripheral speed of the inner surface of cylinder 111 was 0.13 m / s, the same as in Example A2.

[0093] 9 shows a micrograph of capsule 10 according to Example B. In capsule 10 according to Example B, the sphericity was 98±2%; the wall thickness uniformity was 91±16%; the success rate before drying was 100%; the success rate after drying was 100%; and the content rate of the encapsulated substance was 71%.

[0094] [Example C] The mono-core capsule 10 shown in FIG. 1A was manufactured using a capsule manufacturing apparatus 100 shown in FIG. 2. The encapsulated substance 11 according to this example is made of tetradecane, which is a heat storage material. Here, the heat storage material is a substance that can store thermal energy and release it when needed. The wall material 12 according to this example is made of gelatin. A gelatin aqueous solution with a concentration of 20% by mass was used as the wall material precursor liquid 21.

[0095] Specifically, mono-core capsules 10 were manufactured under the conditions that the flow rates of tetradecane as encapsulation substance 11 and the gelatin aqueous solution as wall material precursor liquid 21 from dripping device 130 shown in Fig. 3 were both 0.25 mL / min, and the peripheral speed of the inner surface of cylinder 111 was 0.19 m / s. The other manufacturing conditions were the same as in Example A. As a result, mono-core capsules 10 encapsulating tetradecane as a heat storage material were obtained.

[0096] The tetradecane content in the obtained capsules 10 was 91% by volume after drying. Furthermore, the capsules 10 according to this example had a sphericity of 98±1%, a wall thickness uniformity of 61±8%, and a success rate of 100% both before and after drying.

[0097] By encapsulating the heat storage material as the encapsulated substance 11 of the capsule 10, the specific surface area of ​​the heat storage material can be increased compared to when the same heat storage material is used in bulk form. This allows for quicker storage and release of heat. Therefore, the capsule 10 according to this embodiment contributes to energy conservation.

[0098] In the conventional method of producing capsules in a liquid phase, it was difficult to efficiently encapsulate the heat storage material in the capsules and to increase the content of the heat storage material in the capsules. In contrast, according to this embodiment, capsules 10 encapsulating the heat storage material could be obtained one after another efficiently. In addition, the content of tetradecane in the capsules 10 could be increased to 91%.

[0099] [Second embodiment] 2, in the first embodiment, the solid particles 30 are arranged on the inner surface of the cylindrical body 111, but the arrangement of the solid particles 30 may be omitted. This will be specifically described below.

[0100] 10, in this embodiment, inside the cylinder 111, droplets of the raw material liquid 20 come into direct contact with the inner surface of the guide groove 112. That is, in this embodiment, the powder placement step S1 shown in FIG.

[0101] Nevertheless, because the pitch P of the spiral guide groove 112 is larger than the diameter of the droplets of the raw material liquid 20, a gap is secured between adjacent droplets of the raw material liquid 20. This prevents adjacent droplets of the raw material liquid 20 from coalescing into one. This makes it possible to efficiently manufacture a large number of capsules, just like in the first embodiment.

[0102] In order to enhance the effect of suppressing the coalescence of droplets of the raw material liquid 20, the pitch P of the guide groove 112 is preferably 1.2 times or more the average diameter of the droplets, more preferably 1.5 times or more, and even more preferably 2 times or more.

[0103] For example, when the droplets of the raw material liquid 20 are 30 μL, the average diameter of the droplets is about 3.8 mm. In this case, the pitch P of the guide grooves 112 is preferably 4.5 mm or more, more preferably 5.7 mm or more, and even more preferably 7.6 mm or more.

[0104] Furthermore, it is preferable that the droplets of raw material liquid 20 maintain a substantially spherical shape on the inner surface of guide groove 112 due to their own surface tension. To achieve this, it is preferable that the inner surface of cylinder 111, including the inner surface of guide groove 112, is liquid-repellent with respect to raw material liquid 20.

[0105] When the inner surface of cylinder 111, including the inner surface of guide groove 112, exhibits a contact angle of 100° or more, preferably 150° or more, with respect to raw material liquid 20, it can be said that the inner surface of cylinder 111, including the inner surface of guide groove 112, is liquid-repellent with respect to raw material liquid 20. Specifically, cylinder 111 itself, or the surface layer of the inner surface of cylinder 111, including the surface layer of the inner surface of guide groove 112, may be made of any of the materials exemplified above as the material for solid microparticles 30. This makes it possible to impart liquid-repellency to cylinder 111.

[0106] [Third embodiment] FIG. 2 illustrates a cylindrical body 111 as an example of a cylindrical body surrounding the imaginary center line VL. The cylindrical body 111 has a straight shape in which the distance between the inner surface and the imaginary center line VL is constant along the length of the imaginary center line VL, i.e., the generatrix is ​​parallel to the imaginary center line VL. However, the cylindrical body does not necessarily have to have a straight shape. In this specification, the concept of a "cylinder" surrounding the imaginary center line VL also includes a shape having a portion where the distance between the inner surface and the imaginary center line VL changes along the length of the imaginary center line VL, for example, a tapered shape in which the generatrix is ​​inclined with respect to the imaginary center line VL.

[0107] 2 illustrates a spiral guide groove 112, the guide groove in which the droplets roll may be formed in a circular shape. As another example of the cylindrical body, an embodiment using a tapered cylindrical body with a circular guide groove formed on its inner surface will be described below.

[0108] 11, the cylindrical body 114 according to this embodiment has a shape that gradually widens in its inner diameter in the longitudinal direction parallel to the imaginary center line VL from the end where the dripping device 130 is disposed to the end where the capsule 10 is discharged. The guide groove 115 according to this embodiment is composed of a plurality of circumferential grooves 115a aligned in the longitudinal direction parallel to the imaginary center line VL.

[0109] In this embodiment, droplets of each liquid raw material 20 roll in the guide groove 115 in the form of liquid marbles 40. Because the generatrix of the cylinder 114 slopes downward as it moves away from the dripping device 130, each rolling liquid marble 40 moves downward along the generatrix under its own weight while oscillating in the circumferential direction of the cylinder 115. During this movement, the wall material liquid precursor 21 in each liquid marble 40 solidifies. Other configurations and functions are the same as those of the first embodiment.

[0110] The above describes the embodiments and examples. The following modifications (1) to (5) are also possible.

[0111] (1) FIG. 3 illustrates droplets of raw material liquid 20 in which mononuclear encapsulated substances 11 are covered with wall material precursor liquid 21. These droplets are suitable for producing capsule 10 shown in FIG. 1A. For example, the dripping nozzle for dripping raw material liquid 20 in dripping device 130 may be configured with a multi-tube structure including three or more tubes. This allows for the formation of droplets of raw material liquid 20 in which polynuclear encapsulated substances 11 are covered with wall material precursor liquid 21. These droplets are suitable for producing capsule 10 shown in FIG. 1B. Because the encapsulation of raw material liquid 20 progresses while the droplets of raw material liquid 20 roll, the position of encapsulated substances 11, which serve as nuclei, is less likely to be biased when producing polynuclear capsule 10 shown in FIG. 1B.

[0112] 1C can also be produced by using raw material liquid 20 in which encapsulated substance 11 is dispersed at the molecular level in wall material precursor liquid 21, or raw material liquid 20 in which encapsulated substance 11 is dissolved in wall material precursor liquid 21. Since encapsulation of raw material liquid 20 progresses while droplets of raw material liquid 20 roll, when producing capsule 10 shown in FIG. 1C, the internal structure can be made uniform.

[0113] (2) Although FIG. 3 illustrates an example of a configuration in which encapsulated substance 11 and wall material precursor liquid 21 are dropped together, encapsulated substance 11 and wall material precursor liquid 21 may be dropped separately. Separately dropped encapsulated substance 11 and wall material precursor liquid 21 may be encapsulated in the process of rolling in guide groove 112. In this case, the concept of "encapsulation" includes covering encapsulated substance 11 with wall material precursor liquid 21 and solidifying wall material precursor liquid 21 that has covered encapsulated substance 11. Note that when encapsulated substance 11 and wall material precursor liquid 21 are dropped separately, the powder placement step S1 described above may be omitted.

[0114] (3) Figures 2 and 11 illustrate an example of a rotating cylinder 110 in which the imaginary center line VL is horizontally disposed. The imaginary center line VL may have a slight inclination angle θ with respect to the horizontal plane, specifically, an inclination angle θ of, for example, 60° or less, preferably 30° or less. In this specification, the term "sideways posture" includes a case in which the imaginary center line VL has such a slight inclination angle θ. For example, in the configuration shown in Figure 2, by providing an inclination angle θ to the imaginary center line VL, the cylinder 111 may be inclined downward from the end where droplets are dropped toward the end where capsules 10 are ejected.

[0115] 12 shows a cylinder 111 with an inclination angle θ to the imaginary center line VL. Each liquid marble 40 rolling on the inner surface of the cylinder 111 oscillates circumferentially around the cylinder 111 and moves downward under its own weight along a generatrix parallel to the imaginary center line VL. In this configuration, as in the third embodiment, the guide groove 115 may be formed by multiple circumferential grooves 115a aligned in the longitudinal direction parallel to the imaginary center line VL.

[0116] (4) Figures 11 and 12 show an example of a configuration in which a circular guide groove 115 is formed on cylinders 114 and 111 whose generating lines are arranged at an angle with respect to the horizontal plane. A spiral guide groove 112 may be formed on cylinders 114 and 111 whose generating lines are arranged at an angle with respect to the horizontal plane. Also, Figure 2 shows an example of a configuration in which a spiral guide groove 112 is formed on cylinder 111 whose generating lines are arranged horizontally, but the same effect can be obtained by forming a circular guide groove 115 on cylinder 111 whose generating lines are arranged horizontally.

[0117] (5) In Figures 2 and 11, as examples of a cylindrical body surrounding the imaginary center line VL, cylindrical bodies 111 and 114 having a circular cross section perpendicular to the imaginary center line VL are shown. In this specification, the term "circular" is intended to include not only a perfect circle but also an ellipse. However, the cross section of the "cylinder" surrounding the imaginary center line VL does not necessarily have to be circular.

[0118] Specific examples of the encapsulated substance 11 will be described below.

[0119] The encapsulated substance 11 can be selected depending on the application of the capsule 10. Either an oil-soluble or water-soluble substance can be used as the encapsulated substance 11. The encapsulated substance 11 may be used alone or in combination of two or more kinds.

[0120] Examples of the oil-soluble encapsulated substance 11 include oil-soluble pesticides, adhesives, inks, heat storage materials, pharmaceuticals, etc. Specifically, examples of the oil-soluble encapsulated substance 11 that can be used include a heat / cold medium such as tetradecane, fat-soluble vitamins such as α-tocopherol, and anticancer drugs such as doxorubicin.

[0121] Examples of the water-soluble encapsulated substance 11 include water-soluble pesticides, adhesives, inks, heat storage materials, pharmaceuticals, etc. Specifically, solvents such as water, and proteins such as bovine serum albumin can be used as the water-soluble encapsulated substance 11.

[0122] The encapsulated substance 11 may be volatile or non-volatile. The encapsulated substance 11 may also be used by dissolving it in a solvent. The solvent can be appropriately selected depending on the encapsulated substance 11 used. When the encapsulated substance 11 is oil-soluble, for example, organic solvents such as acetone, methanol, ethanol, dimethyl sulfoxide, dichloroethane, dichloromethane, hexane, xylene, ethyl acetate, chloroform, and diethyl ether can be used. When the encapsulated substance 11 is water-soluble, for example, a solvent such as water can be used.

[0123] The present invention can be modified in various ways without departing from its broad spirit and scope. The above-described embodiments and examples are intended to illustrate the present invention and do not limit the scope of the present invention. The scope of the present invention is defined by the claims, not by the embodiments and examples. Various modifications made within the scope of the claims and within the meaning of the invention equivalent thereto are considered to be within the scope of the present invention.

[0124] This application is based on Japanese Patent Application No. 2021-98149 filed in Japan on June 11, 2021. The entire specification, claims, and drawings of Japanese Patent Application No. 2021-98149 are incorporated herein by reference. [Explanation of symbols]

[0125] 10…capsules, 11...Encapsulated substances, 12...wall materials, 13...composite matrix, 20...raw material liquid, 21...wall material precursor liquid, 30...solid fine particles, 40...Liquid Marble, 100...Capsule manufacturing equipment, 110...rotating cylinder, 111...Cylindrical body (cylindrical body), 112...guide groove, 113...rotation axis, 114...Cylindrical body (cylindrical body), 115...guide groove, 115a...Circumferential groove, 120...Rotating device, 130...Dripping device, 131...Inner pipe, 132...Outer tube, 140...solidification accelerator, VL...virtual center line.

Claims

1. A capsule manufacturing method using a cylindrical body formed in a cylindrical shape surrounding an imaginary center line, the cylindrical body having a spiral or circumferential guide groove formed on an inner surface around the imaginary center line, a dropping step of dropping an encapsulation substance and a wall material precursor liquid, which is a precursor of a wall material that covers the encapsulation substance, onto the inner surface of the cylindrical body; an encapsulation step in which the droplets dropped in the dropping step roll while contacting the inner surface of the guide groove of the cylindrical body rotating around the imaginary center line, thereby encapsulating the encapsulated substance and the wall material precursor liquid; a capsule discharging step in which capsules obtained by the encapsulation process are discharged from the cylindrical body; and a powder arranging step of arranging powder of solid fine particles smaller than the droplets in advance in the guide groove of the cylindrical body before the dropping step; and In the encapsulation process, the liquid droplets roll in the guide groove of the rotating cylinder together with the solid fine particles, thereby forming liquid marbles in which the solid fine particles are sprinkled on the surface of the liquid droplets, and the liquid droplets roll in the guide groove in the form of liquid marbles. Capsule manufacturing method.

2. the inner surface of the guide groove of the cylindrical body is liquid-repellent to the droplets; The method for producing capsules according to claim 1.

3. the amount of the droplet dropped at one time in the dropping step is 15 μL or less; a peripheral speed of the inner surface of the cylindrical body in the dropping step and the encapsulation step is 0.08 m / s or more and 0.24 m / s or less; The method for producing capsules according to claim 1.

4. the wall material precursor liquid has a gelling property, the encapsulation proceeds by the gelation of the wall material precursor liquid; The method for producing a capsule according to any one of claims 1 to 3.

5. the wall material precursor liquid contains a monomer, the encapsulation proceeds by polymerization of the monomer; The method for producing a capsule according to any one of claims 1 to 3.

6. the wall material precursor liquid contains a solvent, the encapsulation proceeds by removal of the solvent; The method for producing a capsule according to any one of claims 1 to 3.

7. a cylindrical body formed in a cylindrical shape surrounding an imaginary center line, the cylindrical body having a spiral or circumferential guide groove formed on its inner surface around the imaginary center line; a rotation device that rotates the cylindrical body around the imaginary center line; a dripping device that drips an encapsulation substance and a wall material precursor liquid that is a precursor of a wall material that covers the encapsulation substance onto the inner surface of the cylindrical body; Equipped with a powder of solid fine particles smaller than the droplets dropped by the dropping device is placed in advance in the guide groove of the cylindrical body; The droplets dropped by the dropping device roll together with the solid fine particles in the guide groove of the cylinder rotated by the rotation device, thereby forming liquid marbles with the solid fine particles coated on the surface of the droplets, and the droplets roll in the guide groove in the form of liquid marbles, and encapsulation of the encapsulated substance and the wall material precursor liquid progresses during the rolling process. Capsule manufacturing equipment.

8. The amount of the droplet dropped by the dropping device at one time is 15 μL or less. The capsule manufacturing apparatus according to claim 7.

9. a solidification promoting device that promotes solidification of the wall material precursor liquid in the droplets rolling in the guide groove of the cylindrical body; The capsule manufacturing apparatus according to claim 7 or 8, further comprising:

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