JP2020145954A - Method for promoting growth of algae - Google Patents

Abstract

To provide a method for promoting growth of algae with high effect.SOLUTION: A method for promoting growth of algae cultures algae in the presence of a composite particle containing a titanium oxide particle, a metal particle and a calcium phosphate particle.SELECTED DRAWING: Figure 1

Description

The present invention relates to a method for promoting the growth of algae. More specifically, the present invention relates to a method for promoting the growth of algae by using composite particles containing titanium oxide particles, metal particles and calcium phosphate particles.

Algae are microscopic-sized algae that live in oceans, rivers, and lakes, and most of them use sunlight like plants to photosynthesize carbon dioxide and synthesize carbohydrates, producing oil as a metabolite. Because of this, it is attracting attention as a new renewable energy source.
In addition to the energy source, algae are also expected to be used for various purposes such as agriculture, food, feed, pharmaceuticals, cosmetics, and biomaterials.
Therefore, there is an urgent need to establish an efficient mass culture technology for algae.

The techniques of Patent Documents 1 and 2 are known as a culture solution for promoting the growth of algae and a method for promoting the growth of algae.
Patent Document 1 discloses a culture solution capable of promoting the growth of diatoms by containing a powdery and granular siliceous material containing water and calcium silicate hydrate as main components in a specific ratio.
Further, Patent Document 2 discloses a method for growing algae by supplying a calcium silicate-containing material and a material for promoting algae growth containing a corrosive substance into water for growing the algae.

By the way, as a photocatalytic technology, in Non-Patent Document 1, "earthplus" (trademark) manufactured and sold by Shinshu Ceramics Co., Ltd. (Nagano Prefecture, Japan) is used for Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa. On the other hand, it is described that it has a bactericidal action. Earth Plus has been known to exert a bactericidal action based on the photocatalytic action of titanium oxide particles, the bactericidal action of silver particles and the adsorption action of hydroxyapatite particles.
However, no attention has been paid to the action of the composite material in which titanium oxide, silver and hydroxyapatite are compounded on the growth promotion of algae, and there is no disclosure or suggestion.

Japanese Unexamined Patent Publication No. 2015-167538 JP-A-2017-184731

An object of the present invention is to provide a novel method for promoting the growth of algae.

The present inventors have found that the growth can be promoted by growing algae in the presence of composite particles containing titanium oxide particles, metal particles and calcium phosphate particles, and have completed the present invention. As described above, since it was known that composite particles containing titanium oxide particles, metal particles and calcium phosphate particles have an effect of killing microorganisms (Non-Patent Document 1), titanium oxide particles and metal particles It was predicted that the composite particles containing the calcium phosphate particles and the calcium phosphate particles might inhibit the growth of algae. However, contrary to expectations, the present invention has revealed for the first time that the composite particles of the present invention have an effect of promoting the growth of algae.

Specifically, the present invention has the following configuration.
(1) A method for promoting the growth of algae, which comprises culturing algae in the presence of composite particles containing titanium oxide particles, metal particles and calcium phosphate particles.
(2) A material for promoting the growth of algae, which contains composite particles containing titanium oxide particles, metal particles and calcium phosphate particles.
(3) The material for promoting the growth of algae according to (2), wherein the material is any one selected from containers, concrete products, and non-woven fabrics.
(4) An algae growth promoter containing composite particles containing titanium oxide particles, metal particles and calcium phosphate particles as an active ingredient.
(5) A coating material for promoting the growth of algae, which contains composite particles containing titanium oxide particles, metal particles and calcium phosphate particles.
(6) A composition for culturing algae, which comprises composite particles containing titanium oxide particles, metal particles, and calcium phosphate particles.
(7) The culture composition according to (6), wherein the crystal structure of titanium oxide is anatase type.
(8) The culture composition according to (6), wherein the calcium phosphate is hydroxyapatite.

According to the present invention, the growth of algae can be promoted by growing the algae in the presence of composite particles containing titanium oxide particles, metal particles and calcium phosphate particles. The obtained algae can be used as an energy source and for various purposes such as agriculture, food, feed, pharmaceuticals, cosmetics, biomaterials, oil, and fuel.

A photograph of the inside of the concrete container one month after the start of the test is shown. A is a concrete container in the control plot, and B is a concrete container in the test plot. (Test Example 1) The photograph which observed the water in the concrete container of the test group at 100 times is shown. The photograph which observed the water in the concrete container of the test group at 400 times is shown. A photograph of the glass container after the start of the test taken from the side is shown. A is a photograph 0 days after the start of the test, B is a photograph 2 weeks later, and C is a photograph 7 months later. In each photograph, the right side is the glass container of the test plot, and the left side is the control glass container.

(Algae)
In the present invention, the algae to be promoted for growth is a general term for organisms that perform photosynthesis, excluding moss plants, fern plants, and seed plants that mainly inhabit the ground, and is a unicellular cyanobacteria (Cyanobacteria). From cyanobacteria), it means that eukaryotes that are unicellular and multicellular organisms are also included. Examples of eukaryotes that are unicellular organisms include diatoms, yellow-green algae, whirlpool algae, and green algae, and examples of multicellular organisms include seaweeds such as red algae, brown algae, and green algae. Diatoms are preferred.

(Composite particles)
The composite particles used in the present invention include one or more titanium oxide particles, one or more metal particles, and one or more calcium phosphate particles.
The number of titanium oxide particles per composite particle may be one or two or more. The number of titanium oxide particles per composite particle is usually two or more.

The form of the titanium oxide particles contained in the composite particles is not particularly limited, and examples thereof include spherical, granular, needle-like, flaky, and indefinite shapes. The composite particles may contain two or more titanium oxide particles having different morphologies.

The particle size of the titanium oxide particles contained in the composite particles is not particularly limited as long as it is smaller than the particle size of the composite particles, and can be appropriately adjusted according to the particle size of the composite particles. The titanium oxide particles contained in the composite particles are, for example, nanoparticles or submicron particles.

Examples of the crystal structure of titanium oxide constituting the titanium oxide particles include anatase type, rutile type, and brookite type, and among these, anatase type is preferable.

The number of metal particles per composite particle may be one or two or more. The number of metal particles per composite particle is usually two or more.

The form of the metal particles contained in the composite particles is not particularly limited, and examples thereof include spherical, granular, needle-like, flaky, and indefinite shapes. The composite particle may include two or more metal particles having different morphologies.

The particle size of the metal particles contained in the composite particles is not particularly limited as long as it is smaller than the particle size of the composite particles, and can be appropriately adjusted according to the particle size of the composite particles. The metal particles contained in the composite particles are, for example, nanoparticles or submicron particles.

The metal particles contained in the composite particles are selected from the group consisting of, for example, silver particles, gold particles, platinum particles and copper particles. The metal particles contained in the composite particles are preferably silver particles. The composite particle may contain two or more metal particles of different types.

The number of calcium phosphate particles per composite particle may be one or two or more. The number of calcium phosphate particles per composite particle is usually two or more.

The form of the calcium phosphate particles contained in the composite particles is not particularly limited, and examples thereof include spherical, granular, needle-like, flaky, and indefinite shapes. The composite particles may contain two or more calcium phosphate particles having different morphologies.

The particle size of the calcium phosphate particles contained in the composite particles is not particularly limited as long as it is smaller than the particle size of the composite particles, and can be appropriately adjusted according to the particle size of the composite particles. The calcium phosphate particles contained in the composite particles are, for example, nanoparticles or submicron particles.

Examples of calcium phosphate constituting the calcium phosphate particles include apatite (apatite), tricalcium phosphate, octacalcium phosphate and the like, and among these, apatite is preferable. Examples of apatite include hydroxyapatite, fluorinated apatite, carbonate apatite and the like, and among these, hydroxyapatite (Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ ) is preferable.

The content of titanium oxide particles, metal particles and calcium phosphate particles per composite particle is not particularly limited, but the lower limit of the content of titanium oxide particles is usually 10 parts by mass with respect to 1 part by mass of metal particles. It is preferably 20 parts by mass, more preferably 25 parts by mass, and even more preferably 30 parts by mass, and the upper limit of the content of the titanium oxide particles is usually 300 parts by mass, preferably 300 parts by mass with respect to 1 part by mass of the metal particles. It is 250 parts by mass, more preferably 200 parts by mass, and even more preferably 180 parts by mass. The lower limit of the content of the calcium phosphate particles is usually 1 part by mass, preferably 2 parts by mass, and more preferably 3 parts by mass with respect to 1 part by mass of the metal particles, and the upper limit of the content of the calcium phosphate particles is. , Usually 100 parts by mass, preferably 80 parts by mass, still more preferably 60 parts by mass, and even more preferably 50 parts by mass.

The particle size of the composite particles measured by the dynamic light scattering method is preferably 100 to 600 nm, more preferably 200 to 500 nm, and even more preferably 250 to 350 nm. The particle size measured by the dynamic light scattering method is a commercially available dynamic light scattering type particle size distribution measuring device, preferably a dynamic light scattering type nanotrack particle size distribution measuring device "UPA-EX150" (manufactured by Nikkiso Co., Ltd.). Measured by.

In the composite particles, it is preferable that one or more titanium oxide particles, one or more metal particles, and one or more calcium phosphate particles are arranged three-dimensionally and randomly.

In one embodiment of three-dimensional and random arrangement, at least one metal particle is attached to at least one titanium oxide particle.

In one embodiment of three-dimensional and random arrangement, one or more particles (titanium oxide) are surrounded by one particle (one particle selected from titanium oxide particles, metal particles and calcium phosphate particles). One or more particles selected from particles, metal particles and calcium phosphate particles) are present. In this embodiment, one or more particles of the same type may be adjacent to one particle, or one or more particles of different types may be adjacent to each other. Adjacent particles are preferably bonded and fixed to each other. Examples of the combination of adjacent particles include titanium oxide particles, metal particles, calcium phosphate particles, titanium oxide particles and metal particles, titanium oxide particles and calcium phosphate particles, metal particles and calcium phosphate particles, and the like.

In one embodiment of three-dimensional and random arrangement, a portion of at least one particle selected from titanium oxide particles, metal particles and calcium phosphate particles is exposed on the surface of the composite particles.

In one embodiment of three-dimensional and random arrangement, a portion of at least one titanium oxide particle, a portion of at least one metal particle and a portion of at least one calcium phosphate particle are exposed on the surface of the composite particle. are doing.

In one embodiment of three-dimensional and random arrangement, at least one particle selected from titanium oxide particles, metal particles and calcium phosphate particles is present inside the composite particles without being exposed on the surface of the composite particles. There is.

In one embodiment of three-dimensional and random arrangement, at least one particle selected from titanium oxide particles, metal particles and calcium phosphate particles has a membranous morphology and is present on at least a portion of the surface of the composite particles. ing.

In one embodiment of three-dimensional and random arrangement, two or more particles selected from titanium oxide particles, metal particles and calcium phosphate particles have a film-like morphology as one or a series, and the surface of the composite particles. It is present in at least part of.

Whether one particle has a particle morphology, has a membranous morphology, or has a membranous morphology integrally with or in conjunction with another one or more particles is a composite particle. It may be affected by the compounding ratio of particles when producing. Depending on the compounding ratio, one particle may no longer maintain its particle morphology and may take a membranous morphology that is present on at least a portion of the surface of the composite particle. For example, when particle compositing is performed by a mechanical method such as a bead mill or a ball mill, particles (for example, silver particles) composed of a material having a hardness lower than that of other particles take such a film-like form. obtain.
Two or more of the above embodiments relating to three-dimensional and random arrangement may be combined.

As the composite particles, for example, powder of a composite material sold by Shinshu Ceramics Co., Ltd. under the trade name "earthplus" can be used. Earth Plus is a composite material powder in which titanium oxide, silver and hydroxyapatite are composited, and contains one or more titanium oxide particles, one or more silver particles, and one or more hydroxyapatite particles. Contains composite particles consisting of. In the composite particles, one or more titanium oxide particles, one or more silver particles, and one or more hydroxyapatite particles are arranged three-dimensionally and randomly, and at least one silver particle is at least one. It is fixed to the titanium oxide particles of. Further, in the composite particles, a part of at least one titanium oxide particle, a part of at least one silver particle, and a part of at least one hydroxyapatite particle are exposed on the surface of the composite particle. Conceivable.

The composite particles are prepared by mixing titanium oxide powder, metal powder and calcium phosphate powder in a liquid using, for example, a wet mill, and one or more titanium oxide particles contained in the titanium oxide powder and 1 contained in the metal powder. It can be produced by combining one or more metal particles and one or more calcium phosphate particles contained in the calcium phosphate powder. The composite particles thus produced are then used in the present invention without being sintered.

The titanium oxide content (purity) in the titanium oxide powder is preferably 90% by weight or more, more preferably 95% by weight or more, and even more preferably 98% or more. The upper limit is, for example, 99%.

The particle size of the titanium oxide particles (primary particles) contained in the titanium oxide powder is not particularly limited, but is, for example, 0.03 to 0.1 μm. Since the wet mill can disperse the particle agglomerates into individual particles, the titanium oxide powder may contain agglomerates (secondary particles) of titanium oxide particles. The particle size of the aggregate of titanium oxide particles is, for example, 1 to 2 μm. The particle size of the titanium oxide particles or aggregates thereof is measured using, for example, a transmission electron microscope (TEM) or a scanning electron microscope (SEM).

The metal content (purity) in the metal powder is preferably 80% by weight or more, more preferably 95% by weight or more, and even more preferably 98% or more. The upper limit is, for example, 99.9%.

The particle size of the metal particles (primary particles) contained in the metal powder is not particularly limited, but is, for example, 1.1 to 1.9 μm. Since the wet mill can disperse the particle agglomerates into individual particles, the metal powder may contain agglomerates of metal particles (secondary particles). By freezing and storing the metal powder until use, it is possible to suppress the aggregation of the metal particles contained in the metal powder. The particle size of the metal particles or their aggregates is calculated, for example, based on the specific surface area.

The calcium phosphate content (purity) in the calcium phosphate powder is preferably 90% by weight or more, more preferably 95% by weight or more, and even more preferably 98% by weight or more.

The particle size of the calcium phosphate particles (primary particles) contained in the calcium phosphate powder is not particularly limited, but is, for example, 0.1 to 0.2 μm. Since the wet mill can disperse the particle agglomerates into individual particles, the calcium phosphate powder may contain agglomerates (secondary particles) of calcium phosphate particles. The particle size of the aggregate of calcium phosphate particles is, for example, 4 to 5 μm. The particle size of the calcium phosphate particles or their aggregates is measured by, for example, a laser diffraction / scattering method.

The wet mill disperses and finely pulverizes the particles contained in the titanium oxide powder, the metal powder, and the calcium phosphate powder in a liquid, and uses one or more titanium oxide particles, one or more metal particles, and one or more calcium phosphate. It can be compounded with particles. Examples of the wet mill include a bead mill and a ball mill, and among these, a bead mill is preferable. Examples of the material of the pulverizing medium such as beads and balls used in a mill such as a bead mill and a ball mill include alumina, zircon, zirconia, steel and glass, and among these, zirconia is preferable. The size (diameter) of the pulverized media can be appropriately adjusted according to the particle size and the like of the composite particles to be produced, but is usually 0.05 to 3.0 mm, preferably 0.1 to 0.5 mm. As the pulverizing medium, for example, beads or balls having a size of about 0.1 mm and a mass of about 0.004 mg can be used.

The liquid used for mixing is, for example, an aqueous medium such as water. When the liquid used for mixing is water, the total amount of titanium oxide powder, metal powder and calcium phosphate powder is usually 25 to 45 parts by mass, preferably 30 to 40 parts by mass with respect to 65 parts by mass of water. It is adjusted to be a part.

When mixing raw materials containing titanium oxide powder, metal powder, calcium phosphate powder and liquid with a wet mill, various conditions such as total addition amount of raw material powder, liquid flow rate, peripheral speed of blades in cylinder, stirring temperature, stirring The time and the like can be appropriately adjusted according to the particle size and the like of the composite particles to be produced. The total amount of the raw material powder (titanium oxide powder, metal powder and calcium phosphate powder) added is, for example, 4 kg or more, the cylinder volume is, for example, 0.5 to 4 L, and the flow rate of the liquid is, for example, 0.5 to 3 L / min. The peripheral speed of the blade is, for example, 300 to 900 m / min, the liquid temperature is, for example, 20 to 60 ° C., and the mixing time per 1 kg of the raw material powder is, for example, 0.5 to 2 hours. The upper limit of the total amount of the raw material powder added can be appropriately adjusted according to the cylinder volume and the like. The mixing time can be appropriately adjusted according to the total amount of the raw material powder added and the like.

As the raw material, it is preferable to add a dispersant in addition to titanium oxide powder, metal powder, calcium phosphate powder and liquid. Examples of the dispersant include a high molecular weight dispersant, a low molecular weight dispersant, an inorganic dispersant, and the like, and can be appropriately selected depending on the type of liquid used in the wet mixing. When the liquid used at the time of mixing is an aqueous medium such as water, for example, an anionic polymer-type dispersant, a nonionic polymer-type dispersant, or the like can be used as the dispersant, and an anion Examples of the sex polymer type dispersant include a polycarboxylic acid type dispersant, a naphthalin sulfonate formalin condensation type dispersant and the like, and examples of the nonionic polymer type dispersant include polyethylene glycol and the like. .. The amount of the dispersant added can be adjusted as appropriate, but is, for example, 0.1 to 3% by mass, preferably 0. It is 3 to 1% by mass.

Using a wet mill, the titanium oxide powder, metal powder and calcium phosphate powder are mixed in a liquid to form one or more titanium oxide particles contained in the titanium oxide powder and one or more metal particles contained in the metal powder. , A suspension (slurry) of composite particles can be produced by combining with one or more calcium phosphate particles contained in the calcium phosphate powder. Then, by removing the solvent in the suspension by evaporation or the like, an aggregate of composite particles (dry powder) can be produced. An aggregate (dry powder) of composite particles can also be produced from a suspension (slurry) of composite particles by a known granulation method such as a spray-dry granulation method.

The particle size of the aggregate of composite particles measured by the dynamic light scattering method is, for example, 100 to 600 nm, preferably 200 to 500 nm. The median diameter (d50) of the aggregate of composite particles measured by the dynamic light scattering method on a volume basis is, for example, 250 to 350 nm, preferably about 300 nm. For the particle size by the dynamic light scattering method, a commercially available dynamic light scattering type particle size distribution measuring device, preferably a dynamic light scattering type nanotrack particle size distribution measuring device "UPA-EX150" (manufactured by Nikkiso Co., Ltd.) is used. Is measured.

The produced composite particles can be used as they are in the present invention, but the particle size may be adjusted before using them in the present invention. The particle size can be adjusted, for example, by sieving the composite particles in the powder or suspension state.

In the aggregate of composite particles, the number of titanium oxide particles, metal particles, and calcium phosphate particles per composite particle may be the same or different among the composite particles.

In addition to the composite particles containing one or more titanium oxide particles, one or more metal particles, and one or more calcium phosphate particles, the aggregate of the composite particles is used when the composite particles are produced. Other particles that can be by-produced may be mixed. Examples of other particles include a single titanium oxide particle, a single metal particle, a single calcium phosphate particle, a bond between titanium oxide particles (excluding metal particles and calcium phosphate particles), and a bond between metal particles (oxidation). Titanium particles and calcium phosphate particles are not included), conjugates of calcium phosphate particles (excluding titanium oxide particles and metal particles), conjugates of titanium oxide particles and metal particles (excluding calcium phosphate particles), titanium oxide particles Examples thereof include a bond with calcium phosphate particles (excluding metal particles) and a combination of metal particles and calcium phosphate particles (excluding titanium oxide particles).

(How to grow algae in the presence of composite particles)
The method for growing algae in the presence of the composite particles of the present invention may be any method as long as the composite particles of the present invention are present in the growing environment of the algae, and the present invention is placed in the algae growth container (culture container). Examples thereof include, but are not limited to, a method of immobilizing the composite particles of the above, and a method of placing a material carrying the composite particles of the present invention in the culture solution.
The water used for culturing algae may be any water that can grow algae, such as seawater, fresh water, tap water, or a culture solution (so-called medium) containing these waters and other nutrients. It may be.
In the natural environment, the places where algae grow can be in the sea, in rivers, in ponds, in swamps, in lakes, and so on. Moreover, since algae have various uses as raw materials in the present invention, growing algae can be regarded as producing algae. In addition to the above-mentioned natural environment, algae can be produced in various forms such as industrial production by a large-scale plant, small-scale culture tank, and production by a culture container, and the production environment is indoors or outdoors. It may be any of.

Examples of the method for immobilizing the composite particles of the present invention on the culture container include a method of attaching the composite particles to the completed culture container later and a method of manufacturing the container by including it in the raw material of the material to be the container. Examples of the method of adhesion include a method in which composite particles are mixed with a binder resin or the like and adhered to a container as a paint. An example of adhering to concrete is a method of painting concrete as a binder resin. As the binder resin, a well-known binder resin can be used, but among them, an acrylic copolymer resin is preferable, and Tonan Bond (manufactured by Tonan Bond Co., Ltd.) can be exemplified.
Further, when the material holding the composite particles of the present invention is placed in the algae culture solution, the type of the material may be any material and shape as long as it can be placed in the culture solution.
Examples of the material of the material include concrete, glass, ceramics, pottery, metals such as iron and copper, sponges, non-woven fabrics, fibers, cloths, textile products, resins such as foamed styrol, and paper.
Examples of the form and shape of the material include cloth, string, ball, plate, container, block, and particles.

Typically, there is a method of applying the composite particles of the present invention and a binder kneaded product such as Tonan to a glass container, a resin container, a metal container, a concrete container or the like as a culture container for algae. Alternatively, a form in which a material such as a non-woven fabric, a concrete block piece, or particles carrying the composite particles of the present invention is added to the culture vessel is a typical example.
Further, the material for immobilizing the composite particles of the present invention is preferably a breathable or porous material, and examples thereof include textile products and concrete.

Hereinafter, an example in which the composite particles of the present invention are attached to a breathable sheet (material) via a binder resin will be described as a typical example, and the material can be used for any of the above.
After supplying the breathable sheet with the mixed solution containing the composite particles and the binder resin, or by immersing the breathable sheet in the mixed solution containing the composite particles and the binder resin, the breathable sheet is dried. A breathable sheet in which composite particles are attached via a binder resin can be produced. Further, after supplying the mixed liquid containing the composite particles and the binder resin to the raw fabric of the breathable sheet, or after immersing the raw fabric of the breathable sheet in the mixed liquid containing the composite particles and the binder resin, the air is ventilated. By drying the raw fabric of the sex sheet and then cutting out the breathable sheet from the raw fabric of the breathable sheet, a breathable sheet in which composite particles are attached via a binder resin can be produced.

The amount of the binder resin contained in the mixed solution is preferably 20 to 90 parts by mass, more preferably 30 to 85 parts by mass, and even more preferably 40 to 80 parts by mass with respect to 100 parts by mass of the composite particles. The same applies to the amount of binder resin contained in the breathable sheet.

The total amount of composite particles and binder resin adhered per unit area of the breathable sheet is not particularly limited, but the lower limit of the total amount of adhesion is usually 2 g / m ² , preferably 3 g / m ² , and more preferably 4 g / m. m ² , even more preferably 5 g / m ² , even more preferably 6 g / m ² , and the upper limit of the total adhesion amount is usually 30 g / m ² , preferably 25 g / m ² , still more preferably 20 g / m. ² , even more preferably 15 g / m ² .
As for the present adhesion amount, the same adhesion amount can be mentioned as a preferable range when applied to other materials such as concrete.

As the binder resin, a known resin having adhesiveness can be used alone or in combination of two or more. Examples of the binder resin include natural glues or natural resins such as gelatin, arabic rubber, shelac, dammar, elemy, and sandalak; semi-synthetic glues or semi-synthetic such as methyl cellulose, ethyl cellulose, nitrocellulose, carboxymethyl cellulose, and acetate. Resins; Isophthalic acid-based, terephthalic acid-based, bisphenol-based, vinyl ester-based polyester resins; Acrylic copolymer resins such as ethylene-acrylic acid, ethylene-acrylic acid ester, acrylic ester-vinyl, and methacrylate-vinyl ester; Isocyanurate derivatives or isocyanurate derivatives such as tolylene cisisocianate, 4,4'-diphenylmethane diisocyanate, lysine ester triisocyanate, isocyanate derivatives or isocyanurate derivatives such as tolylene diisocyanate, polyester polyols, polyether polyols, acrylic loylol , Urethane resin formed by reaction with polyol such as phenolic polyol; halogenated polymer such as polyvinyl chloride and polyvinylidene chloride; polyvinyl acetate, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer , Polyacrylic ester, polystyrene, polyvinyl acetal and other acetal resins; polycarbonate resins; cellulose acetate and other cellulose resins; polyolefin resins; urea resins, melamine resins, benzoguanamine resins and other amino resins and other synthetic glues or synthetics. Resins: Silicone resins such as polyalkylsiloxane, polyalkylhydrogensiloxane, polyalkylalkenylsiloxane, polyalkylsilicate, polyalkalialkylsilicate, polyalkylphenylsiloxane, epoxy-modified, amino-modified, urethane-modified, alkyd-modified. , A modified product such as acrylic modification, a silicone resin containing a copolymer, etc .; or a polymer such as tetrafluoroethylene or vinylidene fluoride, a fluororesin such as a copolymer of these monomers and other kinds of monomers, etc. Be done. Of these, urethane-based resins and silicone resins are preferable, and urethane-based resins are particularly preferable, from the viewpoint of adhesiveness and the like. Further, as the binder resin applied to concrete, an acrylic copolymer resin is preferable, and Tonan Bond (manufactured by Tonan Bond Co., Ltd.) can be exemplified.

Inorganic binders may be used alone or in combination of two or more in place of the binder resin or in combination with the binder resin. Examples of the inorganic binder include alkyl silicates, silicon halides, products obtained by decomposing hydrolyzable silicon compounds such as partial hydrolysates thereof, organic polysiloxane compounds and their polycondensates, silica, colloidal silica. , Water glass, silicon compounds, phosphates such as zinc phosphate, metal oxides such as zinc oxide and zirconium oxide, bicarbonate, cement, gypsum, lime, frit for brooms and the like.

The algae growth-promoting agent containing the composite particles containing the titanium oxide particles, metal particles and calcium phosphate particles of the present invention as an active ingredient may be the composite particles themselves or as long as the growth-promoting action of the present invention is not impaired. If there is, other ingredients can be included. Of course, it can also be used in combination with other known methods for promoting the growth of algae. Other known methods for promoting the growth of algae include a method of adding a growth-promoting agent composition and a method of controlling by temperature and light.
The composition for culturing algae containing the composite particles containing the titanium oxide particles, the metal particles and the calcium phosphate particles of the present invention may be any composition containing the composite particles and does not impair the growth promoting action of the present invention. In the range, other known components can be included.

Hereinafter, the present invention will be described in more detail based on Production Examples and Test Examples. However, the scope of the present invention is not limited to these production examples and test examples.

Production Example 1: Production of composite particles In this production example, titanium oxide powder, silver powder and hydroxyapatite powder are used as raw material powders, and one or more titanium oxide particles, one or more silver particles and one or more hydroxya. Composite particles containing apatite particles were produced.

In this production example, two types of composite particles M1 and M2 were produced. The composite particles M1 and M2 differ in the content ratios of titanium oxide, silver and hydroxyapatite. The composite particles M1 and M2 were manufactured in the same manner as "earthplus" (trademark) manufactured and sold by Shinshu Ceramics Co., Ltd. The production of composite particles M1 and M2 was outsourced to Shinshu Ceramics Co., Ltd.

The raw material powders shown in Table 1 were prepared. The particle size of the titanium oxide powder is a value measured using a transmission electron microscope (TEM) or a scanning electron microscope (SEM), and the particle size of the silver powder is a value calculated based on the specific surface area. The particle size of the hydroxyapatite powder is a value measured by a laser diffraction / scattering method. Since the silver powder was stored frozen until use, the aggregation of silver particles contained in the silver powder was suppressed.

Titanium oxide powder by mixing titanium oxide powder, silver powder, hydroxyapatite powder and polycarboxylic acid-based dispersant in water using a commercially available wet bead mill (“Star Mill LME” manufactured by Ashizawa Finetech Co., Ltd.). One or more titanium oxide particles contained in the above, one or more silver particles contained in the silver powder, and one or more hydroxyapatite particles contained in the hydroxyapatite powder are compounded to form a suspension of the composite particles. Slurry) was produced. The wet bead mill used can be finely pulverized while dispersing titanium oxide particles, silver particles and hydroxyapatite particles contained in the raw material powder, and can be finely divided into nanoparticles or submicron particles, and the finely divided particles are combined. Can be transformed into.

The conditions for particle compositing using a wet bead mill are as follows.
Total amount of raw material powder added: 4 kg or more Cylinder volume: 3.3 L
Beads: Zirconia beads (diameter 0.5 mm, mass 0.37 mg)
Liquid flow rate: 2 L / min Peripheral speed of blades in cylinder: 540 m / min Liquid temperature: 35-45 ° C
Mixing time per 1 kg of raw material powder: 30-40 minutes (about 36 minutes)

The total amount of titanium oxide powder, silver powder and hydroxyapatite powder was adjusted to 35 parts by mass with respect to 65 parts by mass of water. The blending amount of the polycarboxylic acid-based dispersant was adjusted to 0.5 parts by mass with respect to 35 parts by mass of the total blending amount of titanium oxide powder, silver powder and hydroxyapatite powder.

In the production of the composite particle M1, the blending amount of the titanium oxide powder is adjusted to about 160 parts by mass (155 to 165 parts by mass) with respect to 1 part by mass of the silver powder, and the blending amount of the hydroxyapatite powder is adjusted to 1 mass by mass of the silver powder. It was adjusted to about 40 parts by mass (39 to 41 parts by mass) with respect to the part.

In the production of the composite particle M2, the blending amount of the titanium oxide powder is adjusted to about 30 parts by mass (29 to 31 parts by mass) with respect to 1 mass part of the silver powder, and the blending amount of the hydroxyapatite powder is 1 mass by mass of the silver powder. It was adjusted to about 3 parts by mass (2.5 to 3.5 parts by mass) with respect to the part.

Composite particles M1 and M2 were produced by drying a suspension (slurry) of composite particles. The particle diameters of the composite particles M1 and M2 measured by the dynamic light scattering method were 200 to 500 nm. The median diameter (d50) of the composite particles M1 and M2 measured by the dynamic light scattering method on a volume basis was about 300 nm. The particle size by the dynamic light scattering method is determined by a commercially available dynamic light scattering type particle size distribution measuring device, specifically, a dynamic light scattering type nanotrack particle size distribution measuring device "UPA-EX150" (manufactured by Nikkiso Co., Ltd.). ) Was used for measurement.

[Test Example 1] Test using composite particles of the present invention (outdoor test)
In this test, water was placed in a container coated with a binder containing the composite particles of the present invention, and the effect of the composite particles of the present invention on promoting the growth of algae was investigated.
1. 1. Test method 1-1. Material (1) Container
(A) Concrete container of the test group In a cylindrical concrete container (inner diameter 45 cm, height 19 cm, content capacity about 30 L) with an open top, the following composite particle solution (i) 30 ml and binder solution (ii) 30 ml of the present invention Of 90 ml of a mixed solution of 30 ml of water, about 25 ml is painted (applied) to a height of about 15 cm on the entire inside of a cylindrical concrete container with a brush, and left at room temperature for 3 days to dry to prepare a test container. Made.
(i) Composite particle solution; an aqueous solution containing 35% by weight of the composite particle M1 of the present invention.
(ii) Binder solution; Product name Tonanbond (manufactured by Tonanbond Co., Ltd.) dissolved in a very small amount of water (b) Concrete container in the control section 30 ml of the binder solution of (ii) above and 60 ml of a mixed solution of 30 ml of water were used. Except for the above, the container was made in the same manner as the concrete container in the test plot.

1-2. Test method 24 L of tap water was put into one concrete container in the control group and 24 L of tap water in the concrete container in the test group, and left under a vinyl sheet tent for about one month to observe the growth and growth of algae. The tent had only a roof and the sides were exposed to the outside air, and a wooden drainboard with a height of about 5 cm was laid on the underside of the container so that the container would not come into direct contact with the ground.

1-3. Test location Tokawa, Hadano City, Kanagawa Prefecture

1-4. Test period November-December 2017

2. 2. Test Results Figure 1 shows a photograph of the inside of the concrete container one month after the start of the test. A is a concrete container in the control plot, and B is a concrete container in the test plot. In the control plot, the water was transparent without algae growing, but in the test plot, algae grew on the water surface and filled the entire water surface, so that the inside could not be seen.
FIG. 2 shows a photograph of water in the concrete container of the test plot observed at 100 times, and FIG. 3 shows a photograph of water observed under a microscope at 400 times. From the photograph of FIG. 2, it was found that a plurality of types of algae were generated in the water of the test plot, and diatoms were contained from the photograph of FIG. 3 in which a part of them was enlarged.
According to this result, a large amount of algae grew and grew in the test plot coated with the composite particles of the present invention and the binder, despite the low temperature period of November. On the other hand, no algae growth was observed in the control group to which only the binder was applied.
From the above, it was found that the composite particles of the present invention have an effect of promoting the growth and growth of algae.

[Test Example 2] Test using composite particles of the present invention (indoor test)
In this test, a concrete block piece coated with a binder containing the composite particles of the present invention was placed in a glass container together with water, and the effect of the composite particles of the present invention on promoting the growth of algae was investigated.
1. 1. Test method 1-1. Material (1) Glass container A cylindrical glass container (inner diameter 5.5 cm, height 11 cm, content capacity about 260 mL) having a top lid was prepared.
(2) Concrete block piece carrying the composite particles of the present invention Of the following composite particle solution (i) 30 ml, binder solution (ii) 30 ml, and water 30 ml mixed solution 90 ml, about 25 ml was painted (applied) with a brush 2 cm. A concrete piece of about × 1.5 cm × 1.5 cm was left at room temperature for 3 days and dried to prepare a concrete piece for testing.
(I) Composite particle solution; Aqueous solution containing 35% by weight of the composite particle M1 of the present invention (ii) Binder solution; Product name Tonanbond (manufactured by Tonanbond Co., Ltd.) dissolved in a very small amount of water 1-2. Test group and control group In the test group, 500 ml of tap water and two concrete block pieces were placed in the above glass container.
In the control group, only 500 ml of tap water was placed in the glass container.

1-3. Test method Add 50 ml of spirulina (diatomaceous algae) (purchased from the company), 200 ml of the culture solution attached to the spirulina culture set, and 30 ml of tap water to the water in the glass container of the control group and the test group, cover and cover the spirulina. The growth was observed.

1-4. Test temperature, test period The static observation was carried out indoors (normal temperature) by the window under natural light for about 7 months. No lighting was provided at night.

2. 2. Test Results Fig. 4 shows a photograph of the glass container after the start of the test taken from the side. A is a photograph 0 days after the start of the test, B is a photograph 2 weeks later, and C is a photograph 7 months later. In each photograph, the right side is the glass container of the test plot, and the left side is the control glass container.
According to this result, spirulina proliferated in both the test group and the control group and the water appeared green in 2 weeks after the start of the test, but after 7 months, the concrete piece coated with the composite particles of the present invention and the binder Spirulina survived and appeared green in the test plot. On the other hand, in the control area where no concrete pieces were put, a brown mass, which seems to be a dead spirulina, sank at the bottom, but the water at the top was translucent to the extent that it was slightly turbid.
From the above, it was found that the composite particles of the present invention have an effect of promoting the survival, growth and growth of algae.

[Test Example 3] Production of material for promoting the growth of algae In Test Examples 1 and 2, the effect was confirmed in a container or a concrete block piece in which composite particles were coated with a binder. In addition, the same effect can be expected with non-woven fabrics, textile products, and expanded polystyrene in which hydrosilver titanium is immobilized.
1. 1. Production of Nonwoven Fabric with Composite Particles A binder resin is added to the suspension (slurry) of composite particles M1 obtained in Production Example 1 to prepare a mixed solution, and then a polyester spunpond nonwoven fabric is immersed in the mixed solution to form a nonwoven fabric. The mixture was impregnated. After the immersion, the non-woven fabric was taken out from the mixed solution and pressed with a roller to squeeze out the excess mixed solution. After pressing, the non-woven fabric was dried at about 130 ° C. for about 1 minute to produce a composite particle-adhered non-woven fabric N1. As the binder resin, a urethane resin (C ₃ H ₇ NO ₂ / NH ₂ COOC ₂ H ₅ ) was used.

By adjusting the concentrations of the composite particles M1 and the binder resin in the mixed solution, the total adhesion amount (total fixed amount) of the composite particles M1 and the binder resin per unit area of the composite particle-adhering non-woven fabric N1 is 4 g / m ² , 6 g. It was adjusted to / m ² , 8 g / m ² or 10 g / m ² .

Breakdown of 4g / ^{m 2,} the titanium oxide 2.27 g / ^{m 2,} hydroxyapatite 0.571 g / ^{m 2,} a silver 0.014 g / ^{m 2,} was a binder resin 1.14 g / ^{m 2.}

The breakdown of 6 g / m ² was titanium oxide 3.41 g / m ² , hydroxyapatite 0.857 g / m ² , silver 0.021 g / m ² , and binder resin 1.71 g / m ² .

Breakdown of 8 g / ^{m 2,} the titanium oxide 4.54 g / ^{m 2,} hydroxyapatite 1.143 g / ^{m 2,} a silver 0.029 g / ^{m 2,} was a binder resin 2.29 g / ^{m 2.}

Breakdown of 10 g / ^{m 2,} the titanium oxide 5.68 g / ^{m 2,} hydroxyapatite 1.428g / ^{m 2,} a silver 0.036 g / ^{m 2,} was a binder resin 2.86 g / ^{m 2.}

The composite particle-adhered nonwoven fabric N2 was produced in the same manner as above, except that the suspension of the composite particles M2 was used instead of the suspension of the composite particles M1.

By adjusting the concentrations of the composite particles M2 and the binder resin in the mixed solution, the total adhesion amount (total fixed amount) of the composite particles M2 and the binder resin per unit area of the composite particle-attached non-woven fabric N2 is 13.5 g / m ^2. Adjusted to.

Breakdown of 13.5 g / ^{m 2,} the titanium oxide 6.525g / ^{m 2,} hydroxyapatite 0.750 g / ^{m 2,} a silver 0.225 g / ^{m 2,} was a binder resin 6.00 g / ^{m 2.}

2. 2. Production of Styrofoam Sheet or Styrofoam Beads with Composite Particles The Styrofoam with composite particles and Styrofoam beads with composite particles were produced by mixing the raw materials of Styrofoam with the composite particles M1 or M2 of the present invention.

3. 3. How to use (1) Immerse the non-woven fabric in the container. Immerse the non-woven fabric in the container. The non-woven fabric N1 or N2 of the above is installed so as to be immersed. At least a part of the fabric may be immersed, the whole fabric may be immersed, the non-woven fabric may be rolled up and immersed, or the non-woven fabric may be laid on the bottom surface. The same effect as when the algae culture container is painted can be expected.

(2) Float the Styrofoam sheet or Styrofoam beads on the surface of the water. Float Styrofoam sheets or Styrofoam beads. Since algae grow on the water surface, the growth of algae can be efficiently promoted by coming into contact with the Styrofoam sheet or Styrofoam beads floating on the water surface.

According to the present invention, the growth of algae can be promoted by a very simple method of growing algae in the presence of composite particles containing titanium oxide particles, metal particles and calcium phosphate particles.

Claims (8)

A method for promoting the growth of algae, which comprises culturing algae in the presence of composite particles containing titanium oxide particles, metal particles and calcium phosphate particles. A material for promoting the growth of algae, which comprises composite particles containing titanium oxide particles, metal particles and calcium phosphate particles. The material for promoting the growth of algae according to claim 2, wherein the material is any one selected from a container, a concrete product, and a non-woven fabric. An algae growth promoter containing composite particles containing titanium oxide particles, metal particles and calcium phosphate particles as an active ingredient. A coating material for promoting the growth of algae, which comprises composite particles containing titanium oxide particles, metal particles and calcium phosphate particles. A composition for culturing algae, which comprises composite particles comprising titanium oxide particles, metal particles and calcium phosphate particles. The culture composition according to claim 6, wherein the crystal structure of titanium oxide is anatase type. The culture composition according to claim 6, wherein the calcium phosphate is hydroxyapatite.