WO2015156164A1

WO2015156164A1 - Algae inhibitor including ion complex

Info

Publication number: WO2015156164A1
Application number: PCT/JP2015/060065
Authority: WO
Inventors: 弘文白馬; 柴谷　滋郎; 久人小林
Original assignee: 東洋紡株式会社
Priority date: 2014-04-08
Filing date: 2015-03-31
Publication date: 2015-10-15
Also published as: JPWO2015156164A1

Abstract

[Problem] To provide an algae inhibitor which is highly safe, and which can be broadly utilized in life-science fields requiring algae-inhibiting properties in water-based equipment such as cooling towers and circulation-type baths. [Solution] The present invention provides an algae inhibitor including a PGA ion complex formed from poly-γ-glutamic acid and a cationic bactericide. Also provided is a method in which the algae inhibitor is used to inhibit algae in a bathroom facility, a pool, a humidifier, a water tank, a plastic greenhouse, an indoor plant-cultivation facility, a cooling tower, a water storage tank, a fountain facility, or an aquaculture facility.

Description

Algae inhibitor containing ion complex

The present invention provides an algal inhibitor containing an ion complex formed from poly-γ-glutamic acid and a cationic fungicide.

In recent years, in order to maintain environmental hygiene, there has been a demand for higher performance of general life materials that are given antibacterial and antifungal properties. Regardless of whether it is outdoors or indoors, in places with high humidity such as water fields, bacteria and fungi are easy to propagate and there are many opportunities for indirect contact. In particular, when drinking water or bath water is used, there is a risk of causing food poisoning and infectious diseases due to pathogenic bacteria. Legionella is a bacterium that infests amoeba inhabiting artificial water with a water temperature of 20 ° C or higher, or grows together with algae and invades the human respiratory system together with aerosols, causing Legionella pneumonia and Pontiac fever It is known that Legionella bacteria tend to be generated in places such as bathtubs, cooling tower cooling water, fountains, humidifiers, etc., because they live in biofilms formed by algae and amoeba. For this reason, according to the guidelines of the Ministry of Health, Labor and Welfare, some public facilities are regularly cleaned to prevent the formation of algae and biofilms in order to prevent the generation of Legionella bacteria, and measures to prevent Legionella disease are taken. Conventional methods of removing biofilms and algae include chemical cleaning methods such as hypochlorous acid, hydrogen peroxide and peracetic acid, ozone and UV disinfection methods, brushing, and water cleaning methods. Regular cleaning and maintenance are carried out. Although the above-mentioned chemical disinfection method is excellent in that algae and biofilm are oxidatively decomposed and removed, there is a problem that the corrosiveness to the base material is high and the aging of the equipment is promoted. In addition, the disinfection method using ozone and UV requires expensive equipment costs.

Other than the above, chemical antiseptics with low corrosive properties include nitrogen antibacterial agents such as benzalkonium chloride and polyhexamethylene biguanidine hydrochloride, and synthetic antibacterial agents such as sulfur antibacterial agents. Biofilms and algae tend to adhere to equipment bases, inner walls, and piping surfaces of water-based equipment. For this reason, even if it disinfects by circulating the chemical | medical agent containing these antibacterial agents, an antimicrobial component will elute in water and there exists a subject that only a temporary effect is acquired.

Patent Document 1 describes an algal inhibitor containing an isothiazoline compound and a cationic polymer. According to the present invention, it is described that by adding the algal inhibitor to aqueous water, the isothiazoline compound and the cationic polymer synergistically suppress the generation of algae and the like effectively. In Patent Document 2, an algal control agent in which isouron and 3- (3,4-dichlorophenyl) -1,1-dimethylurea are combined is described as an anti-algae agent for paint having a low elution property.

The invention described above is an algal inhibitor combining a nitrogen-based antibacterial agent and a synthetic polymer, and is expected as a highly sustainable agent. However, when these antibacterial agents are used in water-based facilities, there are concerns about leakage into rivers and residual toxicity, especially when considering use in facilities that are indirectly in contact with the human body, such as for beverages and bathtubs, Low environmental impact and low toxicity agents are required.

In view of the current situation, as an algae inhibitor, a material that effectively suppresses algae and biofilms and has both low environmental load and safety is required.

JP 2013-14619 A JP 2011-68608 A

In view of the above-mentioned background art, a material having safety to human body, low environmental load, adhesion to base material and antibacterial property is desired as an algal inhibitor.

The present inventor has intensively studied to solve the above-mentioned problems, and an ion complex of poly-γ-glutamic acid (hereinafter referred to as “PGA ion complex” or simply “PGAIC”) is used for algae and biotechnology in an aqueous facility. Focusing on application as a film inhibitor, the present invention has been achieved. That is, typical inventions are as follows.

[1] An algal inhibitor comprising a PGA ion complex formed from poly-γ-glutamic acid and a cationic fungicide.
[2] The algal inhibitor according to [1], wherein the cationic bactericidal agent is quaternary ammonium.
[3] The algal inhibitor according to [1], wherein the cationic fungicide is a biguanide fungicide.
[4] The algal inhibitor according to [1], wherein the cationic fungicide is at least one selected from the group consisting of cetylpyridinium, benzethonium, chlorhexidine, benzalkonium, laurylpyridinium, and chlorhexidine.
[5] The algae inhibitor according to any one of [1] to [4], which comprises a solution containing the PGA ion complex and alcohol and / or hydrocarbon.
[6] The algal inhibitor according to [5], wherein the alcohol is one or more selected from the group consisting of ethanol, methanol, and isopropanol.
[7] The algae inhibitor according to [5] or [6], wherein the PGA ion complex is contained in the solution in an amount of 0.1 to 20 wt%.
[8] The algae inhibitor according to any one of [1] to [7], wherein L-glutamic acid accounts for 90% or more of glutamic acid constituting poly-γ-glutamic acid.
[9] The algal inhibitor according to any one of [1] to [8], wherein the glutamic acid constituting the poly-γ-glutamic acid is L-glutamic acid.
[10] A water pipe that is a water conduit, a water pipe, a water pipe, or a water pipe coated with the algal inhibitor according to any one of [1] to [9] on its inner surface.
[11] A water pipe having the algae inhibitor described in [1] to [9] coated on the inner surface.
[12] A water treatment filter containing the algal inhibitor according to any one of [1] to [9].
[13] A water-absorbent sheet comprising a resin foam, a water-absorbing polymer, or a nonwoven fabric, which has been subjected to an alga-proof treatment using the algal inhibitor according to [1] to [9].
[14] Bathroom facilities, pools, humidifiers, water tanks, greenhouses, indoor plant cultivation facilities, cooling towers, storage water tanks, fountain facilities, or farm facilities using the algae inhibitor described in [1] to [9] A method for controlling algae.
[15] In a bathtub facility, a pool, a humidifier, a water tank, a greenhouse, an indoor plant cultivation facility, a cooling tower, a storage water tank, a fountain facility or a farm facility using the algal inhibitor according to [1] to [9] A method for suppressing the generation of Legionella.

The present invention makes it possible to effectively suppress algae by applying an ion complex formed from poly-γ-glutamic acid and a cationic bactericidal agent to an aqueous facility or compounding a base material. The PGA ion complex of the present invention is a material imparted with algae generation inhibitory property to the adhesiveness and biodegradability derived from poly-γ-glutamic acid, and exhibits water insolubility. It has a high ability and suppresses the loss of the algae-preventing component, thereby showing the durability of the algae-inhibiting effect. Therefore, algae and microorganisms can be continuously prevented from growing in water-based facilities such as a cooling tower, a circulating bath, a fountain, and a humidifier. As a further effect, it is possible to save the maintenance of cleaning, and to keep the equipment that is difficult to clean, such as water pipes, water pipes, and drainage pumps, out of reach.

(PGA ion complex)
Poly-γ-glutamic acid (hereinafter sometimes referred to as PGA), which is a natural polymer, is a polyamino acid in which the α-amino group and γ-carboxyl group of glutamic acid are formed by amide bonds. PGA has come to be known as the main component of natto stringing, but since it is a substance produced by microorganisms, it has high affinity with microorganisms and also has adhesiveness, biodegradability, and biocompatibility .

The type of PGA is not particularly limited. For example, there are those consisting only of L-glutamic acid, those consisting only of D-glutamic acid, and those containing both, any of which can be used. However, the higher one ratio is, the better the stereoregularity, the higher the strength, etc., and the better the melting point (about 150 ° C.) when dried. This melting point becomes clearer by using an ion complex. Furthermore, since L-glutamic acid is superior in biodegradability, it is preferable to use PGA having a L-glutamic acid content of 90% or more.

The molecular size of the PGA used is not particularly limited, but an average molecular weight of 10 kD or more is preferable. In general, the larger the molecular size, the higher the adhesion performance to the skin. On the other hand, PGA having an excessively large molecular size is expensive to produce and may be technically difficult to produce.

If there is a commercially available PGA, it may be used or manufactured separately. However, since poly-α-glutamic acid is obtained when glutamic acid is polymerized under normal conditions, it is preferably biosynthesized using a microorganism. Examples of microorganisms that produce PGA include Bacillus subtilis (Bacillus natto), Bacillus subtilis (Sengoku soy sauce), Bacillus megaterium, Bacillus anthracis, Bacillus halodurans, and Naturalbaeagae. Examples of microorganisms that can produce PGA with a large molecular size include Bacillus subtilis, which is a Bacillus subtilis, and Naturalba aegyptica, which is a hyperhalophilic archaea. Among these, it is preferable to use PGA produced by Naturalba aegyiaca, which is a microorganism that produces PGA consisting only of L-glutamic acid.

The PGA ion complex of the present invention (hereinafter sometimes referred to as PGAIC) has a PGA and a cationic bactericide that is a counter cation bound by an ionic bond, and PGA exhibits water solubility, The PGA ion complex is insoluble in water.

The cationic fungicide contained in the PGA ion complex of the present invention is not particularly limited, but a quaternary ammonium salt and a biguanide fungicide are preferred, and a quaternary ammonium salt is more preferred. Examples of quaternary ammonium salts include cetylpyridinium chloride, laurylpyridinium chloride, benzethonium chloride, benzalkonium chloride, distearyldimethylammonium chloride, stearyldimethylbenzylammonium chloride, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, lauryl chloride. And trimethylammonium. Examples of biguanide fungicides include chlorhexidine hydrochloride, chlorhexidine acetate, chlorhexidine gluconate, alexidine hydrochloride, alexidine acetate, alexidine gluconate and the like. Of these, cetylpyridinium chloride, laurylpyridinium chloride, benzethonium chloride, and benzalkonium chloride are preferable. These cationic fungicides may form a PGA ion complex only by one kind, or may be a PGA ion complex containing two or more kinds.

As the PGA ion complex according to the present invention, those containing glutamic acid constituting the PGA and the cationic fungicide in an equimolar amount or in an arbitrary molar ratio can be used. In order to overcome the disadvantages, those that are sufficiently modified with a cationic fungicide are preferred. More specifically, the proportion of the cationic bactericidal agent in PGAIC is preferably 0.5 mol times or more, more preferably 0.6 mol times or more with respect to glutamic acid constituting PGA, 0 More preferably, it is 7 mol times or more. In particular, those containing equimolar or substantially equimolar amounts of glutamic acid and cationic fungicide constituting PGA are suitable. Here, “substantially equimolar” means that the number of moles of both is substantially equal. Specifically, the amount of the cationic fungicide for glutamic acid constituting PGA is 0.8 mol times or more and 1.2 mol times or less. In particular, it means 0.9 mole times or more and 1.1 mole times or less.

The PGA ion complex of the present invention can be produced very easily only by mixing PGA and a cationic fungicide such as a quaternary ammonium salt or a biguanide fungicide in a solvent.

As the solvent used here, water is suitable. This is because the raw material PGA can be dissolved well and the target compound PGA ion complex is insoluble in water, which is convenient for isolation and purification of the target product after the reaction. However, depending on the water solubility of the cationic disinfectant, in order to increase the solubility in the reaction solution, an alcohol such as methanol or ethanol; an ether such as THF; a water-soluble organic solvent such as dimethylformamide or dimethylacetamide is reacted. It may be added to the liquid. However, considering the separation of the PGA ion complex after completion of the reaction, it is preferable to use only water as the solvent.

The salt may be used as PGA as a raw material. Examples of the salt include alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as calcium salt and magnesium salt. Further, even when a salt is used, it is not necessary that all carboxy groups are salts, and only a part thereof may be a salt. However, since polyvalent metal salts such as alkaline earth metal salts may have low solubility in water, a PGA free body or a monovalent metal salt of PGA is preferably used.

Quaternary ammonium salts or biguanide fungicides are usually present as halide salts. Therefore, in the present invention, a quaternary ammonium salt or biguanide fungicide may be added directly to the reaction solution, or the salt may be added after dissolving in an aqueous solvent. The quaternary ammonium salt or biguanide fungicide is preferably used in a sufficient amount relative to PGA in order to sufficiently modify PGA.

Since the PGA ion complex of the present invention is insoluble in water and can be easily separated from an aqueous solvent, the concentration of each component in the reaction solution is not particularly limited. For example, the concentration of PGA in the reaction solution can be about 0.5 w / v% or more and about 10 w / v% or less, and the concentration of the cationic bactericidal agent can be about 1.0 w / v% or more and about 10 w / v% or less. .

The reaction solution is preferably heated moderately to promote complex formation. The heating temperature can be, for example, about 40 ° C. or higher and 80 ° C. or lower. The reaction time may be adjusted as appropriate, but can usually be about 1 hour or more and 20 hours or less.

Since the PGA ion complex of the present invention is insoluble in water, it can be easily separated from an aqueous solvent by filtration or centrifugation. Further, the separated PGAIC can be washed with water to remove excess PGA, cationic fungicide, and other salts. The aqueous solvent can be easily removed by washing with acetone or the like.

(Algae inhibitor)
The algal inhibitor containing the PGA ion complex according to the present invention exhibits an excellent algal inhibitory effect. In addition, since poly-γ-glutamic acid, which is at least the main skeleton of the ion complex, which is an active ingredient, is biodegradable, the burden on the environment is low even after use. Cationic antibacterial agents become insoluble by ion binding with poly-γ-glutamic acid, have low elution into water, and have a low environmental impact. Moreover, since PGA ion complex has high moldability, it is an algal inhibitor that can be applied to various materials including plastic, film, fiber, wood, paper, concrete, metal, ceramic, glass and the like. Furthermore, the coating agent which melt | dissolved or disperse | distributed the algal inhibitor which concerns on this invention in the solvent shows the outstanding algal inhibitory effect. The coating agent of this invention is very useful as what can form the coating film and film which have a high algal control effect.

Algae here refers to organisms that perform photosynthesis that live in the presence of water, and the present invention relates to cyanobacteria that are eubacteria, unicellular algae such as red algae, green algae, diatoms, and dinoflagellates, brown algae, Euglena It can be applied to a wide range of algae such as algae. Furthermore, by suppressing the generation and growth of algae, the formation of biofilms by algae can be suppressed, and the growth of pathogenic bacteria such as Legionella that grow in the biofilm can be suppressed.

The algae inhibitor according to the present invention is particularly preferably applied to water-based equipment, and since antibacterial components do not flow out due to water and antibacterial sustainability is high, floating organic substances and bacteria adhere, and biofilms and algae adhere. Can be reduced. Furthermore, the PGA ion complex according to the present invention exerts an excellent bacteriostatic effect against Legionella pneumophila, which is a causative bacterium that causes Legionella pneumonia, and both gram-positive and gram-negative bacteria.

As a form in which the algal inhibitor of the present invention is used in an aqueous facility, an algal inhibitory effect can be exhibited by forming a coating film or a film on the inner surface during production of an aqueous facility such as a pipe, pipe, or tank. Furthermore, it is possible to circulate a solution containing a PGA ion complex in an aqueous facility such as a pipe, a pipe, or a tank and apply the PGA ion complex on the surface of the facility. The PGA ion complex of the present invention has adhesiveness, and the PGA ion complex is insoluble in water and does not elute into water, and also exhibits anti-algae properties as described above. When the PGA ion complex of the present invention is used as an anti-algae paint, it is possible to form a coating film or a film exhibiting a continuous anti-algae property by applying or spraying on a substrate or the like.

The PGA ion complex of the present invention can be used alone, or can be dissolved in a solvent and used in the form of a solution. As a solvent, from the viewpoint of safety, water; alcohols such as ethanol, methanol and isopropanol; solvents of hydrocarbons such as n-hexane are preferable. In addition, ketones, esters, fatty acids, silicone oils and the like are preferable. Various solvents can also be used. These solvents may be used alone or in combination of two or more. In the case of a solution, the solution preferably contains 0.1 wt% or more of PGA ion complex, and preferably contains 0.1 to 20 wt%. If the amount is less than 0.1 wt%, the effect of preventing algae may not be sufficiently exhibited. Although an upper limit is not specifically limited, When it melt | dissolves in a solvent etc., it is preferable that the said PGAIC is 20 wt% or less.

In the case of using the PGA ion complex of the present invention as an anti-algae paint, a pigment, a surfactant, a crosslinking agent, and other paint additives may be appropriately blended in addition to the PGA ion complex and the solvent. When applying an algae-proofing treatment to industrial products and substrates using the algae-proofing paint of the present invention, powder coating, brushing, spraying, dipping, dipping, coating, printing, etc. The treatment may be performed by this method, and is not particularly limited. In this case, examples of the base material that can be applied include ceramics, metals, metal oxides, plastics, rubbers, ores, and wood. Specifically, examples of ceramics include glass, ceramics, cement, refractory bricks, and firewood. Examples of metals include simple metals such as iron, aluminum, zinc, magnesium, gold, silver, chromium, germanium, molybdenum, nickel, lead, platinum, silicon, titanium, thorium, tungsten, carbon steel, nickel steel, Examples of the alloy include chromium steel, chromium molybdenum steel, stainless steel, aluminum alloy, brass and bronze. Examples of metal oxides include alumina, silica, magnesia, tria, zirconia, iron sesquioxide, iron tetroxide, titanium oxide, calcium oxide, zinc oxide, lead oxide and the like. Examples of plastics include general purpose plastics such as polyvinyl chloride, polyethylene, polypropylene, polystyrene, polyethylene terephthalate, and polyvinyl alcohol, engineering plastics such as polyamide, polycarbonate, polyacetal, polyvinylidene fluoride, polyethersulfone, and polyamideimide, and phenolic resins. And thermosetting resins such as epoxy resins, silicone resins, and polyurethanes. Examples of ores include marble and granite.

The PGA ion complex of the present invention may be processed into an inner wall of a water system facility, a molded product, piping, a filter, or a water absorbent sheet. Specifically, examples of the water system facilities include water conduits, water supply pipes, water distribution pipes, and water supply pipes used as water pipes. Furthermore, it can be used for various water pipes, for example, water heaters, humidifiers, water storage tanks, cold water machines, washing machines, cooling towers, fountains, farms, plant factories, etc. be able to. It can also be used for bathroom facilities and the like, and can be processed into a bathtub, shower, jacuzzi, and the like.

The present invention can suppress algae generated in a filter by using it in a filter for water treatment or liquid treatment. Further, the present invention can be used for water absorbent sheets and water absorbent fibers made of a resin foam, a water absorbent polymer, or a nonwoven fabric. For example, water absorbency used in soil water retention agents, seedling beds, plant culture equipment and hydroponics. Effective in suppressing the generation and growth of algae in the sheet.

Since the PGA ion complex is a biodegradable polymer, it can be used as a highly safe and low environmental load algae control agent. As processing methods, PGA ion complex or PGA ion complex is applied to the water-based equipment, filter, water-absorbing sheet, powder coating method, brush coating, spraying method, dipping method, dipping method, coating method, printing method, etc. Can be surface treated.

Furthermore, the PGA ion complex of the present invention may be blended into a polymer resin by master batch blending, dry blending, or compounding. When the PGA ion complex of the present invention is used as an algal control material blended with a polymer resin or the like, the type of the polymer resin is not particularly limited, and can be freely selected according to the use of the resin composition. Specific examples of resins that can be used include, for example, vinyl chloride polymers, urethane polymers, acrylic polymers, olefin polymers, ethylene polymers, propylene polymers, amide polymers, ethylene-vinyl acetate copolymers, chlorides. Examples include vinylidene polymers, styrene polymers, ester polymers, nylon polymers, cellulose derivatives, carbonate polymers, fluorine resins, silicone resins, vinyl alcohol polymers, vinyl ester polymers, synthetic rubbers, natural rubbers, etc. . In the resin composition, a plasticizer, a filler, a colorant (dye, pigment, etc.), an ultraviolet absorber and the like may be appropriately blended as necessary.

The algae inhibitor of the present invention includes a bathtub, a pool, a sauna, a jacuzzi, a shower, a humidifier, an aquarium fish tank, a greenhouse, an indoor plant factory and other indoor equipment such as a residence, a hospital, and a public facility, a cooling tower, stored water, When applied to outdoor facilities such as fountains and farms, algae can be suppressed and generation of Legionella can be prevented.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

(Production Example 1) Production of PGAIC (IC100) Poly-γ-L-glutamic acid sodium salt (40 g) having an average molecular weight of 1000 kD derived from the hyperhalophilic archaeon Natrialva edipitiaca was dissolved in purified water, and 18 w / V% solution. A 0.2M aqueous solution (1551 g) of cetylpyridinium chloride (CPC) kept at 60 ° C. was added to the solution. After confirming that a water-insoluble material was formed immediately after the addition of CPC from an aqueous solution of the raw material poly-γ-L-glutamic acid sodium salt (the content of the polymer is 90% or more), the mixture was further kept at 60 ° C. for 4 hours. . The obtained water-insoluble material was collected by filtration and then washed three times with 1000 mL of purified water. Furthermore, it dehydrated by washing | cleaning with acetone, Then, it vacuum-dried and collect | recovered PGAIC (93g) as a powder. From the result of ¹ H-NMR of the obtained PGAIC, it was confirmed that L-PGA and cetylpyridinium were bonded at a molar ratio of 100: 100.

(Production Example 2) Production of PGAIC (IC60) Poly-γ-L-glutamic acid sodium salt (80 g) having an average molecular weight of 1000 kD derived from the hyperhalophilic archaeon Natrialva edipitiaca (80 g) was dissolved in purified water. / V% solution. To the solution, 2.0 M hydrochloric acid (80 g) was added to adjust the pH to 4, and then a 0.2 M aqueous solution (668 g) of cetylpyridinium chloride (CPC) was added. After confirming that a water-insoluble material was formed immediately after CPC addition from an aqueous solution of poly-γ-L-glutamic acid sodium salt as a raw material, the mixture was stirred at 60 ° C. for 4 hours. The obtained water-insoluble material was collected by filtration and then washed three times with 600 mL of purified water. After washing, the wet water-insoluble material was vacuum dried to recover PGAIC (67 g) as a powder. From the result of ¹ H-NMR of the obtained PGAIC, it was confirmed that L-PGA and cetylpyridinium were bonded at a molar ratio of 100: 60.

(Production Example 3) Production of PGAIC (L-PGA / BAC) Poly-γ-L-glutamic acid sodium salt (1 g) having an average molecular weight of 1000 kD derived from the hyperhalophilic archaeon Natrialva Egyptiacia (1 g) in purified water Dissolved to give a 2 w / v% solution. To the solution was added a 0.3M aqueous solution (26 g) of benzalkonium chloride (BAC). After confirming that a water-insoluble material was formed immediately after the addition of BAC from an aqueous solution of the raw material poly-γ-L-glutamic acid sodium salt, the mixture was further stirred at 25 ° C. for 2 hours. The obtained water-insoluble material was collected by filtration and then washed 3 times with 30 mL of purified water. It vacuum-dried and PGAIC (3g) was collect | recovered. From the result of ¹ H-NMR of the obtained PGAIC, it was confirmed that L-PGA and benzalkonium were bound at a molar ratio of 100: 100.

(Production Example 4) Production of PGAIC (L-PGA / LPC) Poly-γ-L-glutamic acid sodium salt (2 g) having an average molecular weight of 1000 kD derived from the hyperhalophilic archaeon Natrialva Ediptiaca is used as purified water. It melt | dissolved and it was set as the solution of 18 w / v%. To the solution was added a 0.6 M aqueous solution (28 g) of laurylpyridinium chloride (LPC). After confirming that a water-insoluble material was formed immediately after LPC addition from an aqueous solution of poly-γ-L-glutamic acid sodium salt as a raw material, the mixture was further stirred at 25 ° C. for 2 hours. The obtained water-insoluble material was collected by filtration and then washed twice with 30 mL of purified water. It vacuum-dried and collect | recovered PGAIC (4g). From the result of ¹ H-NMR of the obtained PGAIC, it was confirmed that L-PGA and laurylpyridinium were bonded at a molar ratio of 100: 100.

(Production Example 5) Production of PGAIC (L-PGA / BTC) Poly-γ-L-glutamic acid sodium salt (1 g) having an average molecular weight of 1000 kD derived from the hyperhalophilic archaeon Natrialva Egyptiacia (1 g) was added to purified water. It melt | dissolved and it was set as the solution of 18 w / v%. A 0.2M aqueous solution of benzethonium chloride (BTC) (32 g) was added. After confirming that a water-insoluble material was formed immediately after addition of BTC from an aqueous solution of poly-γ-L-glutamic acid sodium salt as a raw material, the mixture was further stirred at 25 ° C. for 2 hours. The obtained water-insoluble material was collected by filtration and then washed twice with 30 mL of purified water. It vacuum-dried and PGAIC (3g) was collect | recovered. From the result of ¹ H-NMR of the obtained PGAIC, it was confirmed that L-PGA and benzethonium were bound at a molar ratio of 100: 100.

(Example 1) PGAIC dissolution test The PGAIC (1 wt%) produced in Production Example 1 was put in water and stirred at 600 rpm with a magnetic stirrer at 40-60 ° C and pH 7 for one week. The dissolution test of PGAIC in water was performed. The PGAIC dissolution test was evaluated by measuring the ¹ H-NMR spectrum of the supernatant. As shown in Table 1, PGAIC and degradation products were not observed under the conditions of 40 to 60 ° C., and no elution of PGAIC was observed under any of the conditions.
The evaluation criteria are as follows.
-: Not detected.
+: Detection.

(Example 2) Algae suppression test of PGAIC Ethanol: water mixed solutions (5: 5) containing 0.01 and 0.10% of PGAIC produced in Production Examples 2 and 3, respectively, were produced. The solution was put into a test tube, stirred, dried, washed with water, and the inner wall was coated. The water of the pond was put in, and after standing at room temperature for 2 weeks under sunlight, the growth of algae on the inner wall surface was visually evaluated. As shown in Table 2, when PGAIC was coated with a solution containing 0.1%, an algae growth inhibitory effect was observed.
The evaluation criteria are as follows.
-: Not detected.
+: Detection.

Example 3 Production of PGAIC (L-PGA / CPC) Coating Film PGAIC (20 g) obtained in Production Example 1 was dissolved in ethanol to obtain a 20 wt% solution. The obtained ethanol solution was applied onto a PET film with an applicator, and the solvent was dried to prepare a PGAIC coating film having a thickness of 50 μm.

Example 4 Production of PGAIC (L-PGA / BAC) Coating Film A PGAIC coating film was prepared in the same manner as in Example 3 except that the PGAIC (L-PGA / BAC) obtained in Production Example 3 was used. Manufactured.

Example 5 Production of PGAIC (L-PGA / LPC) Coating Film A PGAIC coating film was prepared in the same manner as in Example 3 except that the PGAIC (L-PGA / LPC) obtained in Production Example 4 was used. Manufactured.

Example 6 Production of PGAIC (L-PGA / BTC) Coating Film A PGAIC coating film was prepared in the same manner as in Example 3 except that the PGAIC (L-PGA / BTC) obtained in Production Example 5 was used. Manufactured.

(Example 7) Antibacterial test against Legionella The antibacterial test was conducted according to JIS L1902. The PGAIC coating films obtained in Examples 3 to 6 were cut into 1 cm squares and used as test pieces, and an untreated PET film was used as a control test piece. After applying Legionella pneumophila GIFU 9143 to a B-CYEα agar medium at a bacterial concentration of 1.6 × 10 ⁷ / mL, the test piece is allowed to stand and cultured at 37 ° C. for 7 days. The presence or absence of formation of a halo (proliferation prevention zone) against Legionella was determined. As a result, as shown in Table 3, the PET film coated with PGAIC was confirmed to be halo against Legionella.
The evaluation criteria are as follows. The parenthesis indicates the halo width.
-: Do not accept halo +: Accept halo

Example 8 Production of Vinyl Chloride Plate Coated with PGAIC (L-PGA / CPC) The PGAIC (L-PGA / CPC) produced in Production Example 1 was dissolved in ethanol, and 0.01 wt% and 0. 10 wt% and 1.00 wt% solutions were prepared. A vinyl chloride test piece cut into 5 cm × 5 cm was immersed in each solution for 5 minutes at room temperature, then taken out and air-dried at room temperature for 24 hours.

(Example 9) Production of SUS plate coated with PGAIC (L-PGA / CPC) A SUS304 test piece was used in the same manner as in Example 8 except that a SUS304 test piece was used instead of the vinyl chloride test piece.

(Example 10) Production of vinyl chloride plate coated with PGAIC (L-PGA / BAC) Instead of PGAIC (L-PGA / CPC) produced in Production Example 1, PGAIC (L-PGA) produced in Production Example 3 was used. / BAC) was used in the same manner as in Example 8.

(Example 11) Production of vinyl chloride plate coated with PGAIC (L-PGA / BAC) Example 8 except that the PGAIC (L-PGA / BAC) produced in Example 3 and a test piece made of SUS304 were used. It produced similarly.

(Example 12) Field test in drainage channel Using each test piece (made of vinyl chloride, made of SUS304) manufactured in Examples 8 to 11, the algal inhibition effect after being immersed in the drainage yard for 2 months was evaluated. did. In this test, the water temperature in the drainage yard: 20 to 31 ° C., air temperature: 20 to 36 ° C., pH: 7.4 to 7.6, BOD: 2.1 to 8.5 ppm, COD: 4.0 to 9.8 ppm The experiment was carried out under water under sunlight. Evaluation of the test piece after the field test was carried out by determining the presence or absence of algae, the amount of deposits, and the amount of biofilm by visual inspection. As a result, as shown in Table 4, when the PGAIC was coated on the vinyl chloride plate than the control, it was confirmed that the adhesion of algae was small. On the other hand, with the SUS plate, the adhesion of algae was hardly seen on the test piece coated with PGAIC.
The evaluation criteria are as follows.
X: Adherence of a large amount of algae is observed.
Δ: A small amount of algae attached.
○: Slightly attached algae
A: Almost no algae attached.

The algae inhibitor of the present invention includes a bathtub, a pool, a sauna, a jacuzzi, a shower, a humidifier, an aquarium fish tank, a greenhouse, an indoor plant factory and other indoor equipment such as a residence, a hospital, and a public facility, a cooling tower, stored water, In fields where algae control is required in outdoor facilities such as fountains and farms, it can be used for excellent algal growth suppression and Legionella growth control.

Claims

An algae inhibitor comprising a PGA ion complex formed from poly-γ-glutamic acid and a cationic fungicide.
The algal inhibitor according to claim 1, wherein the cationic bactericidal agent is quaternary ammonium.
The algal inhibitor according to claim 1, wherein the cationic bactericide is a biguanide bactericide.
The algal inhibitor according to claim 1, wherein the cationic fungicide is at least one selected from the group consisting of cetylpyridinium, benzethonium, chlorhexidine, benzalkonium, laurylpyridinium, and chlorhexidine.
The algae inhibitor according to any one of claims 1 to 4, comprising a solution containing the PGA ion complex and alcohol and / or hydrocarbon.
The algal inhibitor according to claim 5, wherein the alcohol is at least one selected from the group consisting of ethanol, methanol, and isopropanol.
The algae inhibitor according to claim 5 or 6, wherein the PGA ion complex is contained in the solution in an amount of 0.1 to 20 wt%.
The algal inhibitor according to any one of Claims 1 to 7, wherein the proportion of L-glutamic acid in the glutamic acid constituting poly-γ-glutamic acid is 90% or more.
The algal inhibitor according to any one of claims 1 to 8, wherein the glutamic acid constituting the poly-γ-glutamic acid comprises L-glutamic acid.
A water pipe which is a water conduit, water pipe, water pipe or water pipe coated with the algal inhibitor according to any one of claims 1 to 9.
A water flow pipe coated with the algae inhibitor according to claim 1 on its inner surface.
A water treatment filter containing the algal inhibitor according to any one of claims 1 to 9.
A water-absorbent sheet comprising a resin foam, a water-absorbing polymer or a nonwoven fabric which has been subjected to an alga-proof treatment using the algae inhibitor according to claim 1.
A method for suppressing algae in a bathroom facility, a pool, a humidifier, a water tank, a greenhouse, an indoor plant cultivation facility, a cooling tower, a storage water tank, a fountain facility, or a farm facility using the algae inhibitor according to claim 1 .
Generation of Legionella in bathtub facilities, pools, humidifiers, aquariums, greenhouses, indoor plant cultivation facilities, cooling towers, storage water tanks, fountain facilities or aquaculture facilities using the algal inhibitor of claims 1-9 How to suppress.