JP5253995B2 - Method for producing sustained release slime control composition and method for installing the same - Google Patents

Description

  In the present invention, bacteria such as iron bacteria and sulfate-reducing bacteria grow in water collection paths such as tunnels and dams, and agar-like substances (slime) are produced to block water collection holes and drainage channels. It is related with the manufacturing method which manufactures the sustained-release slime control composition which suppresses and prevents this harmful phenomenon over a long term safely and efficiently, and the installation method which makes it manifest safely and effectively over a long term.

  A tunnel is a kind of huge concrete cylinder. When this pipe is buried in the earth or rock, if no measures are taken, the water that flows out of the earth or rock presses the back (outside) of the tunnel, and the pressure causes the concrete cylinder to be modulated, which is unexpected. There is a risk of causing an accident. Therefore, if a hole (hereinafter referred to as a water collection pipe) is formed through the inside and back of the tunnel, the water that flows out is removed through the water collection pipe, so that it is possible to prevent an unexpected accident from occurring. On the other hand, a hole similar to a water collecting pipe is also installed in the dam to release the pressure of the stored water. Therefore, water collection pipes are installed in many tunnels and dams, and the water collected there is stored in a drainage basin (tank) through a drainage channel and then discarded outside.

  Inside the tunnel, brown agar-like sludge (slime) is generated at the leaked site due to bacteria such as iron bacteria. This is caused by the accumulation of iron bacteria living in the ground on the side wall of the tunnel due to water leakage, regardless of salt water or fresh water. This sludge not only impairs the aesthetics of the tunnel, but also causes problems such as clogging the hook and drainage grooves. In addition, when the water retained due to a drainage failure contains salt, it causes corrosion of reinforcing bars in the concrete structure. Conventionally, work for removing this sludge is performed by regular cleaning, but in reality, regular cleaning requires a lot of labor. Therefore, a method for preventing this over a long period is strongly desired.

  The generation of this slime has caused many harmful effects on tunnels and dams. For example, if a large amount of slime is produced, the water collecting pipe will eventually be blocked. If this happens, the tunnel or dam will be the same as when there is no water collecting pipe, and the pressure of the water will cause modulation of the concrete wall of the tunnel or dam, causing an unexpected accident. Not only that, the slime clogs the drainage ditch and the water overflows, leaking water outside the drainage ditch, and adversely affecting it. It takes a lot of human power to remove it. In addition, the slime splatters in the tunnel due to the wind pressure of the running train, and the train, equipment, and tunnel are contaminated, and cleaning is difficult. In addition, the water collected in the drainage pond is pumped up and discarded outside the tunnel. If slime flows into this, the slime must be separated and processed, which requires extra work. In recent years, there is also a submarine tunnel, and seawater flows through the water collecting pipe, where similar bacteria propagate.

Bacteria that affect tunnel construction include iron bacteria (such as Gallionella ferruginea), sulfate-reducing bacteria (such as Desulfovibrio desulfuricans), and sulfur-oxidizing bacteria (such as Thiobacillus thioparus). In particular, since iron bacteria are generated at locations where water leakage comes into contact with air, a method of placing a chemical on the upstream side of the water leakage as much as possible or contacting with a control chemical without touching the air is desired.
In the present invention, an iron bacterium for the purpose of inhibiting growth is also called an iron-oxidizing bacterium. It is an aerobic chemical autotrophic organism that uses molecular oxygen to oxidize divalent iron ions (Fe ²⁺ ) to trivalent iron ions (Fe ³⁺ ) and uses this energy to fix carbon dioxide. When the bacteria propagate, they produce slime (brown agar-like material), and when they are produced in large quantities, for example, they block the water collecting holes opened in the concrete in the tunnel. A low temperature of 18 ° C. or lower is the optimum growth temperature.
In the present invention, a sulfate-reducing bacterium for the purpose of inhibiting growth is also referred to as a sulfate-reducing bacterium. It is a bacterium that uses sulfate as a final electron acceptor to oxidize organic matter or hydrogen to obtain energy and live. Although it is said that it is a symbiotic bacterium of iron bacteria and does not produce slime, it is said that the growth of iron bacteria can also be inhibited by inhibiting the growth of this bacterium.

Conventionally, for example, a sustained-release slime control composition disclosed in Patent Document 1 has been proposed as a drug containing a bactericidal active ingredient that inhibits the growth of bacteria such as iron bacteria and sulfate-reducing bacteria.
The sustained-release slime control composition disclosed in Patent Document 1 includes a bactericidal active ingredient such as benzethonium chloride, copper sulfate, copper terephthalate, and dimethyldidecyl ammonium chloride, polyvinyl alcohol, higher fatty acids, polyethylene glycol, and inorganic It is characterized by containing one or more additives selected from neutral salts.
In addition, as a method for producing this composition, there is described a production method in which a material is dissolved and kneaded in an organic solvent such as chloroform, and the kneaded product is molded into a granular shape, a cylindrical shape or a plate shape and then dried. ing.
Furthermore, as its usage, when used in a tunnel, it is described that it is left in the water collecting pipe, under the water collecting port or under the water collecting port, or in the vicinity thereof.
JP 11-246309 A

  However, in the prior art disclosed in Patent Document 1, when producing a sustained-release slime control composition, if it is dried using chloroform, which is a deleterious substance, it is used for toxic problems due to inhalation, etc. There are serious problems and it cannot be said to be a safe manufacturing method. Even if an organic solvent other than chloroform is used, a volatile solvent is used, and its flammability countermeasures are also a problem.

  In addition, there is a concern that the composition may be washed away by water pressure or blown away by the wind pressure of a vehicle passing through the tunnel if it is left alone in the tunnel. It does not describe how to install and use it safely.

  The present invention has been made in view of the above circumstances, and provides a sustained-release slime containing a substance that inhibits the growth of bacteria such as iron bacteria and sulfate-reducing bacteria that exhibit harmful effects by producing an agar-like substance (slime). It aims at providing the safe and efficient manufacturing method of a control composition, and the method which can be installed concretely irrespective of freshwater seawater.

In order to achieve the above object, the present invention provides:
Without using organic solvents
(A) a higher fatty acid and polyethylene glycol which are monovalent carboxylic acids having 11 or more carbon atoms, which are solid at room temperature as a binder;
(B) One or more selected from the group consisting of dimethyldidecyl ammonium chloride, dimethyl isononyl decyl ammonium chloride, dimethyl dioctyl ammonium chloride, benzethonium chloride, copper sulfate, copper terephthalate as a bactericidal component;
(C) Polyvinyl alcohol, oil-absorbing fine powder, surfactant, water, mineral fine powder, salt, water-soluble polymer, citric acid, succinic acid, saccharides, urea, xanthan gum, calcium stearate and buoyant auxiliary as auxiliary agents One or more selected from the group consisting of:
And a step of pouring the liquid composition obtained by heating and mixing into a mold, allowing it to stand naturally, or forcing it to lower the product temperature to solidify and molding. A method for producing a sustained release slime control composition is provided.

The present invention also provides
Without using organic solvents
(A) While the higher fatty acid and polyethylene glycol, which are solid carboxylic acids having 11 or more carbon atoms, which are solid at room temperature as a binder , are heated to a melting point or higher and melted,
(B) One or more selected from the group consisting of dimethyldidecyl ammonium chloride, dimethyl isononyl decyl ammonium chloride, dimethyl dioctyl ammonium chloride, benzethonium chloride, copper sulfate, copper terephthalate as a bactericidal component;
(C) Polyvinyl alcohol, oil-absorbing fine powder, surfactant, water, mineral fine powder, salt, water-soluble polymer, citric acid, succinic acid, saccharides, urea, xanthan gum, calcium stearate and buoyant auxiliary as auxiliary agents A step of adding and mixing one or more selected from the group consisting of: and then pouring the resulting liquid composition into a mold and allowing it to stand naturally or forcibly reduce the product temperature to solidify it. And a process for producing a sustained-release slime control composition characterized by comprising a step of molding.

In the method for producing a sustained release slime control composition of the present invention, the higher fatty acid is one or two selected from castor oil, castor hydrogenated oil, beef tallow oil, beef tallow fatty acid and beef tallow slightly hydrogenated fatty acid. It is preferable.
In the method for producing a sustained-release slime control composition of the present invention, (b) the bactericidal component is preferably dimethyldidecyl ammonium chloride.

  In the method for producing a sustained-release slime control composition of the present invention, the mold to be used is one selected from the group consisting of a paper mold, a wooden mold, a resin mold, and a metal mold, or these molds It is preferable to comprise a composite mold frame in which two or more types of frames are combined.

  In the method for producing a sustained-release slime control composition of the present invention, a water-soluble or water-dispersible film is spread on a formwork to be used, and the liquid composition is poured onto the formwork to form a solid by lowering the product temperature. It is preferable to do.

  The present invention also provides a formwork in which the sustained-release slime control composition obtained by the production method according to the present invention is placed in the outflow location of water containing harmful substance-producing bacteria, or is water-soluble or water-dispersible. It is taken out together with the film and fixed and installed so that water and the sustained-release slime control composition are in direct contact with each other, and a method for installing the sustained-release slime control composition is provided.

  The present invention also provides a formwork in which the sustained-release slime control composition obtained by the production method according to the present invention is placed in the outflow location of water containing harmful substance-producing bacteria, or is water-soluble or water-dispersible. It is taken out together with the film, and a method for installing the sustained-release slime control composition is provided, wherein a water-absorbing material is sandwiched and fixed between water and the sustained-release slime control composition.

  Further, the present invention provides a sustained release property obtained by the above-described production method according to the present invention, in which an outflow point of water containing harmful substance-producing bacteria and a container having a water inlet and a water outlet are connected by a hose. There is provided a method for installing a sustained-release slime control composition which is characterized in that the slime control composition is placed as it is or removed from the mold with a water-soluble or water-dispersible film.

  Further, the present invention is still in a form in which a sustained-release slime control composition obtained by the production method according to the present invention is placed in a water tank installed so that water containing harmful substance-producing bacteria enters, or Provided is a method for installing a sustained-release slime control composition, which is taken out from a mold together with a water-soluble or water-dispersible film.

  According to the method for producing a sustained release slime control composition according to the present invention, it can be produced safely and efficiently without using an organic solvent which is worried about toxicity, flammability and environmental pollution. When installed, it can be installed regardless of a concrete wall, water channel, or water tank as an installation location.

  According to the method of installing the sustained release slime control composition according to the present invention, the sustained release slime control composition can be reliably and effectively installed without being damaged by hydraulic power or wind pressure. It is possible to effectively prevent long-term growth of sulfate-reducing bacteria which are symbiotic bacteria and generation of slime due to them.

  As a result of intensive studies, the present inventors have used higher fatty acids and polyethylene glycol that are solid at room temperature as binders, and dimethyldidecylammonium chloride, dimethylisononyldecylammonium chloride, dimethyldioctylammonium chloride, benzethonium chloride, sulfuric acid as bactericidal components. Use one or more selected from copper and copper terephthalate, use one or more selected from polyvinyl alcohol, oil-absorbing fine powder, physicochemical regulator as auxiliary agent, and heat all raw materials After mixing and liquefying, it is cast directly into a mold. Alternatively, a water-soluble or water-dispersible film is spread on the mold and cast on it. As a method of use, the composition is taken out of the form or with a water-soluble or water-dispersible film, and the water-absorbent material such as a sponge or the like is directly taken into the water outflow location containing the title bacteria. Between the composition and placed with a fixing band or the like. Or it installs in the container which has the inlet_port | entrance which takes in the water containing bacteria, and a drain outlet. Or put it in a water storage tank that contains water containing bacteria. Obtaining these findings, the present invention has been completed.

The method for producing a sustained-release slime control composition according to the present invention comprises:
(A) a higher fatty acid and polyethylene glycol that are solid at room temperature as a binder;
(B) One or more selected from the group consisting of dimethyldidecyl ammonium chloride, dimethyl isononyl decyl ammonium chloride, dimethyl dioctyl ammonium chloride, benzethonium chloride, copper sulfate, copper terephthalate as a bactericidal component;
(C) one or more selected from the group consisting of polyvinyl alcohol, oil-absorbing fine powder, physicochemical regulator as an auxiliary agent,
And a step of pouring the liquid composition obtained by heating and mixing into a mold, allowing it to stand naturally, or forcing it to lower the product temperature to solidify and molding. .

  In the production method of the present invention, (a) a higher fatty acid and polyethylene glycol that are solid at room temperature as a binder are heated to a melting point or higher and melted, and then the (b) bactericidal component, the (c) auxiliary agent, The resulting liquid composition can be poured into a mold and allowed to stand naturally, or it can be forced to lower the product temperature to be solidified and molded.

In the production method of the present invention, (a) a higher fatty acid used as a binder is a monovalent carboxylic acid represented by a general formula C _n H _m COOH having 11 or more carbon atoms (n and m are integers). Yes, preferably one or two selected from castor oil, castor hydrogenated oil, beef tallow hardened oil, beef tallow fatty acid and beef tallow slightly hydrogenated fatty acid, and more preferably castor hardened oil or castor hardened oil and It is beef tallow oil. The content of the higher fatty acid is preferably in the range of 1 to 50% by mass, more preferably in the range of 3 to 40% by mass. A suitable content ratio of castor oil and beef tallow oil is in the range of 1: 1 to 1: 3.

Castor hydrogenated oil is a wax-like substance having a melting point: 85 ° C. obtained by catalytic reduction of castor oil. It contains a C ₁₆ -C ₂₀ hydroxy saturated higher fatty acid (containing 80% or more of 12-hydroxy stearic acid) or a C ₁₆ -C ₂₀ hydroxy unsaturated higher fatty acid. Beef tallow oil is a wax-like substance obtained by catalytic reduction of beef fatty acids. It mainly contains C ₁₄ -C ₁₈ saturated higher fatty acids or C ₁₄ -C ₁₈ unsaturated higher fatty acids. Some have a melting point of 43 ° C. to 55 ° C., but a melting point of about 51 ° C. is preferred.

  In the production method of the present invention, (a) polyethylene glycol used as a binder is produced by polymerizing ethylene oxide, and its molecular weight is preferably in the range of 1000 to 20000, and more preferably in the range of 1500 to 6000. . The content varies depending on the sterilizing component and other additives, but is preferably in the range of 15 to 60% by mass, more preferably in the range of 20 to 50% by mass, but is not particularly limited.

  In the production method of the present invention, (b) the bactericidal component is a kind selected from the group consisting of dimethyldidecyl ammonium chloride, dimethyl isononyl decyl ammonium chloride, dimethyl dioctyl ammonium chloride, benzethonium chloride, copper sulfate, and copper terephthalate. Or 2 or more types of compounds are mentioned. A particularly preferred bactericidal component is dimethyl didecyl ammonium chloride.

  The content of this (b) sterilizing component varies depending on the amount of components and other additives, but is preferably in the range of 10 to 70% by mass, more preferably in the range of 30 to 50% by mass, but is not particularly limited. Absent. About benzethonium chloride, copper sulfate, and dimethyl didecyl ammonium chloride, it is particularly preferably about 40% by mass.

In the production method of the present invention, the (c) auxiliary agent may be one or more selected from the group consisting of polyvinyl alcohol, oil-absorbing fine powder, and physicochemical regulator.
Among these, polyvinyl alcohol is a substance produced by saponifying polyvinyl acetate produced by polymerizing vinyl acetate, and the degree of polymerization is preferably in the range of 100 to 2000, and more preferably in the range of 500 to 1000. The saponification degree is preferably in the range of 70 to 90 mol%, more preferably in the range of 85 to 90 mol%. The content varies depending on the active ingredient and other additives, but is preferably in the range of 1 to 25% by mass, more preferably 5 to 20% by mass, but is not particularly limited.

  In the present invention, (c) oil-absorbing fine powder used as an auxiliary agent includes white carbon that is hydrous amorphous silicon oxide, specially processed starch that is pregelatinized starch and enzyme-modified dextrin, fine powder derived from plants such as conifers and kenaf, etc. Is mentioned. Among these, white carbon is preferable. The content varies depending on the bactericidal component and other additives, but is preferably in the range of 5 to 25% by mass, more preferably 10 to 20% by mass, but is not particularly limited.

  In the present invention, as the auxiliary agent (c), a physicochemical modifier such as a surfactant, a liquid solvent, and other auxiliary agents is used to further optimize the physicochemical properties of the obtained sustained release slime control composition. Can be contained.

  As the surfactant that can be added to the sustained-release slime control composition, various surfactants generally used in the field of production of the composition can be used. For example, polyethylene glycol higher fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl ether, Nonionic surfactants such as oxyethylene alkyl aryl ethers, polyoxyethylene aryl phenyl ethers, sorbitan monoalkylates, acetylene alcohols and acetylenic diols and their alkylene oxide adducts, alkyl aryl sulfonates, dialkyl sulfonates, Lignin sulfonate, naphthalene sulfonate and its condensate, alkyl sulfate, alkyl phosphate, alkyl aryl sulfate, alkyl aryl phosphate, Anionic surfactants such as oxyethylene alkyl ether sulfates, polyoxyethylene alkyl aryl ether sulfates, polyoxyethylene aryl phenyl ether sulfates, polycarboxylic acid type polymer surfactants, and silicone Fluorine-based surfactants and the like can be mentioned, and among them, nonionic surfactants are preferable. Moreover, surfactant can be used 1 type or in mixture of 2 or more types. The content of the surfactant is preferably in the range of 0.1 to 20% by mass, more preferably in the range of 0.5 to 10% by mass, but is not particularly limited.

  As the liquid solvent that can be added to the sustained-release slime control composition, (b) a liquid solvent that does not react with the sterilizing component is suitable, and one or two or more kinds selected from generally used liquid solvents can be used. . For example, ethanol, phthalate ester, alkylnaphthalene, alkylpyrrolidone, phenylxylylethane, glycerin, alkylene glycol, xylene, kerosene, and other alcohols, methane series hydrocarbons, fatty acid esters, polybasic acids, etc. These organic solvents and water can be used, but are not limited thereto. The liquid solvent to be used is preferably as low a toxicity as possible, easily biodegradable and environmentally friendly. For example, the combined use of water and a lower alcohol such as ethyl alcohol is excellent. The content of the liquid solvent is preferably in the range of 0.1 to 20% by mass, more preferably in the range of 0.5 to 10% by mass, but is not particularly limited. In addition, when using together with water and a lower alcohol, it is desirable to manufacture with the closed system apparatus using a local exhaust apparatus.

  In the present invention, the sustained-release slime control composition includes a fine mineral powder, salts, water-soluble polymer, physical property improver, component in addition to the surfactant and liquid solvent in order to further optimize physicochemical properties. Adjuvants such as stabilizers and bulking agents can be added. These auxiliary agents may be solid or liquid in nature, and may be insoluble or easily soluble in water. For example, fine mineral powder such as clay, calcium carbonate, bentonite, talc, diatomaceous earth, ammonium sulfate, ammonium bicarbonate, ammonium nitrate, ammonium chloride, potassium chloride, sodium sulfate, magnesium sulfate, sodium citrate, sodium carbonate, sodium bicarbonate, etc. Examples include salts of organic or inorganic acids, organic acids such as citric acid and succinic acid, sugars such as sucrose, lactose, xanthan gum, starch and dextrin, urea, xanthan gum, calcium stearate, etc., but are not limited thereto. . The content of the adjuvant is preferably in the range of 0.1 to 20% by mass, more preferably in the range of 0.5 to 10% by mass, but is not particularly limited.

  Furthermore, when using in a water storage tank etc., a floating auxiliary agent can also be used in order to use it floating on the water surface. Such floating aids include, for example, minerals such as pumice, vermiculite, pearlite, plant materials such as straw, sugar cane, rice straw, wheat straw, eggplant, banana, bamboo, straw, corn core, wood, etc. Other than that, it is made of foamed shirasu made of shirasu, phyllite baked in aluminosilicate system, microballoon made of foamed sodium silicate or borax, fly ash, ceramic hollow body and other inorganic substances, phenol resin Organic substances such as phenol microballoon, ecosphere made of epoxy resin, polyurethane foam made of polyurethane, and microsphere made of vinylidene chloride-acrylonitrile copolymer can be mentioned. As the microspheres, those diluted 5 to 10 times with water, calcium carbonate, titanium oxide or the like can be used. The content of the floating aid is preferably in the range of 0.1 to 20% by mass, more preferably in the range of 0.5 to 10% by mass, but is not particularly limited.

As an embodiment of the method for producing a sustained release slime control composition according to the present invention,
(1) The above-mentioned (a) binder, (b) bactericidal component, (c) auxiliary agent, which is an essential component of the sustained release slime control composition, and other additives added as necessary are heated and mixed. , Pouring the liquid composition obtained into a mold, allowing it to stand naturally, or forcibly lowering the product temperature to solidify and mold,
(2) The (a) binder is preheated to a melting point or higher and melted, and the (b) bactericidal component and the (c) auxiliary agent are added and mixed therein to obtain a liquid obtained A method of pouring the composition into a mold, allowing it to stand naturally, or forcibly lowering the product temperature to solidify and mold,
Is mentioned.

Although the heating conditions depend on the raw materials, a range of 40 to 100 ° C. is preferable, a range of 50 to 90 ° C. is more preferable, and a raw material capable of obtaining a viscosity that can be handled in the temperature range is used.
The apparatus for heating and mixing each material can use various mixers and extruders such as a hot water jacketed stirring mixer generally used in the pharmaceutical field, synthetic resin manufacturing field, and the like, and is not particularly limited.

  The mold used in the production method of the present invention is a paper mold, a wooden mold, a resin mold, a kind selected from the group consisting of metal, or a composite mold formed by combining two or more of these molds. Can be used. A resin mold is preferable, and a polyethylene mold, a polypropylene mold, and a polystyrene mold are particularly preferable. Moreover, it is preferable that a formwork has the heat resistance of the grade which can endure the product temperature more than the time of a composition manufacture. The durability temperature is preferably 100 ° C. or higher, more preferably 150 ° C. or higher. The formwork to be used is preferably one with a lid, and one having a divided interior can also be used. In the case with a lid, the lid is covered immediately after pouring the heated composition and can be stacked in a natural state, or it can be solidified by being immersed in cooling water to forcibly reduce the product temperature.

  In the production method of the present invention, the mold can be formed by pouring a composition mixed with a water-soluble or water-dispersible film and heated and mixed thereon. By doing so, it is easy to take out the solidified composition from the mold, and there is an advantage that safety in handling can be ensured because it is not in direct contact with the drug by human hands. In use, it is effective because the water-dispersible film dissolves or disperses in water when it comes into contact with water containing bacteria, and the solidified sustained-release slime control composition comes into contact with water containing bacteria.

  The amount of the composition of the present invention put into the mold is in the range of 20 g to 400 g, preferably in the range of 40 g to 200 g, and more preferably in the range of 60 to 150 g. When the inside of the formwork is divided, the amount that can be put in a single frame corresponds. In the present invention, the shape of the sustained-release slime control composition to be produced can be selected depending on the formwork, and is usually a cylindrical shape, a rectangular parallelepiped shape, a hemispherical shape, a plate shape or a lump shape, but is not particularly limited.

  Examples of water-soluble or water-dispersible films spread on the formwork include polyvinyl alcohol films, polyoxypolyalkylene glycol films, hydroxypropylcellulose films, hydroxypropylmethylcellulose films, methylcellulose films, and sodium carboxymethylcellulose. Examples include films, sodium polyacrylate films, alginic acid films, gelatin films, pullulan films, solubilized starch films, paper, and the like, and preferably polyvinyl alcohol films that dissolve in water. Although the thickness of a film is not specifically limited, Generally it is 20 micrometers-100 micrometers, and the range of 25 micrometers-40 micrometers is preferable. Moreover, you may carry out multiple packaging using the film of the same or different composition.

  The method for installing the sustained-release slime control composition according to the present invention is the safe and effective installation of the sustained-release slime control composition obtained by the above-described production method according to the present invention at a target position, which is stable for a long time. In particular, the following (1) to (4) embodiments can be mentioned.

(1) In a form where the sustained-release slime control composition obtained by the production method according to the present invention described above is put in the outflow site of water containing harmful substance-producing bacteria, or in a water-soluble or water-dispersible form The installation method which takes out with a film and fixes and installs so that water and the said sustained release slime control composition may contact directly.
(2) In the form where the sustained-release slime control composition obtained by the production method according to the present invention described above is put in the outflow location of water containing harmful substance-producing bacteria, or in a water-soluble or water-dispersible form The installation method of the sustained release slime control composition which takes out with a film and fixes and installs a water absorbing material between water and the said sustained release slime control composition.
(3) A controlled release slime obtained by the above-described production method according to the present invention, in which the outflow location of water containing harmful substance-producing bacteria and a container having a water inlet and a water outlet are connected by a hose. A method for installing a sustained-release slime control composition in which the control composition is placed in a form or taken out of the form together with a water-soluble or water-dispersible film.
(4) As a formwork in which the sustained-release slime control composition obtained by the production method according to the present invention described above is placed in a water storage tank installed so that water containing harmful substance-producing bacteria enters, or water-soluble To install a sustained-release slime control composition that is taken out from the mold together with a water-soluble or water-dispersible film.

  The amount of the sustained release slime control composition to be installed varies depending on the outflow amount of water flowing out and the amount of bacteria contained therein. For example, the amount of the sustained release slime control composition in the range of 50 to 150 g is usually 1 to 10, preferably 4 to 7 per 26 kL (0.2 L / min × 3 months) of the total water flowing out. However, the present invention is not limited to this.

  Hereinafter, although the effect of the present invention is explained in detail in an example and a comparative example, the present invention is not limited only to these examples. In the following examples and comparative examples, “part” represents part by mass.

[Example 1]
Hot water at 90 ° C. is passed through a stirring mixer with a hot water jacket, 12 parts of higher fatty acid (manufactured by NOF Corporation: beef tallow oil / melting point 51 ° C.), higher fatty acid (manufactured by NOF Corporation: castor oil hardening oil / melting point 81 ° C.) 4 Parts and 16 parts of polyethylene glycol (manufactured by Sanyo Chemical Industries Co., Ltd .: PEG # 4000S / melting point 56 ° C.) are sequentially added and melt mixed. There, 50 parts of dimethyl didecyl ammonium chloride (manufactured by Keisei Chemical Co., Ltd .: Keisanit BP-80) (consisting of 80% effective bactericidal component, balance water, etc.), 8 parts of polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Co., Ltd .: Gohsenol GL-05S) and chloride Four parts of a mixture obtained by sequentially adding 10 parts of sodium (manufactured by Kanto Chemical Co., Ltd .: reagent grade 1) in a polyethylene mold with a lid (inner diameter 15 cm × width 20 cm × depth 2 cm: capacity 100 ml × 4 divisions) A total of 400 g was poured into each 100 ml, and naturally cooled to obtain a sustained-release slime control composition according to the present invention.

[Example 2]
Hot water at 90 ° C. is passed through a stirring mixer with a hot water jacket, and 10 parts of higher fatty acid (manufactured by NOF Corporation: beef tallow oil / melting point 51 ° C.), higher fatty acid (manufactured by NOF Corporation: castor oil hardening oil / melting point 81 ° C.) 5 Next, 20 parts of polyethylene glycol (manufactured by Sanyo Chemical Co., Ltd .: PEG # 4000S / melting point 56 ° C.) are sequentially added and melt mixed. There, 50 parts of dimethyl didecyl ammonium chloride (manufactured by Keisei Kasei Kogyo Co., Ltd .: Keisanit BP-80) (consisting of 80% effective sterilizing component, remaining water, etc.), polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Co., Ltd .: Gohsenol GL-05S) 5 Part, white carbon (manufactured by Tosoh Silica Co., Ltd .: Nipseal NS) was added sequentially, and a polyethylene mold with a lid (inner diameter 15 cm × width 20 cm × depth 2 cm: capacity 100 ml × 4 divisions) A water-soluble film (manufactured by Nippon Synthetic Chemical Co., Ltd .: Hi-Selon S-400, thickness 30 μm, length 30 cm × width 40 cm) is laid down, poured 100 g each into four places, wrapped with a water-soluble film and sealed with a polypropylene lid. In order to prevent the cooling water from entering the cooling water having a water temperature of 20 ° C. A lime control composition was obtained.

[Example 3]
Hot water at 90 ° C. is passed through a stirring mixer with a warm water jacket, 15 parts of higher fatty acid (manufactured by NOF Corporation: beef tallow oil / melting point 51 ° C.), higher fatty acid (manufactured by NOF Corporation: castor oil hardening oil / melting point 81 ° C.) 10 Parts and 30 parts of polyethylene glycol (manufactured by Sanyo Chemical Co., Ltd .: PEG # 4000S / melting point 56 ° C.) are sequentially added and melt mixed. 25 parts of dimethyldidecylammonium chloride (manufactured by Keiai Kasei Co., Ltd .: Keisanit BP-80) (consisting of 80% effective bactericidal component, remaining water, etc.), 10 parts of polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Co., Ltd .: Gohsenol GL-05S) Then, 400 g of a mixture obtained by sequentially adding 10 parts of white carbon (manufactured by Tosoh Silica Co., Ltd .: Nipseal NS) is poured into a paper cup form (inner diameter 8 cm × depth 10 cm: capacity about 500 ml), and then naturally cooled. The sustained release slime control composition according to the present invention was obtained.

[Example 4]
Hot water at 90 ° C. is passed through a stirring mixer equipped with a hot water jacket, 15 parts of higher fatty acid (manufactured by NOF Corporation: beef tallow oil / melting point 51 ° C.), higher fatty acid (manufactured by NOF Corporation: castor oil hardening oil / melting point 81 ° C.) 5 Next, 13 parts of polyethylene glycol (manufactured by Sanyo Chemical Industries, Ltd .: PEG # 4000S / melting point: 56 ° C.) are sequentially added and melt mixed. There, 25 parts of dimethyl didecyl ammonium chloride (manufactured by Keisei Kasei Co., Ltd .: Keisanit BP-80) (consisting of 80% effective sterilizing component, remaining water, etc.), 20 parts of benzethonium chloride (manufactured by Lonza Japan), polyvinyl alcohol (Nippon Synthesis) Chemical Co., Ltd .: Gosenol GL-05S) 10 parts, White Carbon (manufactured by Tosoh Silica Co., Ltd .: Nipsil NS) and polyoxyethylene polyoxypropylene block polymer (Sanyo Chemical Industries, Ltd .: New Pole PE-68 / melting point 53 ° C.) 400 g of the mixture obtained by sequentially adding 2 parts is poured into a paper cup form (inner diameter 8 cm × depth 10 cm: capacity 500 ml), naturally cooled, and the sustained release slime control composition according to the present invention is obtained. Obtained.

[Example 5]
Hot water at 90 ° C. is passed through a stirring mixer equipped with a warm water jacket, 10 parts of higher fatty acid (manufactured by NOF Corporation: beef tallow hardened oil / melting point 51 ° C.), 10 parts of higher fatty acid (manufactured by NOF Corporation: castor oil hardened oil / melting point 81 ° C.) 10 Then, 20 parts of polyethylene glycol (manufactured by Sanyo Chemical Industries Co., Ltd .: PEG # 4000S / melting point 56 ° C.) are sequentially added and melt mixed. Thereto, 40 parts of benzethonium chloride (Lonza Japan), 10 parts of polyvinyl alcohol (Nippon Gosei Co., Ltd .: Gohsenol GL-05S) and 10 parts of white carbon (manufactured by Tosoh Silica Co., Ltd .: Nipsil NS) are sequentially added. 400 g of the obtained mixture was poured into a paper cup form (inner diameter: 8 cm × depth: 10 cm: capacity: 500 ml) and naturally cooled to obtain a sustained-release slime control composition according to the present invention.

[Example 6]
Hot water at 90 ° C. is passed through a stirring mixer equipped with a hot water jacket, and 25 parts of higher fatty acid (manufactured by NOF Corporation: beef tallow oil / melting point 51 ° C.), higher fatty acid (manufactured by NOF Corporation: castor oil hardening oil / melting point 81 ° C.) 10 8 parts of polyethylene glycol (manufactured by Sanyo Chemical Co., Ltd .: PEG # 4000S / melting point 56 ° C.) are sequentially added and melt mixed. There, 40 parts of copper sulfate (manufactured by Kanto Chemical Co., Ltd .: first grade reagent), 10 parts of polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Co., Ltd .: Gohsenol GL-05S), polyoxyethylene polyoxypropylene block polymer (manufactured by Sanyo Chemical Industries, Ltd .: New Pole) A mixture obtained by sequentially adding 2 parts of PE-68 / melting point 53 ° C. and 5 parts of sodium chloride (manufactured by Kanto Chemical Co., Ltd .: first grade reagent) was added to a polyethylene mold with a lid (inner diameter 15 cm × width 20 cm × depth). A total of 400 g was poured into four portions each having a length of 2 cm (capacity: 100 ml × 4 divisions), followed by natural cooling to obtain a sustained-release slime control composition according to the present invention.

[Comparative Example 1]
The comparative example 1 corresponds to the composition “C-5” described in the example of Patent Document 1 (Japanese Patent Laid-Open No. 11-246309).
50 parts of dimethyldidecylammonium chloride (manufactured by Keisei Chemical Co., Ltd .: Keisanit BP-80) (consisting of 80% effective bactericidal component, balance water, etc.), 8 parts of polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Co., Ltd .: Gohsenol GL-05S), white 13 parts of carbon (Nippon Gosei Co., Ltd .: Nipsea NS), 4 parts of higher fatty acid (manufactured by Nippon Oil & Fats: castor oil hardened oil / melting point 81 ° C.), higher fatty acid (manufactured by Nippon Oil & Fats Co., Ltd .: beef fat slightly hydrogenated fatty acid / melting point 51 ° C. ) 4 parts and 21 parts of polyethylene glycol (manufactured by Sanyo Kasei Co., Ltd .: PEG # 4000S) were added in order, 30 parts of chloroform was added, and the mixture was kneaded and molded into a cylindrical shape. Chloroform was distilled off and dried to obtain the composition of Comparative Example 1.

[Comparative Example 2]
The comparative example 2 corresponds to the composition “A-5” described in the example of Patent Document 1 (Japanese Patent Laid-Open No. 11-246309).
40 parts of benzethonium chloride (manufactured by Lonza Japan), 10 parts of polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Co., Ltd .: GOHSENOL GL-05S), 10 parts of higher fatty acid (manufactured by NOF Corporation: castor oil hardened oil / melting point 81 ° C.), polyethylene glycol ( 36 parts of Sanyo Chemical Co., Ltd .: PEG # 4000S), 2 parts of polyethylene glycol (manufactured by Sanyo Chemical Co., Ltd .: PEG # 1540), and 2 parts of polyethylene glycol (manufactured by Sanyo Kasei Co., Ltd .: PEG # 1000) were sequentially added, followed by 30 parts of chloroform. Was added, dissolved and kneaded, molded into a cylindrical shape, and then chloroform was distilled off and dried in a chamber with a local exhaust device to obtain a composition of Comparative Example 2.

[Comparative Example 3]
Comparative Example 3 corresponds to the composition “B-2” described in the example of Patent Document 1 (Japanese Patent Laid-Open No. 11-246309).
40 parts of copper sulfate (manufactured by Kanto Chemical Co., Ltd .: first grade reagent), 15 parts of polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Co., Ltd .: Gohsenol GL-05S), 35 parts of higher fatty acid (manufactured by NOF Corporation: castor oil hardened oil / melting point 81 ° C.) After adding 10 parts of sodium chloride (Kanto Chemical Co., Ltd .: first grade reagent) sequentially, adding 30 parts of chloroform, kneading and forming into a cylindrical shape, and then distilling and drying chloroform in a chamber with a local exhaust device Thus, a composition of Comparative Example 3 was obtained.

<Bacteria prevention test>
Concrete blocks were stacked to prepare a concrete wall surface having a height of 100 cm, a hole having a diameter of 1 cm was formed at a position having a height of 80 cm, and a hose having a diameter of 1 cm was passed through the hole. Using an artificial seawater spring device, 0.2 L (288 L / day) was allowed to flow from the hole in the concrete wall through the artificial seawater containing iron bacteria from the hose. The compositions manufactured in Examples 1 to 6 and Comparative Examples 1 to 3 described above were installed so as to be 400 g each. As the installation method, any of the installation methods shown in the following (1) to (5) was adopted.

Installation method (1): Anchors were hit at four locations around the water outlet of the concrete wall, and the composition was placed in the mold at the water outlet and fixed with a wire from all directions.
Installation method (2): Anchors were placed at four locations around the concrete wall water outlet, and the composition was placed on the water outlet with a 2 cm thick sponge and fixed with a wire from all directions.
Installation method (3): Anchors were hit at four locations around the water outlet of the concrete wall, and the composition was installed at the water outlet while being wrapped with a water-soluble film from the mold, and fixed with metal bands from all sides. The comparative example was fixed with metal bands from four sides as it was.
Installation method (4): It connected with the hose from the outflow location of water to the 5L container which has a water inlet and a water outlet. The composition was taken out from the mold together with the water-soluble film and placed in the container.
Installation method (5): Water was collected in a 50 L bucket from the water outflow location with a hose. The water-soluble film was taken out from the mold containing the composition and placed. The comparative example was placed in a 50 L bucket as it was.

Observations were made every 15 days, and the growth of bacteria (iron bacteria) and the formation of slime were observed with the naked eye, and were determined according to the “determination criteria for inhibitory effect in Table 1. The results are summarized in Table 1.
Moreover, the component of each composition of Examples 1-6 is put together in Table 2, and is described.
Furthermore, the components of the compositions of Comparative Examples 1 to 3 are collectively shown in Table 3.

From the results in Table 1, the sustained-release slime control compositions of Examples 1 to 6 produced by the production method according to the present invention are the compositions of Comparative Examples 1 to 3 based on the prior art described in Patent Document 1. In comparison with the above, the bacteria suppression effect was prolonged. Therefore, according to the present invention, it is possible to provide a sustained-release slime control composition that can exert a stable bacteria-suppressing effect for a long period of time.
Moreover, the sustained-release slime control composition of Examples 1-6 is manufactured by heat-mixing each material, without using the toxic solvent like chloroform used in manufacture in Comparative Examples 1-3. Therefore, manufacturing can be performed safely and extra work such as solvent recovery can be omitted.
Moreover, the sustained-release slime control composition of Examples 1-6 could be applied to any of the installation methods (1) to (5), and all were able to obtain a good fungus suppression effect.

Claims (10)

Without using organic solvents
(A) a higher fatty acid and polyethylene glycol which are monovalent carboxylic acids having 11 or more carbon atoms, which are solid at room temperature as a binder;
(B) One or more selected from the group consisting of dimethyldidecyl ammonium chloride, dimethyl isononyl decyl ammonium chloride, dimethyl dioctyl ammonium chloride, benzethonium chloride, copper sulfate, copper terephthalate as a bactericidal component;
(C) Polyvinyl alcohol, oil-absorbing fine powder, surfactant, water, mineral fine powder, salt, water-soluble polymer, citric acid, succinic acid, saccharides, urea, xanthan gum, calcium stearate and buoyant auxiliary as auxiliary agents One or more selected from the group consisting of:
And a step of pouring the liquid composition obtained by heating and mixing into a mold, allowing it to stand naturally, or forcing it to lower the product temperature to solidify and molding. A method for producing a sustained release slime control composition. Without using organic solvents
(A) While the higher fatty acid and polyethylene glycol, which are solid carboxylic acids having 11 or more carbon atoms, which are solid at room temperature as a binder , are heated to a melting point or higher and melted,
(B) One or more selected from the group consisting of dimethyldidecyl ammonium chloride, dimethyl isononyl decyl ammonium chloride, dimethyl dioctyl ammonium chloride, benzethonium chloride, copper sulfate, copper terephthalate as a bactericidal component;
(C) Polyvinyl alcohol, oil-absorbing fine powder, surfactant, water, mineral fine powder, salt, water-soluble polymer, citric acid, succinic acid, saccharides, urea, xanthan gum, calcium stearate and buoyant auxiliary as auxiliary agents A step of adding and mixing one or more selected from the group consisting of: and then pouring the resulting liquid composition into a mold and allowing it to stand naturally or forcibly reduce the product temperature to solidify it. A method for producing a sustained-release slime control composition, which comprises a step of molding.   The production of the sustained-release slime control composition according to claim 1, wherein the higher fatty acid is one or two selected from castor oil, castor hydrogenated oil, beef tallow oil, beef tallow fatty acid and beef tallow slightly hydrogenated fatty acid. Method. (B) The bactericidal component is dimethyldidecylammonium chloride, The method for producing a sustained-release slime control composition according to any one of claims 1 to 3 . The formwork to be used is composed of a single form selected from the group consisting of paper formwork, wooden formwork, resin formwork, metal formwork, or a composite formwork that combines two or more of these formwork. The manufacturing method of the sustained-release slime control composition of any one of Claims 1-4 characterized by the above-mentioned. Water soluble mold to be used, or spread of water-dispersible film, pouring the liquid composition thereon claim 1-5, characterized in that molded into a solid shape by reduction product temperature 1 The manufacturing method of the sustained-release slime control composition of claim | item. A form containing the sustained-release slime control composition obtained by the production method according to any one of claims 1 to 6 in the outflow location of water containing harmful substance-producing bacteria, A method for installing a sustained-release slime control composition, which is taken out together with a water-dispersible film and fixed and installed so that water and the sustained-release slime control composition are in direct contact with each other. A form containing the sustained-release slime control composition obtained by the production method according to any one of claims 1 to 6 in the outflow location of water containing harmful substance-producing bacteria, A method for installing a sustained-release slime control composition, which is taken out together with a water-dispersible film and fixedly installed with a water-absorbing material sandwiched between water and the sustained-release slime control composition. The outflow location of water containing harmful substance-producing bacteria and a container having a water inlet and a water outlet are connected by a hose, and the container is obtained by the production method according to any one of claims 1 to 6. An installation method for a sustained-release slime control composition, wherein the release-release slime control composition is placed in a form-mold containing the sustained-release slime control composition or taken out of the mold together with a water-soluble or water-dispersible film. A mold in which a sustained-release slime control composition obtained by the production method according to any one of claims 1 to 6 is placed in a water tank installed so that water containing harmful substance-producing bacteria enters. A method for installing a sustained-release slime control composition, which is taken out from a mold and installed together with a water-soluble or water-dispersible film.