WO2018194108A1 - Agent for preventing adhesion of aquatic organism, resin composition for preventing adhesion of aquatic organism, molded product using coating for preventing adhesion of aquatic organism and resin composition for preventing adhesion of aquatic organism, and method for preventing adhesion of aquatic organism - Google Patents
Agent for preventing adhesion of aquatic organism, resin composition for preventing adhesion of aquatic organism, molded product using coating for preventing adhesion of aquatic organism and resin composition for preventing adhesion of aquatic organism, and method for preventing adhesion of aquatic organism Download PDFInfo
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- WO2018194108A1 WO2018194108A1 PCT/JP2018/016047 JP2018016047W WO2018194108A1 WO 2018194108 A1 WO2018194108 A1 WO 2018194108A1 JP 2018016047 W JP2018016047 W JP 2018016047W WO 2018194108 A1 WO2018194108 A1 WO 2018194108A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/06—Aluminium; Calcium; Magnesium; Compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
Definitions
- Example 4 (1) Preparation of paint containing basic magnesium sulfate 79.2% by mass of epoxy resin [manufactured by Nissin Resin Co., Ltd., low viscosity epoxy resin / Z-1, bisphenol A liquid epoxy resin], curing agent [Nisshin Resin Co., Ltd., 50 minute mold / curing agent] 15.8% by mass and fibrous basic magnesium sulfate particles [MOS / HIGE P powder product, manufactured by Ube Materials Co., Ltd., average fiber length: 15 ⁇ m, Average fiber diameter: 0.5 ⁇ m] was mixed at a ratio of 5.0% by mass to obtain a coating material according to Example 4 having an epoxy resin as a main component.
- epoxy resin manufactured by Nissin Resin Co., Ltd., low viscosity epoxy resin / Z-1, bisphenol A liquid epoxy resin
- curing agent [Nisshin Resin Co., Ltd., 50 minute mold / curing agent] 15.8% by mass
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- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Plant Pathology (AREA)
- Inorganic Chemistry (AREA)
- Pest Control & Pesticides (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The agent for preventing adhesion of aquatic organisms according to the present invention is characterized by containing basic magnesium sulfate. Further, the method for preventing adhesion of aquatic organisms according to the present invention is characterized by using an agent, for preventing adhesion of aquatic organisms, which contains basic magnesium sulfate to prevent adhesion of aquatic organisms.
Description
本発明は、水生生物付着防止剤、水生生物付着防止用樹脂組成物、水生生物付着防止用塗料及び水生生物付着防止用樹脂組成物を用いてなる成形体、並びに水生生物付着防止方法に関する。
The present invention relates to an aquatic organism adhesion preventing agent, an aquatic organism adhesion preventing resin composition, an aquatic organism adhesion preventing coating material, a molded article using the aquatic organism adhesion preventing resin composition, and an aquatic organism adhesion preventing method.
船舶や各種港湾施設、あるいは漁網、生簀等の漁獲施設等、海水や淡水に曝されているものには、各種海草、フジツボ、イガイ等の水生生物が付着棲息し、これら施設等の機能低下や耐久性の劣化をもたらしている。
Aquatic organisms such as various seaweeds, barnacles and mussels adhere to inhabited seawater and freshwater such as fishing facilities such as ships and various harbor facilities, fishing nets and ginger, etc. Deterioration of durability is brought about.
水生生物の付着を防止するための水生生物付着防止剤として、亜酸化銅を有効成分として含有するものが従来用いられている。しかしながら、亜酸化銅は水生生物に対し毒性があり、水生生物を殺傷することにより付着を防止するものである。また、亜酸化銅より溶出した銅は分解することなく環境中に残留するため、環境汚染が問題視されている。以上のことから、亜酸化銅を含有せず、生体や環境への影響が少ない代替材料の開発が求められている。
As an aquatic organism adhesion inhibitor for preventing adhesion of aquatic organisms, those containing cuprous oxide as an active ingredient have been conventionally used. However, cuprous oxide is toxic to aquatic organisms and prevents adhesion by killing aquatic organisms. Moreover, since the copper eluted from cuprous oxide remains in the environment without being decomposed, environmental pollution is regarded as a problem. In view of the above, there is a demand for the development of an alternative material that does not contain cuprous oxide and has little influence on the living body and the environment.
特許文献１には、海水中に溶存している陽イオンと陰イオンとから成る塩を塗料成分の一部として含有することで、水生生物が忌避する環境を生成して水生生物の付着を防止することが記載されている。海水中に溶存している塩として、塩化ナトリウム、塩化カリウム、又は硫酸マグネシウムを含有する水生生物の付着防止剤が開示されている。
Patent Document 1 includes a salt composed of a cation and an anion dissolved in seawater as part of a paint component, thereby creating an environment that aquatic organisms avoid and preventing the attachment of aquatic organisms. It is described to do. An aquatic organism anti-adhesion agent containing sodium chloride, potassium chloride, or magnesium sulfate as a salt dissolved in sea water is disclosed.
また、特許文献２には、被覆対象物表面を覆う被覆材に塩基性物質を担持させ、被覆材の表面に作用する水分の塩基性度を高めることにより水生生物の付着を防止する水生生物付着防止被覆材が開示されている。被覆材に担持される塩基性物質として、水酸化カルシウム、水酸化マグネシウム、水酸化バリウム、水酸化ランタン等の水酸化物が好ましいことが記載されている。
Patent Document 2 discloses that an aquatic organism is attached to a covering material that covers the surface of the object to be coated, thereby preventing the attachment of aquatic organisms by increasing the basicity of water acting on the surface of the covering material. A preventive dressing is disclosed. It is described that a hydroxide such as calcium hydroxide, magnesium hydroxide, barium hydroxide, lanthanum hydroxide is preferable as the basic substance supported on the coating material.
しかしながら、特許文献１に記載の付着防止剤は、有効成分として水溶性の塩を用いているため、付着防止効果の持続性が良くないという問題がある。また、特許文献２に記載の水生生物付着防止被覆材は、実施例に記載のように、有効成分として強塩基である水酸化カルシウムを用いていることから、水生生物や、水酸化カルシウムを担持する樹脂に対し悪影響を及ぼす虞がある。
However, since the anti-adhesion agent described in Patent Document 1 uses a water-soluble salt as an active ingredient, there is a problem that the durability of the anti-adhesion effect is not good. Moreover, since the aquatic organism adhesion prevention coating material of patent document 2 uses calcium hydroxide which is a strong base as an active ingredient as described in the Examples, it supports aquatic organisms and calcium hydroxide. May adversely affect the resin used.
そこで、本発明は、生体及び環境への安全性が高く、且つ水生生物付着防止効果の持続性に優れる水生生物付着防止剤、水生生物付着防止用樹脂組成物、水生生物付着防止用塗料及び水生生物付着防止用樹脂組成物を用いてなる成形体、並びに水生生物付着防止方法を提供することを目的とする。
Accordingly, the present invention provides an aquatic organism adhesion inhibitor, a resin composition for preventing aquatic organism adhesion, a paint for aquatic organism adhesion prevention, and an aquatic organism that are highly safe to living organisms and the environment and have excellent sustainability of the aquatic organism adhesion prevention effect. It aims at providing the molded object using the resin composition for biological adhesion prevention, and the aquatic organism adhesion prevention method.
以上の目的を達成するため、本発明者らは鋭意研究を重ねた結果、有効成分として塩基性硫酸マグネシウムを使用することで、生体及び環境への安全性が高く、且つ水生生物付着防止効果の持続性が良くなることを見出した。
In order to achieve the above object, the present inventors have conducted intensive research, and as a result, by using basic magnesium sulfate as an active ingredient, safety to living bodies and the environment is high, and an aquatic organism adhesion preventing effect is achieved. We found that sustainability is improved.
すなわち、本発明に係る水生生物付着防止剤は、塩基性硫酸マグネシウムを含有することを特徴とする。
That is, the aquatic organism adhesion inhibitor according to the present invention is characterized by containing basic magnesium sulfate.
以上のように、本発明によれば、生体及び環境への安全性が高く、且つ水生生物付着防止効果の持続性に優れる水生生物付着防止剤を得ることができる。
As described above, according to the present invention, it is possible to obtain an aquatic organism adhesion preventing agent that is highly safe to living organisms and the environment and is excellent in the sustainability of the aquatic organism adhesion preventing effect.
本発明に係る水生生物付着防止剤は、有効成分として、塩基性硫酸マグネシウムを含有する。塩基性硫酸マグネシウムは、ＭｇＳＯ４・５Ｍｇ（ＯＨ）２・３Ｈ２Ｏで示される化合物である。塩基性硫酸マグネシウムは、従来有効成分として用いられている亜酸化銅等と比較して毒性が低いため、水生生物を殺傷することなく、付着のみを防止することができる。また、塩基性硫酸マグネシウムは、人体内での残留性が低く、発がん性を有しないため、人体においても安全であり、当該塩基性硫酸マグネシウムを含有する水生生物付着防止剤を製造、使用する際の取り扱いも容易である。さらに、環境中での分解性も高く、残留性が低いため、環境への影響も少ない。
The aquatic organism adhesion inhibitor according to the present invention contains basic magnesium sulfate as an active ingredient. Basic magnesium sulfate is a compound represented by MgSO 4 .5Mg (OH) 2 .3H 2 O. Since basic magnesium sulfate is less toxic than cuprous oxide or the like conventionally used as an active ingredient, it is possible to prevent adhesion only without killing aquatic organisms. In addition, since basic magnesium sulfate has low persistence in the human body and is not carcinogenic, it is safe for the human body, and when manufacturing and using an aquatic organism anti-adhesive agent containing the basic magnesium sulfate. Is easy to handle. In addition, it has high environmental degradability and low persistence, so it has little impact on the environment.
本発明に係る水生生物付着防止剤中の塩基性硫酸マグネシウムの水への溶解度は０．０４６ｇ／Ｌ（２０℃）である。塩基性硫酸マグネシウムの水への溶解度が０．０４６ｇ／Ｌであることにより、硫酸マグネシウムや塩化ナトリウム、塩化カリウム等の水溶性塩と比較して溶解度が低いため、水生生物付着防止効果の持続性に優れ、水酸化マグネシウムを使用した場合と比較して溶解度が高いため、より優れた水生生物付着防止効果を示す。
The solubility of basic magnesium sulfate in the aquatic organism adhesion inhibitor according to the present invention in water is 0.046 g / L (20 ° C.). Since the solubility of basic magnesium sulfate in water is 0.046 g / L, its solubility is lower than that of water-soluble salts such as magnesium sulfate, sodium chloride, potassium chloride, etc. Since the solubility is high compared with the case where magnesium hydroxide is used, it shows a more excellent aquatic organism adhesion preventing effect.
また、塩基性硫酸マグネシウム水溶液のｐＨは９．５である。塩基性硫酸マグネシウム水溶液のｐＨが９．５であることにより、水酸化マグネシウムや水酸化カルシウム、水酸化バリウムを使用した場合と比較して塩基性が低いため、水生生物に対する安全性が高く、硫酸マグネシウムや塩化ナトリウム、塩化カリウム等の塩を使用した場合と比較して塩基性が高いため、優れた水生生物付着防止効果を示す。また、ｐＨが９．５であることにより、水生生物付着防止剤中の他の成分、例えば樹脂等への影響も少ない。
The pH of the basic magnesium sulfate aqueous solution is 9.5. Since the basic magnesium sulfate aqueous solution has a pH of 9.5, its basicity is lower than when magnesium hydroxide, calcium hydroxide or barium hydroxide is used. Since the basicity is higher than when using a salt such as magnesium, sodium chloride, potassium chloride, etc., it exhibits an excellent aquatic organism adhesion preventing effect. Moreover, since pH is 9.5, there is little influence on other components, such as resin, in an aquatic organism adhesion prevention agent.
本発明に係る水生生物付着防止剤中の塩基性硫酸マグネシウムとしては、繊維状塩基性硫酸マグネシウムを用いることが好ましい。繊維状塩基性硫酸マグネシウムの平均繊維長は１～１００μｍであり、１～５０μｍであることが好ましく、８～３０μｍであることが特に好ましい。平均繊維長が８～３０μｍであることにより、水生生物付着防止剤に強度を付与することができ、持続性が向上する。また、繊維状であることにより、塗料等の液状樹脂に添加した場合、チキソトロピック性を付与することができるため、施工性が向上し、液だれを防止することができる。
It is preferable to use fibrous basic magnesium sulfate as the basic magnesium sulfate in the aquatic organism adhesion preventive agent according to the present invention. The average fiber length of fibrous basic magnesium sulfate is 1 to 100 μm, preferably 1 to 50 μm, and particularly preferably 8 to 30 μm. When the average fiber length is 8 to 30 μm, strength can be imparted to the aquatic organism adhesion preventive agent, and durability is improved. Moreover, since it is fibrous and it can add thixotropic property when it adds to liquid resins, such as a coating material, construction property improves and it can prevent dripping.
本発明に係る水生生物付着防止剤中の繊維状塩基性硫酸マグネシウムの平均繊維径は０．０１～５μｍであり、０．１～３μｍであることが好ましく、０．３～２．０μｍであることが特に好ましい。繊維状塩基性硫酸マグネシウムの平均繊維長及び平均繊維径は、走査型電子顕微鏡（ＳＥＭ）による拡大画像から、繊維状塩基性硫酸マグネシウム１００本の繊維長及び繊維径を測定し、その個数平均値を求めることにより算出することができる。
The average fiber diameter of fibrous basic magnesium sulfate in the aquatic organism adhesion inhibitor according to the present invention is 0.01 to 5 μm, preferably 0.1 to 3 μm, and preferably 0.3 to 2.0 μm. It is particularly preferred. The average fiber length and average fiber diameter of fibrous basic magnesium sulfate were measured from the magnified image by scanning electron microscope (SEM), and the fiber length and fiber diameter of 100 fibrous basic magnesium sulfates were measured. Can be calculated by obtaining.
本発明に係る水生生物付着防止剤中の塩基性硫酸マグネシウムは、公知の方法により製造することができ、例えば、水酸化マグネシウムと硫酸とを原料として生成することができる。具体的には、硫酸マグネシウム水溶液に水酸化マグネシウム又は酸化マグネシウムを分散させて水熱反応させる方法、可溶性硫酸塩含有水溶液に酸化マグネシウム粉末を分散させた分散液を加熱反応させて繭状物を生成させ、これを強い剪断力で解砕する方法、塩基性硫酸マグネシウムの種粒子と水酸化マグネシウム粒子とを分散させた分散液を硫酸マグネシウム水溶液に混合して加熱することで塩基性硫酸マグネシウムを種粒子の表面に析出させる方法などを挙げることができる。
The basic magnesium sulfate in the aquatic organism adhesion preventive agent according to the present invention can be produced by a known method, and can be produced, for example, using magnesium hydroxide and sulfuric acid as raw materials. Specifically, a method in which magnesium hydroxide or magnesium oxide is dispersed in an aqueous magnesium sulfate solution and subjected to a hydrothermal reaction, and a dispersion in which magnesium oxide powder is dispersed in an aqueous solution containing a soluble sulfate is heated to produce a soot-like material. The basic magnesium sulfate is mixed with a magnesium sulfate aqueous solution and heated to disperse the dispersion of basic magnesium sulfate seed particles and magnesium hydroxide particles. The method of depositing on the surface of particle | grains etc. can be mentioned.
本発明に係る水生生物付着防止剤中の塩基性硫酸マグネシウムの含有量は、特に限定されるものではないが、水生生物付着防止剤全体を１００質量％として、８０質量％以上であることが好ましく、９０質量％であることがより好ましい。
The content of basic magnesium sulfate in the aquatic organism adhesion inhibitor according to the present invention is not particularly limited, but is preferably 80% by mass or more, based on 100% by mass of the entire aquatic organism adhesion inhibitor. 90% by mass is more preferable.
本発明の水生生物付着防止剤は、塩基性硫酸マグネシウム以外の有効成分として、従来水生生物付着防止剤の有効成分として用いられている公知の化合物を含有することができる。このような化合物としては、例えば銅粉、チオシアン酸第一銅、硫酸銅、硫酸亜鉛、硫酸ニッケルなどの無機化合物；オキシン銅、酢酸銅、ナフテン酸銅、銅ピリチオンなどの有機銅系化合物；酢酸ニッケル、ジメチルジチオカルバミン酸ニッケルなどの有機ニッケル系化合物；酢酸亜鉛、カルバミン酸亜鉛、ジメチルジチオカルバミン酸亜鉛、ジンクピリチオンなどの有機亜鉛系化合物、Ｎ－トリクロロメチルチオフタルイミド、Ｎ－フルオロジクロロメチルチオフタルイミドなどのＮ－トリハロメチルチオフタルイミド；ビス（ジメチルチオカルバモイル）ジスルフィド、Ｎ－メチルジチオカルバミン酸アンモニウム、エチレンビス（ジチオカルバミン酸）アンモニウムなどのジチオカルバミン酸；Ｎ－（２，４，６－トリクロロフェニル）マレイミド、Ｎ－４－トリルマレイミド、ｎ－３－クロロフェニルマレイミドなどのＮ－アリールマレイミド；３－ベンジリデンアミノ－１，３－チアゾリジン－２，４－ジオン、３－（４－メチルベンジリデンアミノ）－１，３－チアゾリジン－２，４－ジオンなどの３－置換アミノ－１，３－チアゾリジン－２，４－ジオン；ジチオシアノメタン、ジチオシアノエタン、２，５－ジチオシアノチオフェンなどのジチオシアノ系化合物；２－メチルチオ－４－ｔ－ブチルアミノ－６－シクロプロピルアミノ－Ｓ－トリアジンなどのトリアジン系化合物；２，４，５，６－テトラクロロイソフタロニトリル、Ｎ，Ｎ－ジメチルＮ’－ジクロロフェニル尿素、４，５－ジクロロ－２－ｎ－オクチル－イソチアゾリン－３－オン、Ｎ，Ｎ－ジメチル－Ｎ’－フェニル－（Ｎ－フルオロジクロロメチルチオ）スルファミド、テトラメチルチウラムジスルフィド、３－ヨード－２－プロピニルブチルカルバメート、２－（メトキシカルボニルアミノ）ベンズイミダゾール、２，３，５，６－テトラクロロ－４－（メチルスルフォニル）ピリジン、ジヨードメチルパラトリルスルホン、フェニル（ビスピリジン）ビスマスジクロライド、２－（４－チアゾリル）ベンズイミダゾール、ピリジントリフェニルボランなどを使用することができる。
The aquatic organism adhesion preventive agent of the present invention can contain a known compound conventionally used as an active ingredient of an aquatic organism adhesion preventing agent as an active ingredient other than basic magnesium sulfate. Examples of such compounds include inorganic compounds such as copper powder, cuprous thiocyanate, copper sulfate, zinc sulfate, and nickel sulfate; organic copper compounds such as oxine copper, copper acetate, copper naphthenate, and copper pyrithione; acetic acid Organic nickel compounds such as nickel and nickel dimethyldithiocarbamate; organic zinc compounds such as zinc acetate, zinc carbamate, zinc dimethyldithiocarbamate and zinc pyrithione, N-trihalo such as N-trichloromethylthiophthalimide and N-fluorodichloromethylthiophthalimide Methylthiophthalimide; dithiocarbamic acid such as bis (dimethylthiocarbamoyl) disulfide, ammonium N-methyldithiocarbamate, ethylenebis (dithiocarbamic acid) ammonium; N- (2,4,6-trichloropheny ) N-arylmaleimides such as maleimide, N-4-tolylmaleimide, n-3-chlorophenylmaleimide; 3-benzylideneamino-1,3-thiazolidine-2,4-dione, 3- (4-methylbenzylideneamino)- 3-substituted amino-1,3-thiazolidine-2,4-diones such as 1,3-thiazolidine-2,4-dione; dithiocyano compounds such as dithiocyanomethane, dithiocyanoethane and 2,5-dithiocyanothiophene A triazine compound such as 2-methylthio-4-t-butylamino-6-cyclopropylamino-S-triazine; 2,4,5,6-tetrachloroisophthalonitrile, N, N-dimethyl N′-dichlorophenyl; Urea, 4,5-dichloro-2-n-octyl-isothiazolin-3-one, N, N-di Tyl-N′-phenyl- (N-fluorodichloromethylthio) sulfamide, tetramethylthiuram disulfide, 3-iodo-2-propynylbutylcarbamate, 2- (methoxycarbonylamino) benzimidazole, 2,3,5,6-tetra Chloro-4- (methylsulfonyl) pyridine, diiodomethylparatolylsulfone, phenyl (bispyridine) bismuth dichloride, 2- (4-thiazolyl) benzimidazole, pyridine triphenylborane and the like can be used.
上記のような塩基性硫酸マグネシウム以外の有効成分の含有量は、特に制限なく任意の量を含むことができる。
The content of the active ingredient other than the basic magnesium sulfate as described above can include any amount without any particular limitation.
本発明に係る水生生物付着防止剤は、上記塩基性硫酸マグネシウム及びその他の有効成分を担持するための分散媒を使用することができる。分散媒として特に限定はなく、液体又は固体の分散媒を使用することができる。分散媒として、例えば溶媒、樹脂、油脂、セラミック、セメント、モルタル、コンクリート、金属等が挙げられる。これらは単独で用いてもよいし、２種以上を併用してもよい。
The aquatic organism adhesion inhibitor according to the present invention can use a dispersion medium for supporting the basic magnesium sulfate and other active ingredients. The dispersion medium is not particularly limited, and a liquid or solid dispersion medium can be used. Examples of the dispersion medium include solvents, resins, oils and fats, ceramics, cement, mortar, concrete, metals, and the like. These may be used alone or in combination of two or more.
溶媒としては、公知のあらゆる溶媒を使用することができ、例えば水、石油系混合溶媒、ミネラルスピリット、アルコール系溶媒、炭化水素系溶媒、芳香族化合物系溶媒、ケトン化合物系溶媒、エーテル系溶媒、エステル系溶媒、ハロゲン系溶媒、非プロトン性極性溶媒などを挙げることができる。これらのうち１種を単独で用いることも、２種以上を併用することもできる。
As the solvent, any known solvent can be used, for example, water, petroleum mixed solvent, mineral spirit, alcohol solvent, hydrocarbon solvent, aromatic compound solvent, ketone compound solvent, ether solvent, Examples include ester solvents, halogen solvents, aprotic polar solvents, and the like. Of these, one can be used alone, or two or more can be used in combination.
樹脂として特に限定はないが、水生生物付着防止効果の持続性という観点から、耐水性、耐久性、耐候性に優れるものを使用することが好ましく、例えば、ポリエチレン、ポリプロピレンなどのポリオレフィン樹脂、シリコーン樹脂、ポリウレタン樹脂、ポリウレタンアクリル樹脂、フェノール樹脂、ゴム系樹脂、塩化ビニル樹脂、ポリエステル樹脂、シリコーン樹脂、フッ素樹脂、ポリアミド樹脂、ポリイミド樹脂、尿素樹脂、メラミン樹脂、ポリアセタール樹脂、アクリル樹脂、エポキシ樹脂、種々のゴム及び熱可塑性エラストマー等が挙げられる。これらのうち１種を単独で用いることも、２種以上を併用することもできる。
Although there is no particular limitation on the resin, it is preferable to use a resin excellent in water resistance, durability, and weather resistance from the viewpoint of durability of the aquatic organism adhesion preventing effect. For example, polyolefin resins such as polyethylene and polypropylene, and silicone resins , Polyurethane resin, polyurethane acrylic resin, phenol resin, rubber resin, vinyl chloride resin, polyester resin, silicone resin, fluorine resin, polyamide resin, polyimide resin, urea resin, melamine resin, polyacetal resin, acrylic resin, epoxy resin, various And rubbers and thermoplastic elastomers. Of these, one can be used alone, or two or more can be used in combination.
また、本発明に係る水生生物付着防止剤は、本発明の効果を阻害しない程度に、任意の添加剤を含有することができる。添加剤として、例えば分散剤、乳化剤、乾燥剤、増粘剤、熱安定剤、光安定剤、消泡剤、可塑剤、界面活性剤、染料、顔料、触媒、老化防止剤、紫外線吸収剤、酸化防止剤、帯電防止剤、滑剤、充填剤、架橋剤、発泡剤、ワックス、油脂、脂肪酸、各種溶媒等を、任意の配合割合で含有させることができる。これらのうち１種を単独で用いることも、２種以上を併用することもできる。
Also, the aquatic organism adhesion inhibitor according to the present invention can contain any additive to the extent that the effects of the present invention are not impaired. Examples of additives include dispersants, emulsifiers, drying agents, thickeners, heat stabilizers, light stabilizers, antifoaming agents, plasticizers, surfactants, dyes, pigments, catalysts, anti-aging agents, UV absorbers, Antioxidants, antistatic agents, lubricants, fillers, crosslinking agents, foaming agents, waxes, fats and oils, fatty acids, various solvents, and the like can be contained in any blending ratio. Of these, one can be used alone, or two or more can be used in combination.
本発明に係る水生生物付着防止剤は、例えば水生生物付着防止用樹脂組成物、水生生物付着防止用塗料、水生生物付着防止用水中構造物、水生生物付着防止用コーティング、水生生物付着防止用接着剤等のあらゆる形態で、水中で用いられる種々の防汚目的物に使用することができる。防汚目的物としては、例えば、船底、スクリュウ、取水管、ブイ、鎖、いかだ、アンカー、魚網、魚礁、養殖生け簀用網、係留ロープ、海中建造物、護岸材、浮き岸壁、固定岸壁、海洋ケーブル、送電線、各種工業プラントの海水取水管や送水管、水槽、ろ過砂、泡用の管などが挙げられる。
The aquatic organism adhesion preventing agent according to the present invention includes, for example, an aquatic organism adhesion preventing resin composition, an aquatic organism adhesion preventing coating, an aquatic organism adhesion preventing underwater structure, an aquatic organism adhesion preventing coating, and an aquatic organism adhesion preventing adhesive. It can be used for various antifouling objects used in water in any form such as an agent. Examples of antifouling objects include ship bottoms, screws, intake pipes, buoys, chains, rafts, anchors, fish nets, fish reefs, aquaculture cage nets, mooring ropes, underwater structures, revetments, floating quay walls, fixed quay walls, oceans Examples include cables, power transmission lines, seawater intake pipes and water supply pipes of various industrial plants, water tanks, filtration sand, and foam pipes.
水生生物付着防止用樹脂組成物は、本発明に係る水生生物付着防止剤及び樹脂を含有する。水生生物付着防止用樹脂組成物に用いられる樹脂として、熱可塑性樹脂、熱硬化性樹脂等、特に限定はなく、例えばポリプロピレン、ポリブテン、ポリエチレンなどのオレフィン樹脂、塩化ゴム樹脂、塩化ビニル樹脂、フェノール樹脂、アルキド樹脂、各種変性アルキド樹脂、尿素樹脂、メラミン樹脂、酢酸ビニルなどのビニル樹脂、アクリル樹脂、各種合成ゴム、エポキシ樹脂、ポリエステル樹脂、不飽和ポリエステル樹脂、ポリウレタン樹脂、ポリアミド樹脂、ポリアセタール樹脂、ポリイミド樹脂、アミノ樹脂などが挙げられる。
The aquatic organism adhesion preventing resin composition contains the aquatic organism adhesion preventing agent and resin according to the present invention. The resin used in the resin composition for preventing aquatic organism adhesion is not particularly limited, such as a thermoplastic resin, a thermosetting resin, and the like. For example, olefin resins such as polypropylene, polybutene, and polyethylene, chlorinated rubber resins, vinyl chloride resins, and phenol resins. , Alkyd resins, various modified alkyd resins, urea resins, melamine resins, vinyl resins such as vinyl acetate, acrylic resins, various synthetic rubbers, epoxy resins, polyester resins, unsaturated polyester resins, polyurethane resins, polyamide resins, polyacetal resins, polyimides Examples thereof include resins and amino resins.
水生生物付着防止用樹脂組成物における塩基性硫酸マグネシウムの含有量は、水生生物付着防止用樹脂組成物全体の重量に対して０．１～７５質量％とするのが好ましく、水生生物付着防止効果と樹脂組成物の機械強度等の物性のバランスの点から、１～５０質量％とするのがより好ましい。０．１質量％未満では水生生物付着防止効果をほとんど示さない傾向があり、７５質量％を超えると樹脂成形物の機械強度等の物性が低下する傾向がある。また、水生生物付着防止用樹脂組成物は、本発明の効果を損なわない程度に、可塑剤等の添加剤を含有していてもよい。
The content of basic magnesium sulfate in the aquatic organism adhesion preventing resin composition is preferably 0.1 to 75% by mass with respect to the total weight of the aquatic organism adhesion preventing resin composition, and the aquatic organism adhesion preventing effect From the viewpoint of the balance of physical properties such as mechanical strength of the resin composition, it is more preferably 1 to 50% by mass. If the amount is less than 0.1% by mass, the aquatic organism adhesion preventing effect tends to be hardly exhibited. If the amount exceeds 75% by mass, physical properties such as mechanical strength of the resin molded product tend to be lowered. Moreover, the aquatic organism adhesion prevention resin composition may contain additives such as a plasticizer to the extent that the effects of the present invention are not impaired.
水生生物付着防止用樹脂組成物の製造方法として特に制限はなく、公知の方法により製造することができる。例えば、水生生物付着防止用樹脂組成物は、各成分を混練することにより調製することができる。混練の方法として特に限定はなく、例えば二軸混練機、バンバリーミキサー、ニーダー、ヘンシェルミキサー等の混練機を用いる方法、二軸押出機、単軸押出機等の押出機を用いる方法、混合機と押出機を組み合わせて製造する方法等を挙げることができる。
There is no restriction | limiting in particular as a manufacturing method of the resin composition for aquatic organism adhesion prevention, It can manufacture by a well-known method. For example, the aquatic organism adhesion preventing resin composition can be prepared by kneading each component. There is no particular limitation as a kneading method, for example, a method using a kneader such as a twin screw kneader, a Banbury mixer, a kneader, a Henschel mixer, a method using an extruder such as a twin screw extruder, a single screw extruder, a mixer and the like The method etc. which manufacture combining an extruder can be mentioned.
また、水生生物付着防止用樹脂組成物は、射出成形機などを用いて成形し、成形体とすることができる。成形体の形状として、例えば板状、シート状、パイプ状、綱状、網状、海水や淡水中で用いられる様々な防汚目的物の形状とすることができる。また、水生生物付着防止用樹脂組成物を用いてなる成形体を、防汚目的物の表面に貼り付け等の方法により設けることもできる。また、上記方法により得られた成形体は、適宜その表面を研磨して用いてもよい。
Also, the resin composition for preventing aquatic organism adhesion can be molded into a molded body using an injection molding machine or the like. As a shape of a molded object, it can be set as the shape of various antifouling objectives used, for example in plate shape, sheet shape, pipe shape, rope shape, net shape, seawater, and freshwater. Moreover, the molded object using the resin composition for aquatic organism adhesion prevention can also be provided by methods, such as affixing on the surface of an antifouling objective. Moreover, you may grind | polish and use the molded object obtained by the said method suitably.
以上のように、本発明の水生生物付着防止剤及び水生生物付着防止方法、水生生物付着防止用樹脂組成物及びそれを用いてなる成形体は、生体及び環境への安全性が高く、且つ持続性に優れた付着防止効果を示す。
As described above, the aquatic organism adhesion preventing agent, the aquatic organism adhesion preventing method, the aquatic organism adhesion preventing resin composition of the present invention, and the molded article using the same are highly safe to the living body and the environment and are sustained. Excellent adhesion prevention effect.
また、本発明に係る水生生物付着防止剤は、これを含有する水生生物付着防止用塗料とすることができる。水生生物付着防止用塗料は、本発明に係る水生生物付着防止剤の他、樹脂などの塗膜形成成分、溶媒、顔料、可塑剤などの塗料に一般に用いられる成分、及び必要に応じて公知の他の有効成分等を含有する。水生生物付着防止用塗料は、例えばペイントコンディショナーやホモミキサー等を用いて、上記の各成分を混合分散することにより調製することができる。
Also, the aquatic organism adhesion preventive agent according to the present invention can be a paint for preventing aquatic organism adhesion containing the same. In addition to the aquatic organism adhesion preventing agent according to the present invention, the aquatic organism adhesion preventing coating material is a coating film-forming component such as a resin, components commonly used in coating materials such as solvents, pigments, and plasticizers, and known as necessary. Contains other active ingredients. The aquatic organism adhesion preventing coating can be prepared by mixing and dispersing each of the above components using, for example, a paint conditioner or a homomixer.
水生生物付着防止用塗料に用いられる樹脂などの塗膜形成成分としては、各種天然樹脂や合成樹脂を使用することができ、具体的には、ロジン、ボイル油、クロロプレンゴムなどの塩化ゴム樹脂、塩化ビニル樹脂、フェノール樹脂、アルキド樹脂、各種変性アルキド樹脂、酢酸ビニルなどのビニル樹脂、アクリル樹脂、ポリブテン等のオレフィン樹脂、各種合成ゴム、エポキシ樹脂、ポリエステル樹脂、ポリウレタン樹脂、ポリアミド樹脂、ポリアセタール樹脂、ポリイミド樹脂、エチルアクリレート－スチレン共重合樹脂、メチルアクリレート－酢酸ビニル共重合樹脂等などの合成樹脂乳濁液、スチレン－ブタジエン共重合ゴム、アクリロニトリル－ブタジエン共重合ゴム、メチルメタクリレート－ブタジエン共重合ゴムなどの合成ゴム乳濁液等が挙げられる。これらの樹脂のうち１種を単独で用いることも、２種以上を併用することもできる。
As a film-forming component such as a resin used for an aquatic organism adhesion prevention coating, various natural resins and synthetic resins can be used. Specifically, chlorinated rubber resins such as rosin, boil oil, chloroprene rubber, Vinyl chloride resins, phenol resins, alkyd resins, various modified alkyd resins, vinyl resins such as vinyl acetate, olefin resins such as acrylic resins and polybutenes, various synthetic rubbers, epoxy resins, polyester resins, polyurethane resins, polyamide resins, polyacetal resins, Synthetic resin emulsion such as polyimide resin, ethyl acrylate-styrene copolymer resin, methyl acrylate-vinyl acetate copolymer resin, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, methyl methacrylate-butadiene copolymer rubber, etc. Synthetic rubber Nigoeki, and the like. One of these resins can be used alone, or two or more can be used in combination.
水生生物付着防止用塗料に用いられる溶媒としては、塗膜形成成分との反応性がなく、樹脂を溶解又は分散するものであれば特に制限はなく、例えば、アセトン、メチルエチルケトン、メチルブチルケトン、メチルイソブチルケトン、ジイソブチルケトン、シクロヘキサノンなどのケトン系溶媒、酢酸エチル、酢酸ブチル、プロピオン酸エチルなどのエステル系溶媒、トルエン、キシレンなどの芳香族炭化水素系溶媒、へキサン、シクロヘキサンなどの脂肪族炭化水素系溶媒、テトラヒドロフラン、ジオキサンなどの環状エーテル系溶媒、エチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテルなどの鎖状エーテル系溶媒、メタノール、エタノール、ブタノールなどのアルコール系溶媒、クロロホルム、塩化メチレン、四塩化炭素などのハロゲン系溶媒、ジメチルスルホキシド、ジメチルホルムアミド、Ｎ－メチル－２－ピロリドンなどの非プロトン性極性溶媒等が使用できる。これらの溶媒のうち１種を単独で用いることも、２種以上を併用することもできる。
The solvent used in the aquatic organism adhesion prevention coating is not particularly limited as long as it has no reactivity with the coating film forming component and can dissolve or disperse the resin. For example, acetone, methyl ethyl ketone, methyl butyl ketone, methyl Ketone solvents such as isobutyl ketone, diisobutyl ketone and cyclohexanone, ester solvents such as ethyl acetate, butyl acetate and ethyl propionate, aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbons such as hexane and cyclohexane Solvents, cyclic ether solvents such as tetrahydrofuran and dioxane, chain ether solvents such as ethylene glycol diethyl ether, diethylene glycol dimethyl ether and diethylene glycol diethyl ether, and alcohols such as methanol, ethanol and butanol Lumpur solvents, chloroform, methylene chloride, tetrahalide based solvents such as carbon tetrachloride, dimethyl sulfoxide, dimethylformamide, aprotic polar solvents such as such as N- methyl-2-pyrrolidone can be used. Among these solvents, one kind can be used alone, or two or more kinds can be used in combination.
水生生物付着防止用塗料に用いられる顔料としては、例えば、べんがら、酸化チタン、酸化鉄、カーボンブラックなどの無機顔料、アゾ系、シアニン系、フタロシアニン系、キナクリドン系などの有機顔料、硫酸バリウム、酸化マグネシウム、アルミナ、ゼオライト、炭酸カルシウム、タルクなどの体質顔料、アルミニウムペースト、ガラスビーズ、マイカなどの特殊機能顔料等を用いることができる。
Examples of pigments used in paints for preventing aquatic organism adhesion include inorganic pigments such as bengara, titanium oxide, iron oxide, and carbon black, organic pigments such as azo, cyanine, phthalocyanine, and quinacridone, barium sulfate, and oxidation. For example, extender pigments such as magnesium, alumina, zeolite, calcium carbonate, and talc, and special function pigments such as aluminum paste, glass beads, and mica can be used.
水生生物付着防止用塗料に用いられる可塑剤としては、塗膜形成成分との反応性がないものであれば特に制限はなく、例えば、パルミチン酸エチル、ステアリン酸エチル、フタル酸ジオクチル、フタル酸ジブチル、リン酸トリフェニル、リン酸トリクレジル、トリオクチルホスフィンオキシド、トリフェニルホスフィンオキシド、トリオクチルホスフェート等が使用できる。これらの可塑剤は、単独で又は２種類以上組み合わせて使用することができる。
The plasticizer used in the aquatic organism adhesion prevention coating is not particularly limited as long as it is not reactive with the film-forming component. For example, ethyl palmitate, ethyl stearate, dioctyl phthalate, dibutyl phthalate Triphenyl phosphate, tricresyl phosphate, trioctyl phosphine oxide, triphenyl phosphine oxide, trioctyl phosphate and the like can be used. These plasticizers can be used alone or in combination of two or more.
水生生物付着防止用塗料における塩基性硫酸マグネシウムの含有量は、１～７０質量％、好ましくは３～２０質量％、より好ましくは３～１５質量％、さらに好ましくは４～１２質量％である。１質量％未満では水生生物付着防止効果をほとんど示さない傾向があり、７０質量％を超えると良好な塗膜が形成されにくい傾向がある。
The content of basic magnesium sulfate in the paint for preventing aquatic organism adhesion is 1 to 70% by mass, preferably 3 to 20% by mass, more preferably 3 to 15% by mass, and further preferably 4 to 12% by mass. If the amount is less than 1% by mass, the aquatic organism adhesion preventing effect tends to be hardly exhibited, and if it exceeds 70% by mass, a good coating film tends to be hardly formed.
上記顔料の使用量は特に制限はないが、使用する場合、水生生物付着防止用塗料における塗膜形成成分１００重量部に対して２００重量部以下であることが好ましい。２００重量部を超えると、塗膜の安定性に劣る傾向があるため好ましくない。
The amount of the pigment used is not particularly limited, but when used, it is preferably 200 parts by weight or less with respect to 100 parts by weight of the coating film-forming component in the aquatic organism adhesion preventing coating. When the amount exceeds 200 parts by weight, the coating film tends to be inferior in stability.
水生生物付着防止用塗料は、防汚目的物の表面に塗布、含浸、吹付けなどの方法により、塗膜として用いることができる。
The aquatic organism adhesion prevention coating can be used as a coating film by a method such as coating, impregnation or spraying on the surface of the antifouling object.
また、本発明に係る水生生物付着防止剤は、これを含有する水生生物付着防止用構造物とすることができる。水生生物付着防止用構造物は、本発明に係る水生生物付着防止剤をモルタルやセメント、コンクリート等に混合して成形することにより製造できる。水生生物付着防止用構造物として、具体的には、港湾設備、海底油田の付属設備、ダムの付属設備、化学工業プラントの熱交換器冷却水の取水路などが挙げられる。
Moreover, the aquatic organism adhesion prevention agent which concerns on this invention can be made into the structure for aquatic organism adhesion prevention containing this. The aquatic organism adhesion preventing structure can be produced by mixing and molding the aquatic organism adhesion preventing agent according to the present invention in mortar, cement, concrete or the like. Specific examples of structures for preventing aquatic organism adhesion include harbor facilities, subsea oil field accessory facilities, dam accessory facilities, and heat exchanger cooling water intakes for chemical industrial plants.
また、水生生物の付着繁殖を防止する目的で、本発明の水生生物付着防止剤を懸濁液として、導排水路管等の中へ直接流してもよい。
Also, for the purpose of preventing the aquatic organisms from sticking and breeding, the aquatic organism adhesion preventing agent of the present invention may be directly flowed into the conduit pipe as a suspension.
以下、本発明を実施例に基づいて具体的に説明するが、これらは本発明の目的を限定するものではない。
Hereinafter, the present invention will be specifically described based on examples, but these do not limit the object of the present invention.
以下の材料を用いて、実施例及び比較例に係る水生生物付着防止用樹脂組成物を作成した。
繊維状塩基性硫酸マグネシウム（ＭｇＳＯ４・５Ｍｇ（ＯＨ）２・３Ｈ２Ｏ）・・・宇部マテリアルズ株式会社製、モスハイジ（登録商標） Ａ－１（顆粒品）、Ｐ粉状品（非造粒品）、何れも平均繊維長１５μｍ、平均繊維径０．５μｍ
ポリプロピレン樹脂・・・ＭＦＲ（温度２３０℃、荷重２．１６ｋｇ）：４５ｇ／１０分 The aquatic organism adhesion prevention resin composition which concerns on an Example and a comparative example was created using the following materials.
Fibrous basic magnesium sulfate (MgSO 4 · 5Mg (OH) 2 · 3H 2 O) ... Made by Ube Materials Co., Ltd., Mosheidi (registered trademark) A-1 (granular product), P powdery product (non-fabricated) Granules), both have an average fiber length of 15 μm and an average fiber diameter of 0.5 μm
Polypropylene resin: MFR (temperature 230 ° C., load 2.16 kg): 45 g / 10 min
繊維状塩基性硫酸マグネシウム（ＭｇＳＯ４・５Ｍｇ（ＯＨ）２・３Ｈ２Ｏ）・・・宇部マテリアルズ株式会社製、モスハイジ（登録商標） Ａ－１（顆粒品）、Ｐ粉状品（非造粒品）、何れも平均繊維長１５μｍ、平均繊維径０．５μｍ
ポリプロピレン樹脂・・・ＭＦＲ（温度２３０℃、荷重２．１６ｋｇ）：４５ｇ／１０分 The aquatic organism adhesion prevention resin composition which concerns on an Example and a comparative example was created using the following materials.
Fibrous basic magnesium sulfate (MgSO 4 · 5Mg (OH) 2 · 3H 2 O) ... Made by Ube Materials Co., Ltd., Mosheidi (registered trademark) A-1 (granular product), P powdery product (non-fabricated) Granules), both have an average fiber length of 15 μm and an average fiber diameter of 0.5 μm
Polypropylene resin: MFR (temperature 230 ° C., load 2.16 kg): 45 g / 10 min
［実施例１］
（試験板の作成）
ポリプロピレン樹脂を９０質量％、繊維状塩基性硫酸マグネシウム［ＭＯＳ・ＨＩＧＥ Ａ－１、宇部マテリアルズ(株)製、平均繊維長：１５μｍ、平均繊維径：０．５μｍ］を１０質量％の割合で混合した。得られた混合物を、二軸混練押出機を用いて溶融混練し、溶融混練物をストランド状に押し出した後、切断して、樹脂ペレットを作成した。当該樹脂ペレットを射出成型機にて射出成形することにより、１５ｍｍ×３０ｍｍの平板を作成した。繊維状塩基性硫酸マグネシウムを樹脂表面に出す目的で、５００番のＳｉＣ耐水研磨紙にて平板の表面を研磨し、実施例１に係る試験板とした。 [Example 1]
(Creation of test plate)
Polypropylene resin 90% by mass, fibrous basic magnesium sulfate [MOS • HIGE A-1, manufactured by Ube Materials Co., Ltd., average fiber length: 15 μm, average fiber diameter: 0.5 μm] at a ratio of 10% by mass Mixed. The obtained mixture was melt-kneaded using a twin-screw kneading extruder, the melt-kneaded product was extruded into a strand shape, and then cut to prepare resin pellets. The resin pellet was injection molded with an injection molding machine to prepare a 15 mm × 30 mm flat plate. In order to bring out fibrous basic magnesium sulfate on the resin surface, the surface of the flat plate was polished with No. 500 SiC water-resistant abrasive paper to obtain a test plate according to Example 1.
（試験板の作成）
ポリプロピレン樹脂を９０質量％、繊維状塩基性硫酸マグネシウム［ＭＯＳ・ＨＩＧＥ Ａ－１、宇部マテリアルズ(株)製、平均繊維長：１５μｍ、平均繊維径：０．５μｍ］を１０質量％の割合で混合した。得られた混合物を、二軸混練押出機を用いて溶融混練し、溶融混練物をストランド状に押し出した後、切断して、樹脂ペレットを作成した。当該樹脂ペレットを射出成型機にて射出成形することにより、１５ｍｍ×３０ｍｍの平板を作成した。繊維状塩基性硫酸マグネシウムを樹脂表面に出す目的で、５００番のＳｉＣ耐水研磨紙にて平板の表面を研磨し、実施例１に係る試験板とした。 [Example 1]
(Creation of test plate)
Polypropylene resin 90% by mass, fibrous basic magnesium sulfate [MOS • HIGE A-1, manufactured by Ube Materials Co., Ltd., average fiber length: 15 μm, average fiber diameter: 0.5 μm] at a ratio of 10% by mass Mixed. The obtained mixture was melt-kneaded using a twin-screw kneading extruder, the melt-kneaded product was extruded into a strand shape, and then cut to prepare resin pellets. The resin pellet was injection molded with an injection molding machine to prepare a 15 mm × 30 mm flat plate. In order to bring out fibrous basic magnesium sulfate on the resin surface, the surface of the flat plate was polished with No. 500 SiC water-resistant abrasive paper to obtain a test plate according to Example 1.
（水生生物付着試験）
実施例１に係る試験板の裏面と、ポリプロピレン製試験容器（８０ｍｍ×８０ｍｍ×４５ｍｍ）の底面とを、ホットボンド（大洋電気産業社製）を用いて固定し、ポアサイズ０．４５μｍの混合セルロースメンブレン（東洋濾紙社製）でろ過した天然海水（塩分濃度２．９３％、ｐＨ８．１１）１００ｍＬ、及びタテジマフジツボのキプリス幼生約４０個体を投入した。試験板の試験容器への浸漬は、２２℃±２℃、暗条件下において１２日間行った。タテジマフジツボのキプリス幼生の行動及び状態について、試験開始後１、２、４、５、７、９及び１２日後に、顕微鏡を用いて目視にて観察した。試験開始１２日後の試験板への付着数及びキプリス幼生の投入数により、下記数１により付着率を求めた。実施例１に係る試験板へのフジツボ付着率は、０％であった。結果を表１に示す。 (Aquatic organism adhesion test)
The back surface of the test plate according to Example 1 and the bottom surface of a polypropylene test container (80 mm × 80 mm × 45 mm) are fixed using a hot bond (manufactured by Taiyo Electric Industry Co., Ltd.), and a mixed cellulose membrane having a pore size of 0.45 μm. 100 mL of natural seawater (salt concentration: 2.93%, pH 8.11) filtered through (manufactured by Toyo Roshi Kaisha Co., Ltd.) and about 40 cypris larvae of vertical barnacles were added. The test plate was immersed in a test container at 22 ° C. ± 2 ° C. for 12 days under dark conditions. The behavior and condition of Cypris larvae of the vertical barnacles were visually observed using a microscope after 1, 2, 4, 5, 7, 9 and 12 days after the start of the test. The adhesion rate was determined by the following equation 1 based on the number of adhesions to the test plate 12 days after the start of the test and the number of injected cypris larvae. The barnacle adhesion rate to the test plate according to Example 1 was 0%. The results are shown in Table 1.
実施例１に係る試験板の裏面と、ポリプロピレン製試験容器（８０ｍｍ×８０ｍｍ×４５ｍｍ）の底面とを、ホットボンド（大洋電気産業社製）を用いて固定し、ポアサイズ０．４５μｍの混合セルロースメンブレン（東洋濾紙社製）でろ過した天然海水（塩分濃度２．９３％、ｐＨ８．１１）１００ｍＬ、及びタテジマフジツボのキプリス幼生約４０個体を投入した。試験板の試験容器への浸漬は、２２℃±２℃、暗条件下において１２日間行った。タテジマフジツボのキプリス幼生の行動及び状態について、試験開始後１、２、４、５、７、９及び１２日後に、顕微鏡を用いて目視にて観察した。試験開始１２日後の試験板への付着数及びキプリス幼生の投入数により、下記数１により付着率を求めた。実施例１に係る試験板へのフジツボ付着率は、０％であった。結果を表１に示す。 (Aquatic organism adhesion test)
The back surface of the test plate according to Example 1 and the bottom surface of a polypropylene test container (80 mm × 80 mm × 45 mm) are fixed using a hot bond (manufactured by Taiyo Electric Industry Co., Ltd.), and a mixed cellulose membrane having a pore size of 0.45 μm. 100 mL of natural seawater (salt concentration: 2.93%, pH 8.11) filtered through (manufactured by Toyo Roshi Kaisha Co., Ltd.) and about 40 cypris larvae of vertical barnacles were added. The test plate was immersed in a test container at 22 ° C. ± 2 ° C. for 12 days under dark conditions. The behavior and condition of Cypris larvae of the vertical barnacles were visually observed using a microscope after 1, 2, 4, 5, 7, 9 and 12 days after the start of the test. The adhesion rate was determined by the following equation 1 based on the number of adhesions to the test plate 12 days after the start of the test and the number of injected cypris larvae. The barnacle adhesion rate to the test plate according to Example 1 was 0%. The results are shown in Table 1.
［実施例２］
ポリプロピレン樹脂を７０質量％、繊維状塩基性硫酸マグネシウムを３０質量％としたこと以外は実施例１と同様にして試験板を作成し、水生生物付着試験を行った。結果を表１に示す。 [Example 2]
A test plate was prepared in the same manner as in Example 1 except that 70% by mass of polypropylene resin and 30% by mass of fibrous basic magnesium sulfate were used, and an aquatic organism adhesion test was performed. The results are shown in Table 1.
ポリプロピレン樹脂を７０質量％、繊維状塩基性硫酸マグネシウムを３０質量％としたこと以外は実施例１と同様にして試験板を作成し、水生生物付着試験を行った。結果を表１に示す。 [Example 2]
A test plate was prepared in the same manner as in Example 1 except that 70% by mass of polypropylene resin and 30% by mass of fibrous basic magnesium sulfate were used, and an aquatic organism adhesion test was performed. The results are shown in Table 1.
［実施例３］
実施例２と同様の配合にて平板を作成し、当該平板の表面を研磨せずに実施例３に係る試験板とした。実施例３に係る試験板に対し、実施例１と同様に水生生物付着試験を行った。結果を表１に示す。 [Example 3]
A flat plate was prepared with the same composition as in Example 2, and the surface of the flat plate was not polished to obtain a test plate according to Example 3. The aquatic organism adhesion test was performed on the test plate according to Example 3 in the same manner as in Example 1. The results are shown in Table 1.
実施例２と同様の配合にて平板を作成し、当該平板の表面を研磨せずに実施例３に係る試験板とした。実施例３に係る試験板に対し、実施例１と同様に水生生物付着試験を行った。結果を表１に示す。 [Example 3]
A flat plate was prepared with the same composition as in Example 2, and the surface of the flat plate was not polished to obtain a test plate according to Example 3. The aquatic organism adhesion test was performed on the test plate according to Example 3 in the same manner as in Example 1. The results are shown in Table 1.
［比較例１］
繊維状塩基性硫酸マグネシウムを添加せず、ポリプロピレン樹脂を１００質量％としたこと以外は実施例１と同様にして試験板を作成し、水生生物付着試験を行った。結果を表１に示す。 [Comparative Example 1]
A test plate was prepared in the same manner as in Example 1 except that the fibrous basic magnesium sulfate was not added and the polypropylene resin was 100% by mass, and an aquatic organism adhesion test was performed. The results are shown in Table 1.
繊維状塩基性硫酸マグネシウムを添加せず、ポリプロピレン樹脂を１００質量％としたこと以外は実施例１と同様にして試験板を作成し、水生生物付着試験を行った。結果を表１に示す。 [Comparative Example 1]
A test plate was prepared in the same manner as in Example 1 except that the fibrous basic magnesium sulfate was not added and the polypropylene resin was 100% by mass, and an aquatic organism adhesion test was performed. The results are shown in Table 1.
［比較例２］
試験板の代わりに３０ｍｍ×３０ｍｍのガラス板を用いて、実施例１と同様に水生生物付着試験を行った。結果を表１に示す。 [Comparative Example 2]
An aquatic organism adhesion test was conducted in the same manner as in Example 1 using a 30 mm × 30 mm glass plate instead of the test plate. The results are shown in Table 1.
試験板の代わりに３０ｍｍ×３０ｍｍのガラス板を用いて、実施例１と同様に水生生物付着試験を行った。結果を表１に示す。 [Comparative Example 2]
An aquatic organism adhesion test was conducted in the same manner as in Example 1 using a 30 mm × 30 mm glass plate instead of the test plate. The results are shown in Table 1.
表１に示す結果から明らかなように、繊維状塩基性硫酸マグネシウムを含有する実施例１～３に係る試験板は、フジツボ幼生の付着率が小さく、防汚効果に優れることがわかる。なお、すべての水生生物付着試験において、試験終了時にフジツボ幼生の胸肢突出や無反応などのダメージは見られなかった。
As is clear from the results shown in Table 1, it can be seen that the test plates according to Examples 1 to 3 containing fibrous basic magnesium sulfate have a low adhesion rate of barnacle larvae and an excellent antifouling effect. In all aquatic organism adhesion tests, barnacle larvae did not show any damage such as protruding limbs or no reaction at the end of the test.
［実施例４］
（１）塩基性硫酸マグネシウム含有塗料の作製
エポキシ樹脂［日新レジン（株）製、低粘度エポキシ樹脂・Ｚ-1、ビスフェノールＡ型液状エポキシ樹脂］を７９．２質量％、硬化剤［日新レジン（株）製、５０分型・硬化剤］を１５．８質量％と繊維状塩基性硫酸マグネシウム粒子［ＭＯＳ・ＨＩＧＥ Ｐ粉状品、宇部マテリアルズ(株)製、平均繊維長：１５μｍ、平均繊維径：０．５μｍ］を５．０質量％の割合にて混合しエポキシ樹脂を主成分とする実施例４に係る塗料を得た。 [Example 4]
(1) Preparation of paint containing basic magnesium sulfate 79.2% by mass of epoxy resin [manufactured by Nissin Resin Co., Ltd., low viscosity epoxy resin / Z-1, bisphenol A liquid epoxy resin], curing agent [Nisshin Resin Co., Ltd., 50 minute mold / curing agent] 15.8% by mass and fibrous basic magnesium sulfate particles [MOS / HIGE P powder product, manufactured by Ube Materials Co., Ltd., average fiber length: 15 μm, Average fiber diameter: 0.5 μm] was mixed at a ratio of 5.0% by mass to obtain a coating material according to Example 4 having an epoxy resin as a main component.
（１）塩基性硫酸マグネシウム含有塗料の作製
エポキシ樹脂［日新レジン（株）製、低粘度エポキシ樹脂・Ｚ-1、ビスフェノールＡ型液状エポキシ樹脂］を７９．２質量％、硬化剤［日新レジン（株）製、５０分型・硬化剤］を１５．８質量％と繊維状塩基性硫酸マグネシウム粒子［ＭＯＳ・ＨＩＧＥ Ｐ粉状品、宇部マテリアルズ(株)製、平均繊維長：１５μｍ、平均繊維径：０．５μｍ］を５．０質量％の割合にて混合しエポキシ樹脂を主成分とする実施例４に係る塗料を得た。 [Example 4]
(1) Preparation of paint containing basic magnesium sulfate 79.2% by mass of epoxy resin [manufactured by Nissin Resin Co., Ltd., low viscosity epoxy resin / Z-1, bisphenol A liquid epoxy resin], curing agent [Nisshin Resin Co., Ltd., 50 minute mold / curing agent] 15.8% by mass and fibrous basic magnesium sulfate particles [MOS / HIGE P powder product, manufactured by Ube Materials Co., Ltd., average fiber length: 15 μm, Average fiber diameter: 0.5 μm] was mixed at a ratio of 5.0% by mass to obtain a coating material according to Example 4 having an epoxy resin as a main component.
（２）試験板の作製
上記（１）で作成した塗料を、すき間３００μmのフィルムアプリケータを用いて塩ビ板（４８×４８×５ｍｍT）に塗布し、２３℃、５０％RHで４８時間、次いで５０℃で５時間硬化させ、試験板を作製した。作製した試験板は、塩基性硫酸マグネシウム粒子を樹脂表面に出す目的で、＃１２００のＳiＣ耐水研磨紙にて樹脂表面を研磨し、水生生物付着試験用の試験板とした。 (2) Preparation of test plate The paint prepared in (1) above was applied to a vinyl chloride plate (48 x 48 x 5 mmT) using a film applicator with a gap of 300 µm, and then for 48 hours at 23 ° C and 50% RH. A test plate was prepared by curing at 50 ° C. for 5 hours. The prepared test plate was polished with # 1200 SiC water-resistant abrasive paper for the purpose of putting out basic magnesium sulfate particles on the resin surface, and used as a test plate for aquatic organism adhesion test.
上記（１）で作成した塗料を、すき間３００μmのフィルムアプリケータを用いて塩ビ板（４８×４８×５ｍｍT）に塗布し、２３℃、５０％RHで４８時間、次いで５０℃で５時間硬化させ、試験板を作製した。作製した試験板は、塩基性硫酸マグネシウム粒子を樹脂表面に出す目的で、＃１２００のＳiＣ耐水研磨紙にて樹脂表面を研磨し、水生生物付着試験用の試験板とした。 (2) Preparation of test plate The paint prepared in (1) above was applied to a vinyl chloride plate (48 x 48 x 5 mmT) using a film applicator with a gap of 300 µm, and then for 48 hours at 23 ° C and 50% RH. A test plate was prepared by curing at 50 ° C. for 5 hours. The prepared test plate was polished with # 1200 SiC water-resistant abrasive paper for the purpose of putting out basic magnesium sulfate particles on the resin surface, and used as a test plate for aquatic organism adhesion test.
（３）水生生物付着試験
上記（２）で作成した水生生物付着試験用試験板を前記と同様に海水、フジツボキプリス幼生が投入された試験容器内（２２℃±２、暗条件下）へ浸漬した。フジツボキプリス幼生の行動及び状態については顕微鏡を用いて目視にて観察し、１４日後に塗料の塗布層表面に付着した要請の付着数より下記数１により付着率を求めた。その結果を表２に示す。 (3) Aquatic organism adhesion test The test plate for aquatic organism adhesion test prepared in (2) above is immersed in a test vessel (22 ° C ± 2, dark condition) into which seawater and barnacle crisp larvae are introduced as described above. did. The behavior and state of the barnacle Cyprus larvae were visually observed using a microscope, and the adhesion rate was determined by the following formula 1 from the required number of adhesions that adhered to the coating layer surface after 14 days. The results are shown in Table 2.
上記（２）で作成した水生生物付着試験用試験板を前記と同様に海水、フジツボキプリス幼生が投入された試験容器内（２２℃±２、暗条件下）へ浸漬した。フジツボキプリス幼生の行動及び状態については顕微鏡を用いて目視にて観察し、１４日後に塗料の塗布層表面に付着した要請の付着数より下記数１により付着率を求めた。その結果を表２に示す。 (3) Aquatic organism adhesion test The test plate for aquatic organism adhesion test prepared in (2) above is immersed in a test vessel (22 ° C ± 2, dark condition) into which seawater and barnacle crisp larvae are introduced as described above. did. The behavior and state of the barnacle Cyprus larvae were visually observed using a microscope, and the adhesion rate was determined by the following formula 1 from the required number of adhesions that adhered to the coating layer surface after 14 days. The results are shown in Table 2.
［実施例５］
エポキシ樹脂を７５．０質量％、硬化剤を１５．０質量％と繊維状塩基性硫酸マグネシウム粒子を１０．０質量％の割合にて混合したこと以外は、実施例４と同様にして試験板を作製して、水生生物付着試験を行った。その結果を表２に示す。 [Example 5]
Test plate in the same manner as in Example 4 except that 75.0% by mass of epoxy resin, 15.0% by mass of curing agent, and 10.0% by mass of fibrous basic magnesium sulfate particles were mixed. Was prepared and an aquatic organism adhesion test was conducted. The results are shown in Table 2.
エポキシ樹脂を７５．０質量％、硬化剤を１５．０質量％と繊維状塩基性硫酸マグネシウム粒子を１０．０質量％の割合にて混合したこと以外は、実施例４と同様にして試験板を作製して、水生生物付着試験を行った。その結果を表２に示す。 [Example 5]
Test plate in the same manner as in Example 4 except that 75.0% by mass of epoxy resin, 15.0% by mass of curing agent, and 10.0% by mass of fibrous basic magnesium sulfate particles were mixed. Was prepared and an aquatic organism adhesion test was conducted. The results are shown in Table 2.
［実施例６］
エポキシ樹脂を７５．０質量％、硬化剤を１５．０質量％と繊維状塩基性硫酸マグネシウム粒子を１０．０質量％の割合にて混合したことと、試験片の樹脂表面を＃１２００のＳiＣ耐水研磨紙にて研磨しなかったこと以外は実施例４と同様にして試験板を作製し、水生生物付着試験を行った。その結果を表２に示す。 [Example 6]
The epoxy resin was mixed at a ratio of 75.0% by mass, the curing agent was 15.0% by mass, and the fibrous basic magnesium sulfate particles were mixed at a rate of 10.0% by mass. A test plate was prepared in the same manner as in Example 4 except that it was not polished with water-resistant abrasive paper, and an aquatic organism adhesion test was performed. The results are shown in Table 2.
エポキシ樹脂を７５．０質量％、硬化剤を１５．０質量％と繊維状塩基性硫酸マグネシウム粒子を１０．０質量％の割合にて混合したことと、試験片の樹脂表面を＃１２００のＳiＣ耐水研磨紙にて研磨しなかったこと以外は実施例４と同様にして試験板を作製し、水生生物付着試験を行った。その結果を表２に示す。 [Example 6]
The epoxy resin was mixed at a ratio of 75.0% by mass, the curing agent was 15.0% by mass, and the fibrous basic magnesium sulfate particles were mixed at a rate of 10.0% by mass. A test plate was prepared in the same manner as in Example 4 except that it was not polished with water-resistant abrasive paper, and an aquatic organism adhesion test was performed. The results are shown in Table 2.
［比較例３］
エポキシ樹脂を８３．３質量％、硬化剤を１６．７質量％の割合にて混合し、繊維状塩基性硫酸マグネシウム粒子を配合しないこと以外は、実施例４と同様にして試験板を作製して、水生生物付着試験を行った。その結果を表２に示す。 [Comparative Example 3]
A test plate was prepared in the same manner as in Example 4 except that 83.3 mass% of the epoxy resin and 16.7 mass% of the curing agent were mixed and the fibrous basic magnesium sulfate particles were not blended. The aquatic organism adhesion test was conducted. The results are shown in Table 2.
エポキシ樹脂を８３．３質量％、硬化剤を１６．７質量％の割合にて混合し、繊維状塩基性硫酸マグネシウム粒子を配合しないこと以外は、実施例４と同様にして試験板を作製して、水生生物付着試験を行った。その結果を表２に示す。 [Comparative Example 3]
A test plate was prepared in the same manner as in Example 4 except that 83.3 mass% of the epoxy resin and 16.7 mass% of the curing agent were mixed and the fibrous basic magnesium sulfate particles were not blended. The aquatic organism adhesion test was conducted. The results are shown in Table 2.
Claims (7)
- 塩基性硫酸マグネシウムを含有することを特徴とする水生生物付着防止剤。 An aquatic organism adhesion inhibitor characterized by containing basic magnesium sulfate.
- 請求項１に記載の水生生物付着防止剤を含有することを特徴とする水生生物付着防止用樹脂組成物。 An aquatic organism adhesion preventing resin composition comprising the aquatic organism adhesion preventing agent according to claim 1.
- 請求項１に記載の水生生物付着防止剤を含有する事を特徴とする水生生物付着防止用塗料。 An aquatic organism adhesion preventing paint comprising the aquatic organism adhesion preventing agent according to claim 1.
- 水生生物付着防止剤を１～７０質量％含有する請求項３に記載の水生生物付着防止用塗料。 The paint for preventing aquatic organism adhesion according to claim 3, comprising 1 to 70% by mass of an aquatic organism adhesion preventing agent.
- 水生生物付着防止剤を３～７０質量％含有する請求項３に記載の水生生物付着防止用塗料。 The paint for preventing aquatic organism adhesion according to claim 3, comprising 3 to 70% by mass of an aquatic organism adhesion preventing agent.
- 請求項２に記載の水生生物付着防止用樹脂組成物を用いてなる成形体。 A molded body using the aquatic organism adhesion preventing resin composition according to claim 2.
- 請求項１に記載の水生生物付着防止剤を使用して水生生物の付着を防止することを特徴とする水生生物付着防止方法。 An aquatic organism adhesion prevention method characterized by using the aquatic organism adhesion inhibitor according to claim 1 to prevent adhesion of aquatic organisms.
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| WO2020189414A1 (en) * | 2019-03-15 | 2020-09-24 | 日東化成株式会社 | Antifouling coating composition |
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| JPS6011223A (en) * | 1983-06-27 | 1985-01-21 | Kyowa Chem Ind Co Ltd | Fibrous magnesium oxide and its manufacture |
| JPS61213252A (en) * | 1985-03-18 | 1986-09-22 | Sakai Chem Ind Co Ltd | Vinyl chloride resin composition |
| JPH0565433A (en) * | 1990-05-11 | 1993-03-19 | Suzuki Sogyo Co Ltd | Material for preventing adhesion of aquatic life |
| JPH09255897A (en) * | 1996-03-19 | 1997-09-30 | Ereganto:Kk | Prevent ion of adhesion of aquatic organism and coating material for preventing adhesion of aquatic organism |
| JP2016191036A (en) * | 2015-03-30 | 2016-11-10 | 宇部マテリアルズ株式会社 | Polyolefin resin composition |
| CN106927713A (en) * | 2017-04-06 | 2017-07-07 | 日照市海洋工程研究院 | A kind of maritime concrete anti-crack and anti-seepage additive |
| CN107626215A (en) * | 2017-09-15 | 2018-01-26 | 中国海洋大学 | A kind of antifouling composite hyperfiltration membrane and preparation method thereof |
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| US20160160044A1 (en) * | 2013-06-28 | 2016-06-09 | Mitsui Chemicals. Inc. | Molding resin composition |
| CN105969120A (en) * | 2016-03-28 | 2016-09-28 | 刘辉 | Whisker-type furniture coating and preparation method thereof |
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2018
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6011223A (en) * | 1983-06-27 | 1985-01-21 | Kyowa Chem Ind Co Ltd | Fibrous magnesium oxide and its manufacture |
| JPS61213252A (en) * | 1985-03-18 | 1986-09-22 | Sakai Chem Ind Co Ltd | Vinyl chloride resin composition |
| JPH0565433A (en) * | 1990-05-11 | 1993-03-19 | Suzuki Sogyo Co Ltd | Material for preventing adhesion of aquatic life |
| JPH09255897A (en) * | 1996-03-19 | 1997-09-30 | Ereganto:Kk | Prevent ion of adhesion of aquatic organism and coating material for preventing adhesion of aquatic organism |
| JP2016191036A (en) * | 2015-03-30 | 2016-11-10 | 宇部マテリアルズ株式会社 | Polyolefin resin composition |
| CN106927713A (en) * | 2017-04-06 | 2017-07-07 | 日照市海洋工程研究院 | A kind of maritime concrete anti-crack and anti-seepage additive |
| CN107626215A (en) * | 2017-09-15 | 2018-01-26 | 中国海洋大学 | A kind of antifouling composite hyperfiltration membrane and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020189414A1 (en) * | 2019-03-15 | 2020-09-24 | 日東化成株式会社 | Antifouling coating composition |
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| JPWO2018194108A1 (en) | 2020-05-21 |
| JP7059261B2 (en) | 2022-04-25 |
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