JPWO2016204142A1 - Aquatic organism adhesion prevention material, aquatic organism adhesion prevention paint, aquatic organism adhesion prevention panel, underwater structure, method and molded product for preventing aquatic organisms from adhering to underwater structure - Google Patents

Abstract

To provide a novel aquatic organism adhesion prevention material that is difficult for aquatic organisms to adhere to. An aquatic organism adhesion-preventing material comprising a copolymer containing a fluorine-containing olefin unit and a polymerizable vinyl compound unit having an amide bond.

Description

The present invention relates to an aquatic organism adhesion preventing material, an aquatic organism adhesion preventing paint, an aquatic organism adhesion preventing panel, an underwater structure, a method for preventing aquatic organisms from adhering to the underwater structure, and a molded article.

In various underwater structures such as seawater intake facilities at power plants, a large amount of aquatic organisms (marine organisms) such as barnacles, squirts, cell plastics, mussels, mussels, chrysanthemum moths, blue-necked beetles, blue-tailed seaweeds adhere to the surface. However, there is a concern of causing functional deterioration or functional disorder resulting from it. In the past, mechanical removal methods such as scraping off attached aquatic organisms were also common, but in recent years various antifouling paints have been developed and applied to the surface of underwater structures. The main practice is to prevent the attachment of aquatic organisms.

Antifouling paints include those containing toxic antifouling agents such as organotin compounds, cuprous oxide, zinc pyrithione and copper pyrithione. However, although the adhesion and growth of aquatic organisms can be prevented, a toxic antifouling agent is used, which is undesirable for environmental safety and hygiene during the production and painting of paints. Elutes gradually and may contaminate waters in the long term.

On the other hand, as a material that can control biocompatibility and has no toxicity, Non-Patent Document 1 discloses a copolymer of chlorotrifluoroethylene and N-vinylpyrrolidone and a fluorinated amphiphilic block copolymer comprising polyvinylpyrrolidone. Has a biocompatibility and is not cytotoxic.

Thus, Non-Patent Document 1 describes a copolymer of a fluorinated monomer and vinylpyrrolidone as an artificial material having biocompatibility. In addition to these, as copolymers of fluorinated monomers and vinylpyrrolidone, the following copolymers are known, but the presence or absence of biocompatibility is unknown.

For example, Patent Document 1 discloses that a fluoroolefin, an N-vinyl-lactam compound, a monomer having a crosslinkable functional group, and a monomer copolymerizable therewith are 30 to 70 mol% and 70 to 5 mol, respectively. %, 2 to 40 mol%, and a fluorine-containing copolymer copolymerized at a ratio of 0 to 63 mol%.

Non-Patent Document 2 describes a copolymer of chlorotrifluoroethylene and N-vinylpyrrolidone.

Japanese Patent Laid-Open No. 1-108270

Pucheng Wang, outside five, "Synthesis and properties of a well-defined copolymer of chlorotrifluoroethylene and N-vinylpyrrolidone by xanthate-mediated radical copolymerization under 60Co γ-ray irradiation", Polymer Chemistry, 2014 years, Vol. 5, p. 6358-6364 CAO JIN, two others, “Radiation-Induced Copolymerization of N-Vinylpyrrolidone with Monochlorotrifluoroethylene”, J. Macromol. Sci. Chem. 1985, A22 (3), p. 379-386

An object of this invention is to provide the novel aquatic organism adhesion prevention material which aquatic organism does not adhere easily.

The present invention is an aquatic organism adhesion prevention material comprising a copolymer containing a fluorine-containing olefin unit and a polymerizable vinyl compound unit having an amide bond.

In the aquatic organism adhesion preventing material of the present invention, the content of the fluorine-containing olefin unit in the copolymer is 65 to 5 mol%, and the content of the polymerizable vinyl compound unit having an amide bond is 35 to 95 mol%. It is preferable.

The fluorine-containing olefin is preferably at least one selected from the group consisting of tetrafluoroethylene, chlorotrifluoroethylene, and hexafluoropropylene.

The polymerizable vinyl compound having an amide bond is preferably N-vinyl-2-pyrrolidone.

The present invention is also an aquatic organism adhesion-preventing paint comprising the above-mentioned aquatic organism adhesion-preventing material.

The aquatic organism adhesion preventing paint of the present invention preferably further contains an organic solvent.

This invention is also an aquatic organism adhesion prevention panel which consists of a base material and the coating film which consists of the above-mentioned aquatic organism adhesion prevention coating material formed on the said base material.

The present invention is also an underwater structure including a coating film made of the above-described aquatic organism adhesion preventing paint.

The present invention is also a method for preventing aquatic organisms from adhering to an underwater structure, which includes the step of applying the above-mentioned aquatic organism adhesion preventing paint.

The present invention is also a molded article formed by molding the above-mentioned aquatic organism adhesion prevention material, and is a molded article that is a film, a sheet, or a tube.

The aquatic organism adhesion preventing material of the present invention is less likely to adhere to aquatic organisms. From the aquatic organism adhesion-preventing material of the present invention, it is possible to obtain a paint that is difficult for aquatic organisms to adhere to.

The aquatic organism adhesion-preventing paint of the present invention is unlikely to adhere to aquatic organisms. From the aquatic organism adhesion-preventing paint of the present invention, it is possible to obtain a panel and an underwater structure to which aquatic organisms hardly adhere.

Hereinafter, the present invention will be specifically described.

The aquatic organism adhesion preventing material of the present invention comprises a copolymer containing a fluorine-containing olefin unit and a polymerizable vinyl compound unit having an amide bond. The low aquatic organism adhesion of the copolymer is a characteristic newly found by the present inventors.

Examples of aquatic organisms include barnacles, sea squirts, cell plastics, mussels, crow mussels, chrysanthemum moths, blue sea breams, blue sea lions, sea anemones, oysters, hydroworms, various aquatic microorganisms, various seaweeds (such as green lily, honda walla, blue grass, blue seaweed), cyanobacteria, Green algae (Aomidoro, Azalea, etc.), Euglena algae, yellow green algae, golden algae, diatoms, red algae, crypto algae, flame algae, moss (tea moss etc.) Examples include marine animals (such as Yuzuda Kaimen), blue seaweed, and aquatic plants. Water plants include Anubius, Anubius Nana, Aponogeton, Amazon sword plant, Willow moss, Echinodorus, Giant canadian, Dutch plant, Oyster plant, Cyprinus, Bombardia, Chrysanthemum, Goldfish algae, Cryptocoryne, Black moss, Cocanada, Sagittarius, Water lily, Nymphaea, Examples include Barisneria, Fusamo, Pogostemon helferry, Hossa, Potamogeton, Water hyacinth, Matsumo, Mitsudeherashi, Ludvisia, and Rotara. As aquatic organisms, larvae are preferable, and cypris larvae are more preferable.
The aquatic organism is preferably an aquatic organism (excluding bacteria). Further, the aquatic organism adhesion preventing material is preferably an aquatic organism adhesion preventing material (however, excluding bacteria adhesion preventing material). In addition, aquatic plants may mediate the generation of algae and the like.

In the aquatic organism adhesion preventing material of the present invention, the content of the fluorinated olefin unit in the copolymer is 65 to 5 mol%, and the content of the polymerizable vinyl compound unit having an amide bond is 35 to 95 mol%. Preferably there is. If the content of the fluorinated olefin unit and the polymerizable vinyl compound unit having an amide bond is within the above range, aquatic organisms are less likely to adhere to the aquatic organism adhesion preventing material.

The fluorine-containing olefin unit is more preferably at least 10 mol%, more preferably at least 20 mol%, particularly preferably at least 30 mol%, based on all monomer units constituting the copolymer. Preferably, it is 55 mol% or less, more preferably 45 mol% or less, and particularly preferably 40 mol% or less. When the content of the fluorinated olefin unit is within the above range, aquatic organisms are less likely to adhere to the aquatic organism adhesion preventing material.

The polymerizable vinyl compound unit having an amide bond is more preferably 45 mol% or more, further preferably 55 mol% or more, based on all monomer units constituting the copolymer. It is particularly preferably at least mol%, more preferably at most 90 mol%, further preferably at most 80 mol%, particularly preferably at most 70 mol%. When the content of the polymerizable vinyl compound unit having the amide bond is within the above range, aquatic organisms are less likely to adhere to the aquatic organism adhesion preventing material.

When the number of fluorine-containing olefin units is less than the above range and there are many polymerizable vinyl compound units having an amide bond, the above copolymer is soluble in water, and the copolymer is eluted in water during actual use. Absent.

In the present specification, a copolymer containing a fluorine-containing olefin unit and a polymerizable vinyl compound unit having an amide bond may be described as a polymerizable vinyl compound copolymer having a fluorine-containing olefin / amide bond.

In the above polymerizable vinyl compound copolymer having a fluorinated olefin / amide bond, a good biocompatibility can be obtained, so the molar ratio between the fluorinated olefin unit and the polymerizable vinyl compound unit having an amide bond (fluorine-containing The olefin unit / polymerizable vinyl compound unit having an amide bond) is preferably 1.80 to 0.05, more preferably 0.11 or more, further preferably 0.25 or more, More preferably, it is 0.43 or more, more preferably 1.00 or less, still more preferably 0.82 or less, and still more preferably 0.67 or less.

Examples of the fluorine-containing olefin include tetrafluoroethylene (TFE), hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE), vinylidene fluoride, trifluoroethylene, monofluoroethylene, fluoroalkyl vinyl ether, fluoroalkylethylene, Fluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, hexafluoroisobutene, trifluorostyrene, and general formula: CH ₂ ═CFRf (wherein Rf is a linear or branched fluoro having 1 to 12 carbon atoms) It is preferably at least one selected from the group consisting of fluorine-containing olefins represented by an alkyl group), and at least selected from the group consisting of TFE, CTFE, vinylidene fluoride and HFP Is more preferably one, more preferably at least one selected from the group consisting of TFE, CTFE and HFP, and particularly preferably at least one selected from the group consisting of TFE and HFP. preferable.

The polymerizable vinyl compound has an amide bond, and preferably has a polymerizable vinyl group in addition to the amide bond. The amide bond refers to a bond between a carbonyl group and a nitrogen atom.
Examples of the polymerizable vinyl group include a vinyl group, an allyl group, a vinyl ether group, a vinyl ester group, and an acrylic group.

Examples of the polymerizable vinyl compound having an amide bond include N-vinyl-β-propiolactam, N-vinyl-2-pyrrolidone, N-vinyl-γ-valerolactam, N-vinyl-2-piperidone, and N-vinyl. -N-vinyl lactam compounds such as heptolactam, acyclic N-vinylamide compounds such as N-vinylformamide and N-methyl-N-vinylacetamide, acyclic N such as N-allyl-N-methylformamide and allylurea -Allylamide compounds, N-allyl lactam compounds such as 1- (2-propenyl) -2-pyrrolidone, and acrylamide compounds such as (meth) acrylamide, N, N-dimethylacrylamide and N-isopropylacrylamide.

（式中、Ｒ_１及びＲ_２は独立にＨ又は炭素数１〜１０のアルキル基）で示される化合物、

（式中、Ｒ_１及びＲ_２は独立にＨ又は炭素数１〜１０のアルキル基）で示される化合物等も挙げられる。As the polymerizable vinyl compound having an amide bond,

Wherein R ₁ and R ₂ are independently H or an alkyl group having 1 to 10 carbon atoms,

Examples thereof include compounds represented by the formula (wherein R ₁ and R ₂ are independently H or an alkyl group having 1 to 10 carbon atoms).

Among these, N-vinyl lactam compounds or acyclic N-vinyl amide compounds are preferable, and N-vinyl-β-propiolactam, N-vinyl-2-pyrrolidone, N-vinyl-γ-valerolactam, N-vinyl- More preferred is at least one selected from the group consisting of 2-piperidone and N-vinyl-heptlactam, and at least selected from the group consisting of N-vinyl-2-pyrrolidone and N-vinyl-2-piperidone. One is more preferred, and N-vinyl-2-pyrrolidone is particularly preferred.

The polymerizable vinyl compound copolymer having a fluorine-containing olefin / amide bond is a monomer unit other than the fluorine-containing olefin unit and the polymerizable vinyl compound unit having an amide bond, as long as the effects of the present invention are not impaired. You may have. Other monomer units include vinyl ester monomer units, vinyl ether monomer units, (meth) acrylic monomer units having polyethylene glycol in the side chain, vinyl monomer units having polyethylene glycol in the side chain, and long-chain hydrocarbon groups. (Meth) acryl monomer units, vinyl monomer units having a long-chain hydrocarbon group, and the like. The total of other monomer units may be 0 to 50 mol%, preferably 0 to 40 mol%, more preferably 0 to 30 mol%, and 0 to 20 mol%. More preferably, it is more preferably 0 to 15 mol%, particularly preferably 0 to 10 mol%, and most preferably 0 to 5 mol%.

The polymerizable vinyl compound copolymer having a fluorine-containing olefin / amide bond preferably consists essentially of a fluorine-containing olefin unit and a polymerizable vinyl compound unit having an amide bond.

The polymerizable vinyl compound copolymer having a fluorine-containing olefin / amide bond preferably has a weight average molecular weight of 10,000 or more. More preferably, it is 15000-500000, More preferably, it is 20000-300000. The weight average molecular weight can be determined by gel permeation chromatography (GPC).

The polymerizable vinyl compound copolymer having a fluorine-containing olefin / amide bond can be produced by radical polymerization. There are no particular limitations regarding the type of production process, the type / presence of the medium, uniformity within the polymerization reaction system, etc., for example, solution polymerization, emulsion polymerization, soap-free polymerization, suspension polymerization, precipitation polymerization, dispersion polymerization Or by bulk polymerization.

The aquatic organism adhesion prevention material may be formed as a single molded product such as a film, a sheet or a tube by molding by a casting method, an extrusion method or the like, or a coating film is formed on the surface of an article or structure by painting. Also good. The present invention is also a molded article formed by molding the above-mentioned aquatic organism adhesion prevention material, and is a molded article that is a film, a sheet, or a tube.

This invention is also an aquatic organism adhesion prevention coating material which consists of the above-mentioned aquatic organism adhesion prevention material.
The aquatic organism adhesion preventing paint of the present invention is preferably a paint for underwater structures.

The aquatic organism adhesion-preventing paint of the present invention can form a coating film with a desired film thickness even on a structure having a complicated shape, and the formed coating film prevents aquatic organisms from adhering to a substrate for a long period of time. Can be suppressed. Examples of the method for forming the coating film include spin coating, bar coating, drop casting, dip nip, spray coating, brush coating, dipping, electrostatic coating, and inkjet printing. Of these, spin coating, bar coating, drop casting, and dipping are preferred from the standpoint of simplicity.

The aquatic organism adhesion preventing paint of the present invention preferably contains an organic solvent. As the organic solvent, methanol, ethanol, 2-propanol, 2-butanol, 1-butanol, 1-hexanol, acetone, tetrahydrofuran, methyl ethyl ketone, dimethylacetamide, dimethylformamide and the like can be used. Further, as long as the solvent has a fluorine atom in the molecule and the solubility of the fluorine-containing polymer is good, it may be any of a fluorocarbon compound, alcohol, ether, etc., and aliphatic and aromatic Either may be sufficient. For example, perfluoroaliphatic hydrocarbon, polyfluoroaromatic hydrocarbon, polyfluoroaliphatic hydrocarbon, hydrofluorocarbon (HFC), hydrochlorofluorocarbon (HCFC), hydrofluoroether (HFE), hydrofluoroolefin (HFO) and Alkyl perfluoroalkyl ethers can be used.

The perfluoroaliphatic hydrocarbon is not particularly limited, but preferably has 5 to 12 carbon atoms. Although it does not specifically limit, Perfluorohexane, perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane, perfluorodihydropropanol (pentafluoropropanol), etc. can be used as a specific example.

Although it does not specifically limit as polyfluoro aromatic hydrocarbon, For example, bis (trifluoromethyl) benzene, hexafluoro-m-xylene, etc. can be used.

The polyfluoro aliphatic hydrocarbon is not particularly limited, for _{example, C 6 F 13 CH 2 CH} 3 ( e.g., Asahi Glass ASAHIKLIN Co., Ltd. (TM) AC-6000), 1,1,2,2 , 3,3,4-heptafluorocyclopentane (for example, ZEOLOR (registered trademark) H manufactured by ZEON CORPORATION) can be used.

Although it does not specifically limit as hydrofluorocarbon (HFC), For example, 1,1,1,3,3-pentafluorobutane (HFC-365mfc) etc. can be used.

Hydrochlorofluorocarbon (HCFC) is not particularly limited, but preferably has 2 to 5 carbon atoms. Specific examples include, but are not limited to, HCFC-225 (dichloropentafluoropropane: Asahiklin (registered trademark) AK225), HCFC141b (dichlorofluoroethane), CFC316 (2,2,3,3-tetrachlorohexafluorobutane) ,) And C ₅ H ₂ F ₁₀ (for example, Vertrel (registered trademark) XF manufactured by DuPont) or the like can be used.

The hydrofluoroether (HFE), is not particularly limited, for example, perfluoropropyl methyl ether _{(C 3 F 7 OCH 3)} ( e.g., Sumitomo 3M Limited of Novec (TM) 7000) and _CF 3 CH ₂ OCF ₂ CHF ₂ (for example, Asahi Clin (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.) can be used.

The hydrofluoroolefin (HFO) is not particularly limited. For example, 1,2-dichloro-1,3,3,3-tetrafluoro-1-propene (for example, Vertrel (registered by Mitsui DuPont Fluorochemical) (registered) (Trademark) Scion) etc. can be used.

In the alkyl perfluoroalkyl ether, the perfluoroalkyl group and the alkyl group may be either linear or branched. Specific examples include, but are not limited to, perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) (for example, Novec (trade name) 7100 manufactured by Sumitomo 3M Limited), perfluorobutyl ethyl ether (C ₄ F _9). OC ₂ H ₅ ) (for example, Novec (trade name) 7200 manufactured by Sumitomo 3M Limited) and perfluorohexyl methyl ether (C ₂ F ₅ CF (OCH ₃ ) C ₃ F ₇ ) (for example, manufactured by Sumitomo 3M Limited) Novec (trade name) 7300) and the like.

As a solvent for dissolving the fluorine-containing polymer, only one kind of solvent may be used, or two or more kinds of solvents may be mixed and used. Of these, 2-butanol, 1-butanol, 1-hexanol, and tetrahydrofuran are preferable in that a transparent and uniform coating film can be easily obtained. From the viewpoint of solubility of the fluorine-containing polymer, methanol, ethanol, 2-propanol, tetrahydrofuran, and dimethylformamide are preferable.

The aquatic organism adhesion preventing coating of the present invention may further contain additives as necessary. Such additives are not particularly limited, for example, leveling agent, solid lubricant, pigment, brightening agent, filler, pigment dispersant, surface modifier, viscosity modifier, ultraviolet absorber, light stabilizer, Examples thereof include plasticizers, anti-coloring agents, anti-scratching agents, biological repellents, anticorrosive agents, antibacterial agents, anticorrosive agents, antistatic agents, anti-waxing agents, and matting agents. On the other hand, in order for the coating film obtained from the aquatic organism adhesion-preventing paint to exhibit the effect of preventing adhesion of aquatic organisms, it is preferable that a hydroxyl group is present in the coating film. Therefore, it is preferable that the aquatic organism adhesion preventing coating does not contain a compound that reacts with a hydroxyl group such as a curing agent to eliminate the hydroxyl group.

The aqueous bioadhesion-preventing coating material of the present invention can be produced by mixing and dispersing the above-mentioned aquatic organism adhesion-preventing material and, if necessary, the above-described components by a known method.

The film thickness of the coating film on which the aquatic organism adhesion preventing paint of the present invention is formed is preferably 0.1 to 2,000 μm. The film thickness of the coating film on which the aquatic organism adhesion preventing paint of the present invention is formed is more preferably 500 μm or less, further preferably 100 μm or less, still more preferably 50 μm or less, and further preferably 30 μm or less. Is particularly preferably 20 μm or less, more preferably 0.5 μm or more, still more preferably 1 μm or more, and even more preferably 5 μm or more.

This invention is also an aquatic organism adhesion prevention panel which consists of a base material and the coating film which consists of the above-mentioned aquatic organism adhesion prevention coating material formed on the said base material.
It is preferable that the aquatic organism adhesion prevention panel of this invention is a panel for underwater structures.

Examples of the base material include various plastics such as polyimide, polyamide, polycarbonate, polyethylene terephthalate, vinyl chloride and acrylic resin, and building materials such as metal and slate.

The aquatic organism adhesion prevention panel of the present invention is more preferably composed of a substrate and a coating film made of the aquatic organism adhesion prevention coating material of the present invention formed on the substrate.
The thickness of the coating film is preferably from 0.1 to 2,000 μm, more preferably from 1 to 500 μm, still more preferably from 5 to 100 μm. The said film thickness is a value obtained by measuring by the method of JISK 5600.

This invention is also an underwater structure provided with the coating film which consists of the above-mentioned aquatic organism adhesion prevention coating material.
The underwater structure of the present invention comprises a coating film made of the aqueous biofouling prevention paint of the present invention or the aquatic organism adhesion prevention panel of the present invention.

As an underwater structure, various things are mention | raise | lifted regardless of the use in seawater and freshwater. Further, it may be used on the water surface. For example, although the following articles | goods and structures can be illustrated, it is not limited to these. The structure includes not only fixed structures such as piers, piers, and waterways, but also structures such as mega floats and ships.

Fixed type:
Underwater structures such as bridges, concrete blocks, wave-dissipating blocks, breakwaters, pipelines;
Harbor facilities such as sluice gates, marine tanks and floating piers;
Submarine work facilities such as undersea drilling equipment and underwater communication cable facilities;
Thermal power, nuclear power, tidal power, ocean thermal power generation facilities such as waterway, cover pipe, water chamber, water intake, water outlet, etc .;
Water supply and drainage and storage facilities such as pools, water tanks, water towers, sewers, gutters;
Home equipment such as system kitchen, flush toilet, bathroom, bathtub;

Mobile type:
Ship structures or accessories such as the dredging or bottom of a ship, the submarine exterior, screws, propellers, dredging;
Articles used on the surface of water or in water;
Float materials such as seaplanes;
Fixed type:
Fishing nets such as stationary nets, buoys, ginger and ropes;
Thermal power supplies such as water covers and water chambers, nuclear power, offshore wind power, and ocean thermal power generation products;
Submarine (underwater) laying articles such as underwater (underwater) cables;
Mobile type:
Fishing goods such as bottom nets and longing;

The present invention also includes a method for preventing aquatic organisms from adhering to a substrate or an underwater structure, which includes the step of applying the above-described aquatic organism adhesion preventing paint to the substrate or the underwater structure. is there.

The method for applying the aquatic organism adhesion preventing coating is not particularly limited, and can be applied by a known method.

The present invention also provides a method for preventing attachment of aquatic organisms to an underwater structure, including the step of attaching the aquatic organism adhesion prevention panel of the present invention to the underwater structure.

The method for attaching the aquatic organism adhesion prevention panel of the present invention to the underwater structure of the present invention is not particularly limited, and the aquatic organism adhesion prevention panel of the present invention is obtained by applying an aquatic organism adhesion prevention coating to a substrate. You may attach to an underwater structure.
Examples of the method for attaching the aquatic organism adhesion preventing panel of the present invention to an underwater structure include a method using an adhesive and a method using an attachment such as an anchor bolt.

Examples of the method for forming the coating film include spin coating, bar coating, drop casting, dip nip, spray coating, brush coating, dipping, electrostatic coating, and inkjet printing. Of these, spin coating, bar coating, drop casting, and dipping are preferred from the standpoint of simplicity.

The coating film is preferably obtained by applying a coating composition containing the aquatic organism adhesion preventing material and an organic solvent. As the organic solvent, methanol, ethanol, 2-propanol, 2-butanol, 1-butanol, 1-hexanol, acetone, tetrahydrofuran, methyl ethyl ketone, dimethylacetamide, dimethylformamide and the like can be used. Of these, 2-butanol, 1-butanol, 1-hexanol, and tetrahydrofuran are preferable in that a transparent and uniform coating film can be easily obtained. From the viewpoint of solubility of the aquatic organism adhesion preventing material, methanol, ethanol, 2-propanol, tetrahydrofuran, and dimethylformamide are preferable.

The thickness of the coating film is preferably 0.1 to 2,000 μm. The film thickness of the coating film on which the aquatic organism adhesion preventing paint of the present invention is formed is more preferably 500 μm or less, further preferably 100 μm or less, still more preferably 50 μm or less, and further preferably 30 μm or less. Is particularly preferably 20 μm or less, more preferably 0.5 μm or more, still more preferably 1 μm or more, and even more preferably 5 μm or more.

Next, the present invention will be described with reference to examples, but the present invention is not limited to such examples.

Each numerical value of the examples was measured by the following method.

The molar ratio of the monomer was measured by elemental analysis.

The molecular weight was measured by gel permeation chromatography (GPC) measurement.

Production Example 1
Preparation of copolymer (1) of tetrafluoroethylene and N-vinyl-2-pyrrolidone After the inside of the pressure-resistant reaction vessel that had been subjected to airtightness inspection was sufficiently substituted with nitrogen, deoxygenated methyl isobutyl ketone (90.3 g) and N-vinyl-2-pyrrolidone (9.80 g) was added. Subsequently, tetrafluoroethylene was added under pressure, and while stirring with a stirrer, the internal temperature of the mixture was adjusted to 60 ° C., and azobisisobutyronitrile (0.197 g) was added to initiate the reaction. . One hour after the start of the reaction, the remaining tetrafluoroethylene was removed, and hydroquinone (0.132 g) was added. The reaction mixture was then purified and dried to obtain 3.3 g of the desired copolymer (1). The resulting copolymer (1) has a weight average molecular weight of 6.5 × 10 ⁴ , a molecular weight distribution of 2.0, 34 mol% of tetrafluoroethylene units and 66 mol% of N-vinyl-2-pyrrolidone units. It was a copolymer. The molar ratio of tetrafluoroethylene unit / N-vinyl-2-pyrrolidone unit was 0.52, and the fluorine content was 24% by mass.

Example 1
The copolymer (1) was made into a 1% by weight solution in a methanol solvent, and this was applied onto a polyester plate (40 × 40 × 1 mm) and dried at room temperature to prepare a test plate. In order to evaluate the adherence of Cypris larvae to the test plate (the larvae of the vertical barnacles adhering to the artificial structures in the inner bay sea area), the test plate, 150 ml of seawater, Cypris were placed in a polystyrene container (117 × 84 × 57 mm). 30-50 larvae were introduced and placed in a dark place at 20 ± 1 ° C. Twelve days after the introduction of Cypris larvae, the test plate was taken out of the polystyrene container, and the adhesion rate of Cypris larvae to the test plate was evaluated. The results are shown in Table 1.

Comparative Example 1
The same operation as in Example 1 was performed except that a polyester plate (40 × 40 × 1 mm) not coated with the copolymer (1) was used as a test plate, and the adhesion rate of Cypris larvae to the test plate was evaluated. The results are shown in Table 1.

Production Example 2
Preparation of copolymer (2) of tetrafluoroethylene and N-vinyl-2-pyrrolidone The inside of the pressure-resistant reaction vessel that had been subjected to airtightness inspection was sufficiently purged with nitrogen, then acetone (891.6 g) and N-vinyl-2- Pyrrolidone (60.5 g) was added. Subsequently, tetrafluoroethylene was added under pressure, the internal temperature of the mixture was adjusted to 60 ° C. with stirring, and t-butyl peroxypivalate (2.68 g) was added to initiate the reaction. N-vinyl-2-pyrrolidone (188.7 g) was charged at the start of polymerization. Five hours after the start of the reaction, the inside of the reaction vessel was returned to normal temperature and pressure to stop the polymerization, the remaining tetrafluoroethylene was removed, and 1273 g of an acetone solution of the copolymer (2) (solid content concentration 29.8% by mass). ) The reaction mixture was then purified and dried to obtain 379.4 g of the desired copolymer (2). The resulting copolymer (2) contains a weight average molecular weight of 4.5 × 10 ⁴ , a molecular weight distribution of 1.9, 38 mol% of tetrafluoroethylene units and 62 mol% of N-vinyl-2-pyrrolidone units. It was a copolymer. The molar ratio of tetrafluoroethylene unit / N-vinyl-2-pyrrolidone unit was 0.61, and the fluorine content was 27% by mass.

Production Example 3
Preparation of Copolymer (3) of Tetrafluoroethylene and N-Vinyl-2-pyrrolidone After the inside of the pressure-resistant reaction vessel which had been subjected to airtightness inspection was sufficiently substituted with nitrogen, acetone (891.6 g) and N-vinyl-2- Pyrrolidone (36.1 g) was added. Subsequently, tetrafluoroethylene was added under pressure, and the internal temperature of the mixture was adjusted to 60 ° C. while stirring, and then t-butyl peroxypivalate (3.28 g) was added to initiate the reaction. N-vinyl-2-pyrrolidone (100.2 g) was charged at the start of polymerization. Three hours after the start of the reaction, the inside of the reaction vessel was returned to room temperature and normal pressure to stop the polymerization, the remaining tetrafluoroethylene was removed, and 1095 g of an acetone solution of the copolymer (3) (solid content concentration 20.9% by mass) ) The reaction mixture was then purified and dried to obtain 229.2 g of the desired copolymer (3). The resulting copolymer (3) contains a weight average molecular weight of 4.6 × 10 ⁴ , a molecular weight distribution of 2.2, 48 mol% of tetrafluoroethylene units and 52 mol% of N-vinyl-2-pyrrolidone units. It was a copolymer. The molar ratio of tetrafluoroethylene unit / N-vinyl-2-pyrrolidone unit was 0.92, and the fluorine content was 34% by mass.

Example 2
Copolymer (2) was made into a 1% by weight solution in methyl isobutyl ketone solvent, which was applied to a glass slide for optical microscope (75 × 25 mm) and dried at room temperature. This glass slide was submerged in a water tank containing tap water and aquatic plants (Life Multi Anacharis) and installed in a sunny window. 25 days after installation, the slide glass was pulled up and the surface was observed. The results are shown in Table 2.

Example 3
Copolymer (3) was made into a 1% by weight solution in methyl isobutyl ketone solvent, which was applied to a glass slide for optical microscope (75 × 25 mm) and dried at room temperature. This glass slide was submerged in a water tank containing tap water and aquatic plants (Life Multi Anacharis) and installed in a sunny window. 25 days after installation, the slide glass was pulled up and the surface was observed. The results are shown in Table 2.

Comparative Example 2
A glass slide (75 × 25 mm) not coated with a copolymer was submerged in a water tank containing tap water and aquatic plants (Life Multi Anacharis), and placed on a sunny window. 25 days after installation, the slide glass was pulled up and the surface was observed. The results are shown in Table 2.

Claims (10)

An aquatic organism adhesion prevention material comprising a copolymer containing a fluorine-containing olefin unit and a polymerizable vinyl compound unit having an amide bond. The aquatic organism adhesion prevention material according to claim 1, wherein the content of the fluorine-containing olefin unit in the copolymer is 65 to 5 mol%, and the content of the polymerizable vinyl compound unit having an amide bond is 35 to 95 mol%. . The aquatic organism adhesion preventing material according to claim 1 or 2, wherein the fluorinated olefin is at least one selected from the group consisting of tetrafluoroethylene, chlorotrifluoroethylene and hexafluoropropylene. The aquatic organism adhesion prevention material according to claim 1, 2 or 3, wherein the polymerizable vinyl compound having an amide bond is N-vinyl-2-pyrrolidone. An aquatic organism adhesion preventing paint comprising the aquatic organism adhesion preventing material according to claim 1. Furthermore, the aquatic organism adhesion prevention coating material of Claim 5 containing an organic solvent. The aquatic organism adhesion prevention panel which consists of a base material and the coating film which consists of the aquatic organism adhesion prevention coating material of Claim 5 or 6 formed on the said base material. An underwater structure comprising a coating film made of the aquatic organism adhesion preventing paint according to claim 5. A method for preventing aquatic organisms from adhering to an underwater structure, comprising the step of applying the aquatic organism adhesion-preventing paint according to claim 5 or 6. A molded product obtained by molding the aquatic organism adhesion preventing material according to claim 1, which is a film, a sheet or a tube.