JPWO2016104602A1 - Aquatic organism adhesion prevention material, aquatic organism adhesion prevention coating, aquatic organism adhesion prevention panel, underwater structure and method 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. The present invention is an aquatic organism adhesion-preventing material comprising a fluorine-containing copolymer having a repeating unit of a fluorine-containing olefin and a repeating unit containing a hydroxyl group.

Description

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

In various underwater structures such as seawater intake facilities at power plants, a large number 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 paint that has an effect of preventing the adhesion and growth of aquatic organisms and does not contain a toxic antifouling agent, in Patent Document 1, it is made of a fluororesin so that it has a high aquatic organism adhesion preventing effect without polluting the water area. An aquatic organism adhesion preventing sheet or an aquatic organism adhesion preventing coating that can be used for a long time has been proposed.

Moreover, in patent document 2, it consists of a fluororesin, and since surface roughness Ra is 0.005-0.20 micrometer, it can exhibit a high aquatic organism adhesion prevention effect for a long period, without polluting a water area. Aquatic organism adhesion prevention molded products have been proposed.

In Patent Document 3, at least a part of the surface is composed of a hydrophobic fluorine resin, a fluorine-containing monomer, and a hydrophilic fluorine resin made of a copolymer of a hydrophilic monomer or a monomer that can be made hydrophilic after polymerization. A base material with controlled biocompatibility has been proposed.

Further, in Patent Document 4, an aquatic organism or physiological body that includes a hydrolyzable organometallic compound for hydrophilizing a surface and a binder resin, and forms a coating layer or film having a surface water contact angle of less than 70 degrees. A resin composition for preventing substance adhesion has been proposed.

JP 2012-214739 A JP 2014-88553 A Japanese Patent No. 2957023 International Publication No. 2001/060923

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-preventing material comprising a fluorine-containing copolymer having a repeating unit of a fluorine-containing olefin and a repeating unit containing a hydroxyl group.

The repeating unit containing a hydroxyl group is preferably a repeating unit of vinyl alcohol.

It is preferable that the content rate of the repeating unit of the fluorine-containing olefin in the said fluorine-containing copolymer is 60-10 mol%.

It is preferable that the alternating rate of the repeating unit of a fluorine-containing olefin and the repeating unit containing a hydroxyl group in the said fluorine-containing copolymer is 1 to 80%.

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

The fluorine-containing copolymer preferably has a repeating unit of a fluorine-containing olefin, a repeating unit containing a hydroxyl group, and a repeating unit of a vinyl ester monomer.

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

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.

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 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 does not easily adhere to aquatic organisms.

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 fluorine-containing copolymer having a repeating unit of a fluorine-containing olefin and a repeating unit containing a hydroxyl group. The low aquatic organism adhesion of the fluoropolymer is a characteristic newly found by the present inventors.

Examples of aquatic organisms include barnacles, sea squirts, cell plastics, mussels, crow mussels, chrysanthemum moths, aonori, aosa, sea anemones, oysters, hydroworms, various aquatic microorganisms, various marine algae (such as green squirrel, honda walla, aosa, aonori), cyanobacteria, Green algae (Aomidoro, Azalea, etc.), Euglena algae, yellow green algae, golden algae, diatoms, red algae, crypto algae, flame algae, moss (Brown moss, etc.), annelids (Uzumakigokai, Shiraitogokai, etc.), Sea surface animals (Yuzuda sponge etc.) etc. are mentioned. As aquatic organisms, barnacles, sea squirts, cell plastics, mussels, crow mussels, fusakos, beetles, blue-tailed seaweeds, seaweeds, sea anemones, oysters, hydroworms, various aquatic microorganisms, various seaweeds (such as green lily, hondawala, aosa, aonori), cyanobacteria , Green algae (Aomidoro, Azalea, etc.), Euglena algae, yellow green algae, golden algae, diatoms, red algae, crypto algae, flame algae, moss (tea moss etc.), annelids (Uzumakigokai, Shiraitogokai, etc.) ), Marine animals (Yuzuda sponge etc.), and blue sea bream. As aquatic organisms, barnacles and algae are more preferred. 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).

The fluorine-containing copolymer preferably contains the repeating unit of the fluorine-containing olefin in an amount of 60 to 10 mol% of the repeating units of all monomers constituting the fluorine-containing copolymer. More preferably, it is 60-20 mol%, More preferably, it is 60-30 mol%, More preferably, it is 60-40 mol%. When the content of the repeating unit of the fluorine-containing olefin is within the above range, aquatic organisms are more difficult to adhere to the aquatic organism adhesion preventing material.

The fluorine-containing copolymer preferably has a fluorine-containing olefin repeating unit of 60 to 10 mol% and a hydroxyl group-containing repeating unit of 40 to 90 mol%. As a content rate of each unit, it is more preferable that the repeating unit of a fluorine-containing olefin is 60-20 mol%, the repeating unit containing a hydroxyl group is 40-80 mol%, and the repeating unit of a fluorine-containing olefin is 60. It is more preferable that the repeating unit containing a hydroxyl group is 40 to 70 mol%, the repeating unit of the fluorinated olefin is 60 to 40 mol%, and the repeating unit containing a hydroxyl group is 40 to 40 mol%. Even more preferably, it is 60 mol%. When the content of each unit is within such a range, aquatic organisms are less likely to adhere to the aquatic organism adhesion preventing material.

The said repeating unit of a fluorine-containing olefin represents the polymerization unit based on a fluorine-containing olefin. The fluorine-containing olefin is a monomer having a fluorine atom.

Examples of the fluorine-containing olefin include tetrafluoroethylene [TFE], vinylidene fluoride [VdF], chlorotrifluoroethylene [CTFE], vinyl fluoride, hexafluoropropylene [HFP], hexafluoroisobutene, CH ₂ = CZ. ¹ (CF ₂ ) _n1 Z ² (wherein Z ¹ is H, F or Cl, Z ² is H, F or Cl, and n1 is an integer of 1 to 10), CF ₂ = CF-ORf ¹ (wherein Rf ¹ represents a perfluoroalkyl group having 1 to 8 carbon atoms) and CF ₂ = CF-OCH ₂ -rf ² (wherein, Rf ² is a perfluoroalkyl group having 1 to 5 carbon atoms) selected from the group consisting of alkyl perfluorovinyl ether derivative represented by the It is preferably be at least one kind of fluorine-containing olefin.

Examples of the monomer represented by CH ₂ = CZ ¹ (CF ₂ ) _n1 Z ² include CH ₂ = CFCF ₃ , CH ₂ = CHCF ₃ , CH ₂ = CFCHF ₂ and CH ₂ = CClCF ₃ .

Examples of the PAVE include perfluoro (methyl vinyl ether) [PMVE], perfluoro (ethyl vinyl ether) [PEVE], perfluoro (propyl vinyl ether) [PPVE], perfluoro (butyl vinyl ether), and the like.

As said fluorine-containing olefin, at least 1 sort (s) selected from the group which consists of TFE, CTFE, and HFP is more preferable, and TFE is still more preferable.

Examples of the repeating unit containing a hydroxyl group include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2- Hydroxyl-containing vinyl ethers such as methylbutyl vinyl ether, 5-hydroxypentyl vinyl ether and 6-hydroxyhexyl vinyl ether, hydroxyl-containing allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether and glycerol monoallyl ether, vinyl alcohol And the like. Of these, hydroxyl group-containing vinyl ethers and vinyl alcohol repeating units are preferred, 4-hydroxybutyl vinyl ether, 2-hydroxyethyl vinyl ether and vinyl alcohol repeating units are more preferred, and vinyl alcohol repeating units are more preferred.

Examples of the repeating unit containing another hydroxyl group include units such as hydroxyalkyl esters of (meth) acrylic acid such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.

The fluorine-containing copolymer preferably has an alternating rate of 1 to 80% between the repeating unit of the fluorine-containing olefin and the repeating unit containing a hydroxyl group. When the alternating rate is within the above range, aquatic organisms are less likely to adhere to the aquatic organism adhesion preventing material. More preferably, it is 20-80%, More preferably, it is 50-80%.

The alternating rate of the repeating unit of the fluorine-containing olefin and the repeating unit containing a hydroxyl group is determined by performing ¹ H-NMR measurement of the fluorine-containing copolymer using a solvent in which the fluorine-containing copolymer such as heavy acetone is dissolved. It can be calculated as an alternating rate of three chains from the following formula.
Alternating rate (%) = C / (A + B + C) × 100
A: The number of V combined with two Vs such as -VVVV- B: The number of V combined with V and T as -VVT- C: -TV- Number of V bonded to two T as in T- (T: repeating unit of fluorine-containing olefin, V: repeating unit containing a hydroxyl group)
The number of V units of A, B, and C is calculated from the intensity ratio of H of the main chain bonded to the tertiary carbon of the repeating unit containing a hydroxyl group in ¹ H-NMR measurement. For example, regarding a copolymer comprising a fluorinated olefin and vinyl alcohol, the estimation of the strength ratio of H in the main chain by ¹ H-NMR measurement is based on the fluorinated olefin and vinyl ester that are the fluorinated copolymer before saponification. It carried out with the copolymer of the monomer.

Since the aforesaid fluorine-containing copolymer is more difficult for aquatic organisms to adhere, —CH (OH) —CXY— (wherein X and Y are the same or different and each represents H, F or a fluoroalkyl group. However, it is preferable that at least one of X and Y is F or a fluoroalkyl group. The fluorine-containing copolymer more preferably has a fluorine alcohol structure represented by —CH (OH) —CF ₂ —.

The fluorine-containing copolymer is further represented by —CH ₂ —CH (O (C═O) R) — (wherein R represents a hydrogen atom or a hydrocarbon group having 1 to 17 carbon atoms). It may have a repeating unit of vinyl ester monomer. Thus, one of the preferred embodiments of the present invention is that the fluorine-containing copolymer in the present invention has a repeating unit of a fluorine-containing olefin, a repeating unit containing a hydroxyl group, and a repeating unit of a vinyl ester monomer. It is. Furthermore, it is also a preferred embodiment of the present invention that the copolymer is substantially composed of a repeating unit of a fluorine-containing olefin, a repeating unit containing a hydroxyl group, and a repeating unit of a vinyl ester monomer. is there.

The repeating unit of the vinyl ester monomer is represented by —CH ₂ —CH (O (C═O) R) — (wherein R represents a hydrogen atom or a hydrocarbon group having 1 to 17 carbon atoms). In the above formula, R is preferably an alkyl group having 1 to 11 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms. Particularly preferred is an alkyl group having 1 to 3 carbon atoms.

Examples of the vinyl ester monomer repeating unit include the following vinyl ester repeating units.
Vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valelate, vinyl isovalerate, vinyl caproate, vinyl heptylate, vinyl caprylate, vinyl pivalate, vinyl pelargonate, vinyl caprate, Vinyl laurate, vinyl myristate, vinyl pentadecylate, vinyl palmitate, vinyl margarate, vinyl stearate, vinyl octylate, Veova-9 (manufactured by Showa Shell Sekiyu KK), Veova-10 (Showa Shell Sekiyu KK) )), Vinyl benzoate, vinyl versatate.
Among these, a repeating unit of a monomer derived from vinyl acetate, vinyl propionate, or vinyl versatate is preferable. More preferred are a vinyl acetate monomer repeating unit and a propionic acid vinyl monomer repeating unit, and even more preferred is a vinyl acetate monomer repeating unit.

When the fluorine-containing copolymer has a repeating unit of a fluorine-containing olefin, a repeating unit containing a hydroxyl group, and a repeating unit of a vinyl ester monomer, the content of each unit is as follows. It is preferably 10 mol%, the repeating unit containing a hydroxyl group is more than 0 mol% and less than 70 mol%, and the repeating unit of the vinyl ester monomer is preferably more than 0 mol% and less than 70 mol%. When the content of each unit is within the above range, aquatic organisms are less likely to adhere to the aquatic organism adhesion preventing material. As the content of each unit, the repeating unit of fluorine-containing olefin is 60 to 10 mol%, the repeating unit containing a hydroxyl group is 40 to 90 mol%, and the repeating unit of vinyl ester monomer is 0 to 20 mol%. More preferably, the fluorine-containing olefin repeating unit is 60 to 20 mol%, the hydroxyl group-containing repeating unit is 40 to 80 mol%, and the vinyl ester monomer repeating unit is 0 to 10 mol%. More preferably, the fluorine-containing olefin repeating unit is 60 to 30 mol%, the hydroxyl group-containing repeating unit is 40 to 70 mol%, and the vinyl ester monomer repeating unit is 0 to 10 mol%. It is even more preferable that the fluorine-containing olefin has a repeating unit of 60 to 40 mol% and contains a hydroxyl group. Repeating units is 40 to 60 mol%, and particularly preferably repeating units of the vinyl ester monomer is 0 to 10 mol%.

When the fluorine-containing copolymer has a repeating unit of a fluorine-containing olefin, a repeating unit containing a hydroxyl group, and a repeating unit of a vinyl ester monomer, the repeating unit of the fluorine-containing olefin and the repeating unit containing a hydroxyl group and a vinyl ester monomer The alternating ratio with the repeating unit is preferably 1 to 80%. When the alternating rate is within the above range, aquatic organisms are less likely to adhere to the aquatic organism adhesion preventing material. More preferably, it is 20-80%, More preferably, it is 50-80%.

Alternating indices of the repeating units of the repeating units and vinyl ester monomers containing repeating units and a hydroxyl group of the fluorine-containing olefins, by using a solvent fluorocopolymer such as deuterated acetone dissolves, ¹ of fluorocopolymer An H-NMR measurement is performed, and the alternating rate of three chains can be calculated from the following formula.
Alternating rate (%) = C / (A + B + C) × 100
A: The number of V combined with two Vs such as -VVVV- B: The number of V combined with V and T as -VVT- C: -TV- Number of V bonded to two T as in T- (T: repeating unit of fluorine-containing olefin, V: repeating unit containing hydroxyl group or repeating unit of vinyl ester monomer)
The number of V units of A, B, and C is 3 of repeating units containing a hydroxyl group and vinyl ester monomer repeating units (—CH ₂ —CH (O (C═O) R) —) measured by ¹ H-NMR. It is calculated from the intensity ratio of H of the main chain bonded to the secondary carbon. For example, regarding the copolymer of fluorine-containing olefin, vinyl alcohol and vinyl ester monomer, the estimation of the strength ratio of H of the main chain by ¹ H-NMR measurement is the fluorine-containing olefin which is the fluorine-containing copolymer before saponification. And a vinyl ester monomer copolymer.

The fluorine-containing copolymer has a repeating unit of a fluorine-containing olefin, a repeating unit containing a hydroxyl group, and a repeating unit of another monomer other than the vinyl ester monomer within a range not impairing the effects of the present invention. Also good.

As said other monomer, as a monomer which does not contain a fluorine atom (however, except vinyl alcohol and a vinyl ester monomer), for example, ethylene, propylene, 1-butene, 2-butene, vinyl chloride, vinylidene chloride , At least one fluorine-free ethylenic monomer selected from the group consisting of vinyl ether monomers and unsaturated carboxylic acids is preferred.

The total content of the repeating units of the other monomers is preferably 0 to 50 mol%, more preferably 0 to 40 mol% of the repeating units of all the monomers of the fluorine-containing copolymer. Preferably, it is 0-30 mol%, and it is still more preferable.

In the present specification, the content of the repeating unit of each monomer constituting the fluorine-containing copolymer can be calculated by appropriately combining NMR, FT-IR, and elemental analysis depending on the type of monomer.

The weight average molecular weight of the fluorine-containing copolymer is not particularly limited, but is preferably 10,000 or more. More preferably, it is 12,000-2,000,000, More preferably, it is 12,000-1,000,000.
The weight average molecular weight can be determined by gel permeation chromatography (GPC).

As described later, the fluorine-containing copolymer can be produced by saponifying a copolymer having a repeating unit of a fluorine-containing olefin and a repeating unit of a vinyl ester monomer. This production method is particularly suitable when the repeating unit containing a hydroxyl group is a repeating unit of vinyl alcohol. That is, the fluorine-containing copolymer in the present invention is also a copolymer obtained by saponifying a copolymer having a repeating unit of a fluorine-containing olefin and a repeating unit of a vinyl ester monomer. It is one of the embodiments.

Below, an example of the manufacturing method of the fluorine-containing copolymer in this invention is shown.
The fluorine-containing copolymer in the present invention is produced, for example, by copolymerizing a fluorine-containing olefin such as tetrafluoroethylene and a vinyl ester monomer such as vinyl acetate, and then saponifying the obtained copolymer. can do. As a method for polymerizing the fluorine-containing copolymer, it is preferable to carry out the polymerization under a condition in which the composition ratio of the fluorine-containing olefin and the vinyl ester monomer is kept substantially constant. That is, the fluorine-containing copolymer is polymerized under a condition in which the composition ratio of the fluorine-containing olefin and the vinyl ester monomer is kept substantially constant, so that the copolymer having a fluorine-containing olefin repeating unit and a vinyl ester monomer repeating unit is obtained. Obtained by a production method comprising a step of obtaining a polymer, and a step of saponifying the obtained copolymer to obtain a copolymer having a repeating unit of a fluorine-containing olefin and a repeating unit containing a hydroxyl group It is preferable that

Examples of the vinyl ester monomers include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl isovalerate, vinyl caproate, vinyl heptylate, vinyl caprylate, vinyl pivalate, pelargon. Vinyl acetate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl pentadecylate, vinyl palmitate, vinyl margarate, vinyl stearate, vinyl octylate, Veova-9 (manufactured by Showa Shell Sekiyu KK), Veova 10 (manufactured by Showa Shell Sekiyu KK), vinyl benzoate, vinyl versatate, and the like. Of these, vinyl acetate, vinyl propionate, and vinyl versatate are preferably used because they are easily available and inexpensive.
As said vinyl ester monomer, 1 type of these may be used and 2 or more types may be mixed and used.

Examples of the method of copolymerizing the fluorinated olefin and the vinyl ester monomer include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization and the like, and emulsion polymerization is easy because it is industrially easy to implement. However, it is preferable to produce by solution polymerization or suspension polymerization, but not limited thereto.

In emulsion polymerization, solution polymerization, or suspension polymerization, a polymerization initiator, a solvent, a chain transfer agent, a surfactant, a dispersant, and the like can be used, and those usually used can be used.

The solvent used in the solution polymerization is preferably a solvent capable of dissolving the fluorine-containing olefin, the vinyl ester monomer, and the fluorine-containing copolymer to be synthesized. For example, n-butyl acetate, t-butyl acetate, ethyl acetate Esters such as methyl acetate and propyl acetate; Ketones such as acetone, methyl ethyl ketone and cyclohexanone; Aliphatic hydrocarbons such as hexane, cyclohexane and octane; Aromatic hydrocarbons such as benzene, toluene and xylene; Methanol and ethanol , Tert-butanol, alcohols such as 2-propanol; cyclic ethers such as tetrahydrofuran and dioxane; fluorine-containing solvents such as HCFC-225; dimethyl sulfoxide, dimethylformamide, or a mixture thereof. 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 Examples thereof include alkyl perfluoroalkyl ethers.
The perfluoroaliphatic hydrocarbon is not particularly limited, but preferably has 5 to 12 carbon atoms. Although not particularly limited, specific examples include perfluorohexane, perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane, perfluorodihydropropanol (pentafluoropropanol), and the like.
The polyfluoroaromatic hydrocarbon is not particularly limited, and examples thereof include bis (trifluoromethyl) benzene and hexafluoro-m-xylene.
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 Nippon Zeon Co., Ltd.).
Although it does not specifically limit as hydrofluorocarbon (HFC), For example, 1,1,1,3,3-pentafluorobutane (HFC-365mfc) etc. are mentioned.
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).
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.) and the like can be mentioned.
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) and the like.
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.
Examples of the solvent used in the emulsion polymerization include water, a mixed solvent of water and alcohol, and the like.
As the solvent, only one kind of solvent may be used, or two or more kinds of solvents may be mixed and used.

Examples of the polymerization initiator include peroxycarbonates such as diisopropyl peroxydicarbonate (IPP) and di-n-propyl peroxydicarbonate (NPP), and t-butyl peroxypivalate (for example, NOF Corporation). Oil-soluble radical polymerization initiators typified by peroxyesters such as perbutyl PV), for example, persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, ammonium percarbonate, potassium salt, sodium Water-soluble radical polymerization initiators such as salts can be used. Particularly in emulsion polymerization, ammonium persulfate and potassium persulfate are preferred.

As the surfactant, a commonly used surfactant can be used. For example, a nonionic surfactant, an anionic surfactant, a cationic surfactant and the like can be used. Moreover, you may use a fluorine-containing surfactant.

Examples of the dispersant used in suspension polymerization include partially saponified polyvinyl acetate, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, and other water-soluble cellulose ethers used in ordinary suspension polymerization, and acrylic acid polymers. And water-soluble polymers such as gelatin. The suspension polymerization is carried out under the condition that the water / monomer ratio is usually 1.5 / 1 to 3/1 by weight, and the dispersant is 0.01 to 0 with respect to 100 parts by weight of the monomer. 1 part by weight is used. If necessary, a pH buffer such as polyphosphate can be used.

Examples of the chain transfer agent include hydrocarbons such as ethane, isopentane, n-hexane, and cyclohexane; aromatics such as toluene and xylene; ketones such as acetone; and acetates such as ethyl acetate and butyl acetate; Examples include alcohols such as methanol and ethanol; mercaptans such as methyl mercaptan; halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride, and methyl chloride.
The amount of the chain transfer agent added may vary depending on the size of the chain transfer constant of the compound used, but is usually used in the range of 0.001 to 10% by mass relative to the polymerization solvent.

The polymerization temperature may be in a range where the composition ratio during the reaction of the fluorinated olefin and the vinyl ester monomer is substantially constant, and may be 0 to 100 ° C.

The polymerization pressure may be in a range in which the composition ratio during the reaction of the fluorinated olefin and the vinyl ester monomer is substantially constant, and may be 0 to 10 MPaG.

Saponification of an acetate group derived from vinyl acetate is well known in the art, and can be performed by a conventionally known method such as alcoholysis or hydrolysis. By this saponification, the acetate group (—OCOCH ₃ ) is converted into a hydroxyl group (—OH). Similarly, other vinyl ester monomers can be saponified by a conventionally known method to obtain a hydroxyl group.

The degree of saponification in the case of obtaining a fluorine-containing copolymer in the present invention by saponifying a copolymer having a fluorine-containing olefin repeating unit and a vinyl ester monomer repeating unit is as follows. What is necessary is just the range which the content rate of the repeating unit of a monomer becomes the range mentioned above, Specifically, 50% or more is preferable, 60% or more is more preferable, 70% or more is further more preferable, 80-100% is Even more preferred.

The saponification degree is calculated from the following equation by IR measurement or ¹ H-NMR measurement of the fluorine-containing copolymer.
Saponification degree (%) = D / (D + E) × 100
D: Number of repeating units containing a hydroxyl group in the fluorine-containing copolymer E: Number of repeating units of the vinyl ester monomer in the fluorine-containing copolymer

The said aquatic organism adhesion prevention material may further contain other components other than the said fluorine-containing copolymer in the range which does not impair the effect of this invention. However, the aquatic organism adhesion preventing material is characterized in that it comprises a fluorine-containing copolymer having a repeating unit containing a hydroxyl group, and the hydroxyl group also contributes to the effect of preventing the adhesion of aquatic organisms. Therefore, it is preferable that the aquatic organism adhesion preventing material does not contain a compound that reacts with a hydroxyl group such as a curing agent to eliminate the hydroxyl group.

Examples of the other components include hydrophilic polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, and polyethylene glycol.

The blending amount of the other component is preferably 1 to 30% by mass and more preferably 1 to 10% by mass with respect to 100% by mass of the fluorine-containing copolymer.

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 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 copolymer, 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 fluorinated copolymer, 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.

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 base material and a coating film made of the aquatic organism adhesion prevention paint of the present invention formed on the base material.
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 film thickness is a value obtained by measurement according to the method of JIS K 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.

[Measurement of content of repeating unit of fluorine-containing olefin by fluorine content]
A 10 mg sample was burned by the oxygen flask combustion method, the decomposition gas was absorbed in 20 ml of deionized water, and the fluorine ion concentration in the absorbing solution was measured by the fluorine selective electrode method (mass%). The content (mol%) of the repeating unit of the fluorine-containing olefin in the polymer was calculated from the fluorine content of the polymer before saponification.

[Measurement of alternating rate by NMR (nuclear magnetic resonance)]
¹ H-NMR measurement conditions: 400 MHz (tetramethylsilane = 0 ppm)

(Weight average molecular weight)
The weight average molecular weight was calculated from data measured by gel permeation chromatography (GPC) with tetrahydrofuran (THF) flowing at a flow rate of 1 ml / min as a solvent.
RI was used for the detector, and a polystyrene standard sample was used for the calibration curve sample, and the measurement was performed at a flow rate of 1 ml / min and a sample injection amount of 200 μL.

In the examples, the polymers used are as follows.

Polymer 1: Tetrafluoroethylene (TFE) / vinyl alcohol (VOH) copolymer (TFE / VOH = 54/46 (mol%), weight average molecular weight: 21,000, alternating rate: 74%)
Polymer 2: Tetrafluoroethylene (TFE) / vinyl alcohol (VOH) / vinyl acetate copolymer (TFE / VOH / vinyl acetate = 54/45/1 (mol%), weight average molecular weight: 17,500, alternating rate : 73%)

Example 1
Polymer 1 was made into a 1% by weight solution in a methanol solvent, and this was applied onto the inner wall surface of a glass water tank (size: 103 × 103 × 111 mm), dried at room temperature, and a water tank treated to prevent aquatic organism adhesion was produced. . In this water tank, 500 ml of tap water, two medaka fish, laying sand, and a bundle of aquatic plants (Life Multi Anacharis) were placed and installed in a sunny window. The state of the aquarium 19 days after installation was evaluated. The results are shown in Table 1.

Comparative Example 1
The state of the water tank 19 days after installation was evaluated in the same manner as in Example 1 except that a glass water tank not subjected to the biological adhesion prevention treatment was used. The results are shown in Table 1.

Example 2
Polymer 1 is made into a 1% by weight solution in methanol solvent, and this is applied to a part (30 x 30 mm) of the outer peripheral wall surface of a pot for potting plants, dried at room temperature, and a part of the outer peripheral wall is prevented from attaching aquatic organisms. A treated clay pot was prepared. This clay pot was submerged in a water tank containing tap water, medaka, laid sand, and aquatic plants (Life Multi Anacharis), and placed on a sunny window. The state of the outer peripheral wall of the clay pot 6 months after installation was evaluated. The results are shown in Table 2.

Comparative Example 2
About the outer peripheral wall surface which is not apply | coating the polymer 1 in the unglazed pot for planting of Example 2, it carried out similarly to Example 2, and evaluated the state of the outer peripheral wall of the unglazed pot 6 months after installation. The results are shown in Table 2.

Example 3
The polymer 2 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 3.

Comparative Example 3
The adhesion rate of Cypris larvae to the test plate was evaluated in the same manner as in Example 3 except that a polyester plate (40 × 40 × 1 mm) not coated with the polymer 2 was used as the test plate. The results are shown in Table 3.

Claims (11)

An aquatic organism adhesion prevention material comprising a fluorine-containing copolymer having a repeating unit of a fluorine-containing olefin and a repeating unit containing a hydroxyl group. The aquatic organism adhesion preventing material according to claim 1, wherein the repeating unit containing a hydroxyl group is a repeating unit of vinyl alcohol. The aquatic organism adhesion prevention material of Claim 1 or 2 whose content rate of the repeating unit of the fluorine-containing olefin in the said fluorine-containing copolymer is 60-10 mol%. The aquatic organism adhesion prevention material according to claim 1, 2 or 3, wherein an alternating rate of the repeating unit of the fluorine-containing olefin and the repeating unit containing a hydroxyl group in the fluorine-containing copolymer is 1 to 80%. The aquatic organism adhesion preventing material according to claim 1, wherein the fluorine-containing 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, wherein the fluorine-containing copolymer has a repeating unit of a fluorine-containing olefin, a repeating unit containing a hydroxyl group, and a repeating unit of a vinyl ester monomer. An aquatic organism adhesion-preventing coating material comprising the aquatic organism adhesion-preventing material according to claim 1, 2, 3, 4, 5 or 6. 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 7 formed on the said base material. An underwater structure comprising a coating film made of the aquatic organism adhesion preventing paint according to claim 7. A method for preventing aquatic organisms from adhering to an underwater structure, comprising a step of applying the aquatic organism adhesion preventing paint according to claim 7. A molded article formed by molding the aquatic organism adhesion prevention material according to claim 1, 2, 3, 4, 5, or 6.
Molded articles that are films, sheets or tubes.