JP2012214739A - Sheet for preventing adhesion of aquatic organism and coating material for preventing adhesion of aquatic organism - Google Patents
Sheet for preventing adhesion of aquatic organism and coating material for preventing adhesion of aquatic organism Download PDFInfo
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- C08J5/18—Manufacture of films or sheets
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- 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
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- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/18—Homopolymers or copolymers of tetrafluoroethene
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- 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
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- B63B59/04—Preventing hull fouling
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- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
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- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
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Abstract
Description
本発明は、水中構造物に取り付けることにより水中構造物に水生生物が付着することを防ぐための水生生物付着防止シート、および、水中構造物に塗装することにより水中構造物に水生生物が付着することを防ぐことができる水生生物付着防止塗料に関する。 The present invention relates to an aquatic organism adhesion prevention sheet for preventing aquatic organisms from attaching to an underwater structure by being attached to the underwater structure, and aquatic organisms to adhere to the underwater structure by coating the underwater structure. It is related with the aquatic organism adhesion prevention coating material which can prevent this.
各種の水中構造物、例えば発電所における海水取水施設などにおいては、その表面にフジツボ、ホヤ、セルプラ、ムラサキイガイ、カラスガイ、フサコケムシ、アオノリ、アオサなどの水生生物（海生生物）が多量に付着、生育し、それに起因する機能低下や機能障害を引き起こす懸念がある。従来においては付着した水生生物を定期的に掻き落とすなどの機械的な除去方法も一般的であったが、近年は各種の防汚塗料が開発され、これを水中構造物の表面に適用することで水生生物の付着を防止することが主に実施されている。 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.
防汚塗料としては、有機錫化合物、亜酸化銅、亜鉛ピリチオン、銅ピリチオンなどの毒性防汚剤を含むものがある。例えば、特許文献１では、澱粉又は澱粉分解物における水酸基を１種又は２種以上の脂肪酸アシル基で置換した澱粉脂肪酸エステルからなるバインダーと忌避剤とを含有し、形成塗膜が、塗膜形成要素の水中可溶化により上記忌避剤を徐放する防汚塗料組成物、及び、この防汚塗料組成物の塗膜が形成されてなる防汚パネルが提案されている。 Antifouling paints include those containing toxic antifouling agents such as organotin compounds, cuprous oxide, zinc pyrithione and copper pyrithione. For example, Patent Document 1 contains a binder composed of a starch fatty acid ester in which a hydroxyl group in starch or a starch degradation product is substituted with one or more fatty acid acyl groups and a repellent, and the formed coating film is formed into a coating film. An antifouling paint composition that gradually releases the repellent by solubilizing an element in water and an antifouling panel formed with a coating film of the antifouling paint composition have been proposed.
しかし、水生生物の付着、生育は防止できるものの、毒性防汚剤を用いているために、塗料の製造や塗装時において環境安全衛生上好ましくなく、しかも水中において塗膜から毒性の防汚剤が徐々に溶出し、長期的には水域を汚染するおそれがある。 However, although the adhesion and growth of aquatic organisms can be prevented, a toxic antifouling agent is used. Elutes gradually and may contaminate waters in the long term.
一方、水生生物の付着、生育の防止効果があり、毒性防汚剤を含まない塗料として、特許文献２では室温硬化性シリコーン樹脂及びシリコーンオイルを含有する水中生物付着防止塗料組成物が提案されている。 On the other hand, Patent Document 2 proposes an underwater organism adhesion prevention coating composition containing room temperature curable silicone resin and silicone oil as a coating material that has an effect of preventing adhesion and growth of aquatic organisms and does not contain a toxic antifouling agent. Yes.
また、特許文献３では、表面親水化用の加水分解性有機金属化合物と結合剤用の樹脂とを含み、表面の対水接触角が７０度未満のコーティング層またはフィルムを形成する水生生物または生理物質付着防止用樹脂組成物が提案されている。 Further, in Patent Document 3, an aquatic organism or physiological body that includes a hydrolyzable organometallic compound for surface hydrophilization 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.
しかしながら、これらの塗料では、充分な水生生物付着防止効果は得られていない。 However, these paints do not provide a sufficient aquatic organism adhesion preventing effect.
本発明の目的は、水域を汚染することなく、高い水生生物付着防止効果を長期間発揮することのできる水生生物付着防止シート、ならびに、水生生物付着防止シートが取り付けられた水性生物付着防止パネルおよび水中構造物を提供することである。 An object of the present invention is to provide an aquatic organism adhesion prevention sheet that can exhibit a high aquatic organism adhesion prevention effect for a long period of time without polluting the water area, and an aqueous organism adhesion prevention panel to which the aquatic organism adhesion prevention sheet is attached, and To provide an underwater structure.
本発明の目的は、また、水域を汚染することなく、高い水生生物付着防止効果を長期間発揮することのできる水生生物付着防止塗料、ならびに、水生生物付着防止塗料が適用された水性生物付着防止パネルおよび水中構造物を提供することである。 Another object of the present invention is to provide an aquatic organism adhesion-preventing paint capable of exhibiting a high aquatic organism adhesion-preventing effect for a long period of time without polluting the water area, and an aqueous organism adhesion prevention to which the aquatic organism adhesion-preventing paint is applied. Is to provide panels and underwater structures.
本発明らは鋭意検討した結果、フッ素樹脂からなるシート及び塗膜の表面に水生生物がほとんど付着しないことを見出し、本発明を完成するに至った。 As a result of intensive studies, the present inventors have found that aquatic organisms hardly adhere to the surface of a sheet made of a fluororesin and a coating film, and have completed the present invention.
すなわち、本発明は、フッ素樹脂からなることを特徴とする水生生物付着防止シートである。本発明は、フッ素樹脂を含むことを特徴とする水生生物付着防止塗料でもある。 That is, this invention is an aquatic organism adhesion prevention sheet | seat characterized by consisting of a fluororesin. This invention is also an aquatic organism adhesion prevention coating material characterized by including a fluororesin.
本発明の水生生物付着防止シートは、毒性防汚剤を含有しなくても高い水生生物付着防止効果を奏し、フッ素樹脂自身も化学的に極めて安定であるため、水域を汚染することなく、高い水生生物付着防止効果を長期間発揮することができる。 The aquatic organism adhesion prevention sheet of the present invention has a high aquatic organism adhesion prevention effect even without containing a toxic antifouling agent, and the fluororesin itself is also extremely chemically stable, so it is high without polluting the water area. The aquatic organism adhesion prevention effect can be demonstrated for a long time.
本発明の水生生物付着防止塗料を適用した基材は、毒性防汚剤を含有しなくても高い水生生物付着防止効果を奏し、フッ素樹脂自身も化学的に極めて安定であるため、水域を汚染することなく、高い水生生物付着防止効果を長期間発揮することができる。 The substrate to which the aquatic organism adhesion preventing paint of the present invention is applied exhibits a high aquatic organism adhesion preventing effect even if it does not contain a toxic antifouling agent, and the fluororesin itself is also chemically very stable, so it contaminates the water area. Therefore, a high aquatic organism adhesion preventing effect can be exhibited for a long period of time.
本発明は、フッ素樹脂からなることを特徴とする水生生物付着防止シートである。 This invention is an aquatic organism adhesion prevention sheet | seat characterized by consisting of a fluororesin.
水生生物としては、フジツボ類、ムラサキイガイ、イソギンチャク類、カキ、ホヤ、ヒドロ虫、コケムシ、各種水生微生物、各種海藻類（ミドリゲ、ホンダワラ、アオサ、アオノリなど）、各種珪藻類、環形動物（ウズマキゴカイ、シライトゴカイなど）、海綿動物（ユズダマカイメンなど）等が挙げられる。 As aquatic organisms, barnacles, mussels, sea anemones, oysters, squirts, hydroworms, bryozoans, various aquatic microorganisms, various seaweeds (such as midge, hondawala, aosa, aonori), various diatoms, annelids, , And sponges (such as Yuzuda sponge).
上記フッ素樹脂は、明確な融点を有するものであればとくに限定されないが、溶剤に不溶な樹脂であることが好ましい。 The fluororesin is not particularly limited as long as it has a clear melting point, but is preferably a resin insoluble in a solvent.
上記フッ素樹脂は、融点が１００〜３４７℃であることが好ましく、１５０℃〜３２２℃であることがより好ましい。
上記融点は、昇温速度１０℃／分で示差走査熱量計を用いて測定を行うことにより得られた熱融解曲線の極大値に対応する温度として測定したものである。
The fluororesin preferably has a melting point of 100 to 347 ° C, and more preferably 150 to 322 ° C.
The melting point is measured as a temperature corresponding to the maximum value of a thermal melting curve obtained by performing measurement using a differential scanning calorimeter at a heating rate of 10 ° C./min.
上記フッ素樹脂は、少なくとも１種の含フッ素エチレン性単量体から誘導される繰り返し単位を有する単独重合体又は共重合体であることが好ましい。上記フッ素樹脂は、含フッ素エチレン性単量体のみを重合してなるものであってもよいし、含フッ素エチレン性単量体とフッ素原子を有さないエチレン性単量体を重合してなるものであってもよい。 The fluororesin is preferably a homopolymer or copolymer having a repeating unit derived from at least one fluorine-containing ethylenic monomer. The fluororesin may be obtained by polymerizing only a fluorine-containing ethylenic monomer, or by polymerizing a fluorine-containing ethylenic monomer and an ethylenic monomer having no fluorine atom. It may be a thing.
上記フッ素樹脂は、フッ化ビニル〔ＶＦ〕、テトラフルオロエチレン〔ＴＦＥ〕、フッ化ビニリデン〔ＶｄＦ〕、クロロトリフルオロエチレン〔ＣＴＦＥ〕、へキサフルオロプロピレン〔ＨＦＰ〕、へキサフルオロイソブテン、ＣＨ２＝ＣＺ１（ＣＦ２）ｎＺ２（式中、Ｚ１はＨ又はＦ、Ｚ２はＨ、Ｆ又はＣｌ、ｎは１〜１０の整数である。）で示される単量体、ＣＦ２＝ＣＦ−ＯＲｆ１（式中、Ｒｆ１は、炭素数１〜８のパーフルオロアルキル基を表す。）で表されるパーフルオロ（アルキルビニルエーテル）〔ＰＡＶＥ〕、及び、ＣＦ２＝ＣＦ−Ｏ−ＣＨ２−Ｒｆ２（式中、Ｒｆ２は、炭素数１〜５のパーフルオロアルキル基を表す。）で表されるアルキルパーフルオロビニルエーテル誘導体からなる群より選択される少なくとも１種の含フッ素エチレン性単量体に由来する繰り返し単位を有することが好ましい。 The fluororesin includes vinyl fluoride [VF], tetrafluoroethylene [TFE], vinylidene fluoride [VdF], chlorotrifluoroethylene [CTFE], hexafluoropropylene [HFP], hexafluoroisobutene, CH 2 = A monomer represented by CZ 1 (CF 2 ) n Z 2 (wherein Z 1 is H or F, Z 2 is H, F or Cl, and n is an integer of 1 to 10), CF 2 = Perfluoro (alkyl vinyl ether) [PAVE] represented by CF—ORf 1 (wherein Rf 1 represents a perfluoroalkyl group having 1 to 8 carbon atoms), and CF 2 ═CF—O—CH. 2 -Rf 2 (wherein, Rf 2 represents a perfluoroalkyl group having 1 to 5 carbon atoms.) are selected from the group consisting of alkyl perfluorovinyl ether derivative represented by the Preferably it has a repeating unit derived from one kind of fluorine-containing ethylenic monomers even without.
上記フッ素樹脂は、フッ素原子を有さないエチレン性単量体に由来する繰り返し単位を有してもよく、耐熱性や耐薬品性等を維持する点で、炭素数５以下のエチレン性単量体に由来する繰り返し単位を有することも好ましい形態の一つである。上記フッ素樹脂は、エチレン、プロピレン、１−ブテン、２−ブテン、塩化ビニル、塩化ビニリデン及び不飽和カルボン酸からなる群より選択される少なくとも１種のフッ素非含有エチレン性単量体を有することも好ましい。 The fluororesin may have a repeating unit derived from an ethylenic monomer having no fluorine atom, and is an ethylenic monomer having 5 or less carbon atoms from the viewpoint of maintaining heat resistance and chemical resistance. Having a repeating unit derived from the body is also a preferred form. The fluororesin may have at least one fluorine-free ethylenic monomer selected from the group consisting of ethylene, propylene, 1-butene, 2-butene, vinyl chloride, vinylidene chloride and unsaturated carboxylic acid. preferable.
上記フッ素樹脂としては、ポリテトラフルオロエチレン〔ＰＴＦＥ〕、ポリクロロトリフルオロエチレン〔ＰＣＴＦＥ〕、エチレン〔Ｅｔ〕／ＴＦＥ共重合体〔ＥＴＦＥ〕、Ｅｔ／クロロトリフルオロエチレン〔ＣＴＦＥ〕共重合体、ＣＴＦＥ／ＴＦＥ共重合体、ＴＦＥ／ＨＦＰ共重合体〔ＦＥＰ〕、ＴＦＥ／ＰＡＶＥ共重合体〔ＰＦＡ〕、及び、ポリビニリデンフルオライド〔ＰＶｄＦ〕からなる群より選択される少なくとも１種であることが好ましく、ＰＴＦＥ、ＰＣＴＦＥ、ＥＴＦＥ、ＣＴＦＥ／ＴＦＥ共重合体、ＦＥＰ及びＰＦＡからなる群より選択される少なくとも１種のフッ素樹脂であることがより好ましい。 Examples of the fluororesin include polytetrafluoroethylene [PTFE], polychlorotrifluoroethylene [PCTFE], ethylene [Et] / TFE copolymer [ETFE], Et / chlorotrifluoroethylene [CTFE] copolymer, CTFE. / TFE copolymer, TFE / HFP copolymer [FEP], TFE / PAVE copolymer [PFA], and at least one selected from the group consisting of polyvinylidene fluoride [PVdF] More preferably, it is at least one fluororesin selected from the group consisting of PTFE, PCTFE, ETFE, CTFE / TFE copolymer, FEP and PFA.
上記ＰＴＦＥとしては、非溶融加工性を有するものであれば特に限定されず、ホモＰＴＦＥであっても、変性ＰＴＦＥであってもよい。 The PTFE is not particularly limited as long as it has non-melt processability, and it may be homo-PTFE or modified PTFE.
上記ＰＡＶＥとしては、パーフルオロ（メチルビニルエーテル）〔ＰＭＶＥ〕、パーフルオロ（エチルビニルエーテル）〔ＰＥＶＥ〕、パーフルオロ（プロピルビニルエーテル）〔ＰＰＶＥ〕、パーフルオロ（ブチルビニルエーテル）等が挙げられ、なかでも、ＰＭＶＥ、ＰＥＶＥ又はＰＰＶＥがより好ましい。 Examples of the PAVE include perfluoro (methyl vinyl ether) [PMVE], perfluoro (ethyl vinyl ether) [PEVE], perfluoro (propyl vinyl ether) [PPVE], perfluoro (butyl vinyl ether), etc. Among them, PMVE PEVE or PPVE is more preferable.
上記アルキルパーフルオロビニルエーテル誘導体としては、Ｒｆ２が炭素数１〜３のパーフルオロアルキル基であるものが好ましく、ＣＦ２＝ＣＦ−Ｏ−ＣＨ２−ＣＦ２ＣＦ３がより好ましい。 As the alkyl perfluorovinyl ether derivative, those in which Rf 2 is a C 1 to C 3 perfluoroalkyl group are preferable, and CF 2 ═CF—O—CH 2 —CF 2 CF 3 is more preferable.
上記フッ素樹脂は、パーフルオロポリマーであることがより好ましく、ＰＴＦＥ、ＦＥＰ及びＰＦＡからなる群より選択される少なくとも１種であることが更に好ましい。上記パーフルオロポリマーは、重合体の主鎖を構成する炭素原子の全部にフッ素原子が結合している重合体である。 The fluororesin is preferably a perfluoropolymer, and more preferably at least one selected from the group consisting of PTFE, FEP, and PFA. The perfluoropolymer is a polymer in which fluorine atoms are bonded to all the carbon atoms constituting the main chain of the polymer.
上記フッ素樹脂は、溶融加工可能なフルオロポリマーであることが特に好ましく、ＰＦＡ及びＦＥＰからなる群より選択される少なくとも１種であることが格別に好ましい。 The fluororesin is particularly preferably a melt-processable fluoropolymer, and particularly preferably at least one selected from the group consisting of PFA and FEP.
ＰＦＡとしては、特に限定されないが、ＴＦＥ単位７０〜９９モル％とＰＡＶＥ単位１〜３０モル％からなる共重合体であることが好ましく、ＴＦＥ単位８０〜９８．５モル％とＰＡＶＥ単位１．５〜２０モル％からなる共重合体であることがより好ましい。ＴＦＥ単位が７０モル％未満では機械物性が低下する傾向があり、９９モル％をこえると融点が高くなりすぎ成形性が低下する傾向がある。上記ＰＦＡは、ＴＦＥ及びＰＡＶＥと共重合可能な単量体に由来する単量体単位が０．１〜１０モル％であり、ＴＦＥ単位及びＰＡＶＥ単位が合計で９０〜９９．９モル％である共重合体であることも好ましい。ＴＦＥ及びＰＡＶＥと共重合可能な単量体としては、ＨＦＰ、ＣＺ３Ｚ４＝ＣＺ５（ＣＦ２）ｎＺ６（式中、Ｚ３、Ｚ４及びＺ５は、同一若しくは異なって、水素原子又はフッ素原子を表し、Ｚ６は、水素原子、フッ素原子又は塩素原子を表し、ｎは２〜１０の整数を表す。）で表されるビニル単量体、及び、ＣＦ２＝ＣＦ−ＯＣＨ２−Ｒｆ７（式中、Ｒｆ７は炭素数１〜５のパーフルオロアルキル基を表す。）で表されるアルキルパーフルオロビニルエーテル誘導体等が挙げられる。 Although it does not specifically limit as PFA, It is preferable that it is a copolymer which consists of 70-99 mol% of TFE units and 1-30 mol% of PAVE units, TFE units 80-98.5 mol%, and PAVE units 1.5. More preferably, the copolymer is composed of ˜20 mol%. If the TFE unit is less than 70 mol%, the mechanical properties tend to decrease, and if it exceeds 99 mol%, the melting point becomes too high and the moldability tends to decrease. The PFA has a monomer unit derived from a monomer copolymerizable with TFE and PAVE in an amount of 0.1 to 10 mol%, and a total of TFE unit and PAVE unit is 90 to 99.9 mol%. A copolymer is also preferred. Monomers copolymerizable with TFE and PAVE include HFP, CZ 3 Z 4 = CZ 5 (CF 2 ) n Z 6 (wherein Z 3 , Z 4 and Z 5 are the same or different and are hydrogen represents an atom or a fluorine atom, Z 6 represents a hydrogen atom, a fluorine atom or a chlorine atom, a vinyl monomer n is represented by the representative.) the integer from 2 to 10, and, CF 2 = CF-OCH Examples thereof include alkyl perfluorovinyl ether derivatives represented by 2- Rf 7 (wherein Rf 7 represents a perfluoroalkyl group having 1 to 5 carbon atoms).
ＦＥＰとしては、特に限定されないが、ＴＦＥ単位７０〜９９モル％とＨＦＰ単位１〜３０モル％からなる共重合体であることが好ましく、ＴＦＥ単位８０〜９７モル％とＨＦＰ単位３〜２０モル％からなる共重合体であることがより好ましい。ＴＦＥ単位が７０モル％未満では機械物性が低下する傾向があり、９９モル％をこえると融点が高くなりすぎ成形性が低下する傾向がある。ＦＥＰは、ＴＦＥ及びＨＦＰと共重合可能な単量体に由来する単量体単位が０．１〜１０モル％であり、ＴＦＥ単位及びＨＦＰ単位が合計で９０〜９９．９モル％である共重合体であることも好ましい。ＴＦＥ及びＨＦＰと共重合可能な単量体としては、ＰＡＶＥ、アルキルパーフルオロビニルエーテル誘導体等が挙げられる。 Although it does not specifically limit as FEP, It is preferable that it is a copolymer which consists of 70-99 mol% of TFE units and 1-30 mol% of HFP units, 80-97 mol% of TFE units, and 3-20 mol% of HFP units. More preferably, it is a copolymer comprising If the TFE unit is less than 70 mol%, the mechanical properties tend to decrease, and if it exceeds 99 mol%, the melting point becomes too high and the moldability tends to decrease. FEP has a monomer unit derived from a monomer copolymerizable with TFE and HFP in an amount of 0.1 to 10 mol%, and a total of 90 to 99.9 mol% of the TFE unit and the HFP unit. A polymer is also preferred. Examples of monomers copolymerizable with TFE and HFP include PAVE and alkyl perfluorovinyl ether derivatives.
上述した共重合体の各単量体の含有量は、ＮＭＲ、ＦＴ−ＩＲ、元素分析、蛍光Ｘ線分析を単量体の種類によって適宜組み合わせることで算出できる。 The content of each monomer of the copolymer described above can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis depending on the type of monomer.
本発明の水生生物付着防止シートは、さらに必要に応じて、添加剤類を含んでもよい。このような添加剤類としては特に限定されず、例えば、レベリング剤、固体潤滑剤、顔料、光輝剤、充填剤、顔料分散剤、表面調節剤、粘度調節剤、紫外線吸収剤、光安定剤、可塑剤、色分かれ防止剤、擦り傷防止剤、生物忌避剤、防徴剤、抗菌剤、抗蝕剤、帯電防止剤、シランカップリング剤等が挙げられる。 The aquatic organism adhesion prevention sheet of this invention may also contain additives further as needed. 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 a plasticizer, a color separation inhibitor, an anti-scratch agent, a biological repellent, an anticorrosive agent, an antibacterial agent, an anticorrosive agent, an antistatic agent, and a silane coupling agent.
本発明の水生生物付着防止シートは、厚みが０．０１〜５ｍｍであることが好ましく、０．１〜３ｍｍであることがより好ましい。
本発明の水生生物付着防止シートは、引張強度が１５〜１００ＭＰａであることが好ましく、２０〜９０ＭＰａであることがより好ましい。
上記引張強度は、ＪＩＳ Ｋ ６８９１に記載の方法により測定して得られる値である。
The aquatic organism adhesion preventing sheet of the present invention preferably has a thickness of 0.01 to 5 mm, and more preferably 0.1 to 3 mm.
The aquatic organism adhesion preventing sheet of the present invention preferably has a tensile strength of 15 to 100 MPa, and more preferably 20 to 90 MPa.
The said tensile strength is a value obtained by measuring by the method of JISK6891.
本発明の水生生物付着防止シートは、柔軟性を有するため、幅広い箇所に適用することができる。 Since the aquatic organism adhesion prevention sheet of this invention has a softness | flexibility, it can be applied to a wide location.
本発明の水生生物付着防止シートは、フッ素樹脂を公知の方法により成形することによって製造することができる。生産性の観点からは押出成形、圧縮成形又は射出成形により製造することが好適である。 The aquatic organism adhesion prevention sheet of this invention can be manufactured by shape | molding a fluororesin by a well-known method. From the viewpoint of productivity, it is preferable to produce by extrusion molding, compression molding or injection molding.
本発明は、基材と、上記基材上に取り付けられた上述の水生生物付着防止シートと、からなる水生生物付着防止パネルでもある。 This invention is also an aquatic organism adhesion prevention panel which consists of a base material and the above-mentioned aquatic organism adhesion prevention sheet attached on the said base material.
上記基材としては、ポリイミド、ポリアミド、ポリカーボネート、ポリエチレンテレフタラート、塩化ビニル、アクリル樹脂等の各種プラスチック、金属、スレート等の建築材料が挙げられる。 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.
本発明の水生生物付着防止パネルは、水生生物付着防止シートを基材に強固に取り付けることができることから、水生生物付着防止シートと基材との間に、接着性化合物を含む組成物から形成された接着層を有することが好ましい。接着層を形成することにより、水生生物付着防止シートと基材との接着性を高めることができる。接着性化合物としては、例えば、ポリアリーレンスルファイド、ポリアミドイミド、ポリアミド（ポリアミック酸）、ポリイミド、ポリエーテルスルホン、ポリアリールスルホン、ポリアリーレンエーテルケトン、シリコーンゴムなどのシリコーン系化合物、エポキシ樹脂等が挙げられる。これらの接着性化合物は一種のみを用いてもよいし、二種以上を併用してもよい。 The aquatic organism adhesion prevention panel of the present invention is formed from a composition containing an adhesive compound between the aquatic organism adhesion prevention sheet and the substrate because the aquatic organism adhesion prevention sheet can be firmly attached to the substrate. It is preferable to have an adhesive layer. By forming the adhesive layer, the adhesion between the aquatic organism adhesion preventing sheet and the substrate can be enhanced. Examples of the adhesive compound include polyarylene sulfide, polyamideimide, polyamide (polyamic acid), polyimide, polyethersulfone, polyarylsulfone, polyarylene etherketone, silicone rubber such as silicone rubber, and epoxy resin. It is done. These adhesive compounds may be used alone or in combination of two or more.
本発明の水生生物付着防止パネルは、工場などで製作することができる。 The aquatic organism adhesion prevention panel of the present invention can be manufactured in a factory or the like.
本発明の水生生物付着防止パネルは、例えば、本発明の水生生物付着防止シートに予め接着性化合物を含む組成物を塗布または貼付しておき、これを基材に取り付けることにより製造できる。接着性化合物を含む組成物を塗布または貼付する前に、水生生物付着防止シートにプラズマ処理やコロナ処理などの前処理を行っておくことが好ましい。 The aquatic organism adhesion prevention panel of the present invention can be produced, for example, by applying or pasting a composition containing an adhesive compound in advance to the aquatic organism adhesion prevention sheet of the present invention and attaching it to a substrate. Before applying or sticking the composition containing the adhesive compound, it is preferable to perform a pretreatment such as a plasma treatment or a corona treatment on the aquatic organism adhesion prevention sheet.
本発明の水生生物付着防止パネルには、あらかじめ水生生物付着防止シートが取り付けてあるので、水生生物の付着を防止したい構造物に直接取り付けることで水生生物の付着を長期間抑制することができ、構造物が設置された現場での脱着も容易である。 Since the aquatic organism adhesion prevention sheet of the present invention is attached in advance to the aquatic organism adhesion prevention sheet, it is possible to suppress the adhesion of aquatic organisms for a long period of time by directly attaching it to the structure where the aquatic organism adhesion is desired to be prevented, Detachment at the site where the structure is installed is also easy.
本発明は、水生生物付着防止シートを備えることを特徴とする水中構造物でもある。 This invention is also an underwater structure provided with an aquatic organism adhesion prevention sheet.
水中構造物としては、海水、淡水中での使用を問わず種々のものがあげられる。また、水面で使用するものであってもよい。たとえば、つぎの物品や構造物が例示できるが、これらに限定されるものではない。また、構造物とは橋脚、水路などの固定型の建造物だけでなく、船舶などの移動を主とする建造物も含む。 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. Further, the structure includes not only fixed structures such as bridge piers and waterways but also structures mainly for moving ships.
固定型：
橋梁、コンクリートブロック、消波ブロック、防波堤、パイプラインなどの水中構築物；
水門門扉、海上タンク、浮き桟橋などの港湾施設；
海底掘削設備、海中通信ケーブル施設などの海底作業施設；
導水路、覆水管、水室、取水口、放水口などの火力、原子力、潮力、海洋温度差発電施設；
プール、水槽、給水塔、下水道、雨どいなどの給排水および貯蔵施設；
システムキッチン、水洗便器、浴室、浴槽などの家庭内設備；
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;
移動型：
船舶の吃水部または船底、潜水艦の外装、スクリュー、プロペラ、錨などの船舶構造物または付属物；
水面または水中で使用する物品
固定型：
定置網などの魚網、ブイ、生簀、ロープなどの漁業用物品；
覆水器、水室などの火力、原子力、海洋温度差発電用物品；
海中（水中）ケーブルなどの海底（水底）敷設物品；
移動型：
底引き網、はえなわなどの漁業用物品；
Mobile type:
Ship structures or accessories such as the dredging or bottom of a ship, the submarine exterior, screws, propellers, dredging;
Fixed article for use on water or in water:
Fishing nets such as stationary nets, buoys, ginger and ropes;
Thermal power supplies such as water covers and water chambers, nuclear power, ocean thermal power generation products;
Submarine (underwater) laying articles such as underwater (underwater) cables;
Mobile type:
Fishing goods such as bottom nets and longing;
本発明は上述の水生生物付着防止シートを水中構造物に取り付ける工程を含むことを特徴とする、水中構造物に水生生物が付着することを防止するための方法でもある。 The present invention is also a method for preventing aquatic organisms from adhering to an underwater structure, comprising the step of attaching the above-mentioned aquatic organism adhesion preventing sheet to the underwater structure.
取り付ける方法は特に限定されず、上述の水生生物付着防止シートを直接水中構造物に取り付けてもよいし、基材に上述の水生生物付着防止シートを取り付けて水生生物付着防止パネルとしてから、水生生物付着防止パネルを水中構造物に取り付けてもよい。シート及びパネルは、水中構造物に接着剤を使用して取り付けることもできるし、アンカーボルト等の取付具を使用して取り付けることもできる。 The attachment method is not particularly limited, and the above-mentioned aquatic organism adhesion prevention sheet may be directly attached to the underwater structure, or the above-mentioned aquatic organism adhesion prevention sheet is attached to the base material to form an aquatic organism adhesion prevention panel. You may attach an adhesion prevention panel to an underwater structure. The sheet and the panel can be attached to the underwater structure using an adhesive, or can be attached using a fixture such as an anchor bolt.
本発明は、フッ素樹脂を含むことを特徴とする水生生物付着防止塗料でもある。上記フッ素樹脂は、本発明の水生生物付着防止シートで使用できるフッ素樹脂として上述したフッ素樹脂がそのまま適用できる。 This invention is also an aquatic organism adhesion prevention coating material characterized by including a fluororesin. As the fluororesin, the fluororesin described above can be applied as it is as the fluororesin that can be used in the aquatic organism adhesion prevention sheet of the present invention.
本発明の水生生物付着防止塗料は、複雑な形状の構造物に対しても所望の膜厚で塗膜を形成させることができ、形成した塗膜によって基材への水生生物の付着を長期間抑制することができる。 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 aquatic organism adheres to the substrate for a long time by the formed coating film. Can be suppressed.
本発明の水生生物付着防止塗料は、数百から数千μｍの厚みのある塗膜を容易に設けることができる点で、粉体組成物であることが好ましい。本発明の水生生物付着防止塗料に含まれるフッ素樹脂は、平均粒子径が０．１〜５０μｍであることが好ましい。
上記平均粒子径は、レーザー回折式粒度分布測定機を用いて求めることができる。
The aquatic organism adhesion-preventing paint of the present invention is preferably a powder composition in that a coating film having a thickness of several hundred to several thousand μm can be easily provided. The fluororesin contained in the aquatic organism adhesion preventing paint of the present invention preferably has an average particle size of 0.1 to 50 μm.
The average particle diameter can be obtained using a laser diffraction particle size distribution analyzer.
本発明の水生生物付着防止塗料は、ポリアミドイミド〔ＰＡＩ〕、ポリアミド、及び、ポリアミド酸（ポリアミック酸）からなる群より選択される少なくとも一種のアミド基含有ポリマーを含むものであってもよい。上記ＰＡＩは、アミド基と芳香環とイミド基とを有する重縮合体である。上記ＰＡＩとしては特に限定されず、例えば、従来公知のＰＡＩの他にも、ポリイミド〔ＰＩ〕を酸化することによりアミド基を導入したもの等を用いることができる。上記ポリアミドは、主鎖中にアミド結合（−ＮＨ−Ｃ（＝Ｏ）−）を有する重縮合体である。上記ポリアミドとしては特に限定されず、例えば、ナイロン６、ナイロン６６、ナイロン１１、ナイロン１２等の脂肪族ポリアミド；ポリパラフェニレンテレフタラミド、ポリメタフェニレンイソフタラミド等の芳香族ポリアミド等が挙げられる。上記ポリアミド酸は、アミド基と、カルボキシル基又はカルボキシル基の誘導体とを有する重縮合体である。上記ポリアミド酸としては特に限定されず、分子量が数千〜数万であるポリアミド酸等が挙げられる。 The aquatic organism adhesion-preventing paint of the present invention may contain at least one amide group-containing polymer selected from the group consisting of polyamideimide [PAI], polyamide, and polyamic acid (polyamic acid). The PAI is a polycondensate having an amide group, an aromatic ring, and an imide group. The PAI is not particularly limited, and for example, in addition to the conventionally known PAI, those in which an amide group is introduced by oxidizing polyimide [PI] can be used. The polyamide is a polycondensate having an amide bond (—NH—C (═O) —) in the main chain. The polyamide is not particularly limited, and examples thereof include aliphatic polyamides such as nylon 6, nylon 66, nylon 11, and nylon 12; aromatic polyamides such as polyparaphenylene terephthalamide and polymetaphenylene isophthalamide. . The polyamic acid is a polycondensate having an amide group and a carboxyl group or a carboxyl group derivative. The polyamic acid is not particularly limited, and examples thereof include a polyamic acid having a molecular weight of thousands to tens of thousands.
本発明の水生生物付着防止塗料は、ポリアリーレンスルファイド〔ＰＡＳ〕を含むことが好ましく、アミド基含有ポリマー及びＰＡＳの両方を含むことが好ましい。上記ＰＡＳとしては特に限定されず、例えば、ポリフェニレンスルフィドケトン、ポリフェニレンスルフィドスルフォン、ポリビフェニレンサルファイド、ポリフェニレンサルファイド〔ＰＰＳ〕等が挙げられ、なかでもＰＰＳが好適に用いられる。 The aquatic organism adhesion-preventing paint of the present invention preferably contains polyarylene sulfide [PAS], and preferably contains both an amide group-containing polymer and PAS. The PAS is not particularly limited, and examples thereof include polyphenylene sulfide ketone, polyphenylene sulfide sulfone, polybiphenylene sulfide, and polyphenylene sulfide [PPS]. Among them, PPS is preferably used.
上記ＰＡＳは、上記アミド基含有ポリマーと上記ＰＡＳとの合計の１〜４０質量％であることが好ましく、上記フッ素樹脂は、塗料全体に対して５０〜９５質量％であることが好ましい。 The PAS is preferably 1 to 40% by mass of the total of the amide group-containing polymer and the PAS, and the fluororesin is preferably 50 to 95% by mass with respect to the entire coating material.
本発明の水生生物付着防止塗料は、さらに必要に応じて、添加剤類を含んでもよい。このような添加剤類としては特に限定されず、例えば、レベリング剤、固体潤滑剤、顔料、光輝剤、充填剤、顔料分散剤、表面調節剤、粘度調節剤、紫外線吸収剤、光安定剤、可塑剤、色分かれ防止剤、擦り傷防止剤、生物忌避剤、防徴剤、抗菌剤、抗蝕剤、帯電防止剤、シランカップリング剤、ワキ防止剤、つや消し剤等が挙げられる。 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-scratch agents, biological repellents, anticorrosive agents, antibacterial agents, anticorrosive agents, antistatic agents, silane coupling agents, anti-waxing agents, and delustering agents.
本発明の水性生物付着防止塗料は、上記フッ素樹脂と必要に応じて上述した成分とを、公知の方法で混合、分散させることにより製造することができる。 The aqueous bioadhesion-preventing coating material of the present invention can be produced by mixing and dispersing the above-mentioned fluororesin and, if necessary, the above-described components by a known method.
本発明は、基材と、上記基材上に形成された上述の水生生物付着防止塗料からなる塗膜と、からなる水生生物付着防止パネルでもある。 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.
上記基材としては、ポリイミド、ポリアミド、ポリカーボネート、ポリエチレンテレフタラート、塩化ビニル、アクリル樹脂等の各種プラスチック、金属、スレート等の建築材料が挙げられる。 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.
本発明の水生生物付着防止パネルは、塗膜と基材との間に、接着性化合物を含む組成物（但し、フッ素樹脂を含むものを除く。）から形成された接着層を有することが好ましい。接着層を形成することにより、塗膜と基材との接着性を高めることができる。接着性化合物としては、例えば、ポリアリーレンスルファイド、ポリアミドイミド、ポリアミド（ポリアミック酸）、ポリイミド、ポリエーテルスルホン、ポリアリールスルホン、ポリアリーレンエーテルケトン、シリコーンゴムなどのシリコーン系化合物、エポキシ樹脂等が挙げられる。これらの接着性化合物は一種のみを用いてもよいし、二種以上を併用してもよい。接着性化合物を含む組成物は、液状組成物であっても粉体組成物であってもよい。 The aquatic organism adhesion prevention panel of the present invention preferably has an adhesive layer formed from a composition containing an adhesive compound (excluding those containing a fluororesin) between the coating film and the substrate. . By forming the adhesive layer, the adhesion between the coating film and the substrate can be enhanced. Examples of the adhesive compound include polyarylene sulfide, polyamideimide, polyamide (polyamic acid), polyimide, polyethersulfone, polyarylsulfone, polyarylene etherketone, silicone rubber such as silicone rubber, and epoxy resin. It is done. These adhesive compounds may be used alone or in combination of two or more. The composition containing the adhesive compound may be a liquid composition or a powder composition.
本発明の水生生物付着防止パネルは、基材に接着性化合物を含む組成物を塗布することにより接着層を設け、接着層上に本発明の水生生物付着防止塗料を塗布することにより製造できる。 The aquatic organism adhesion prevention panel of this invention can be manufactured by providing an adhesive layer by apply | coating the composition containing an adhesive compound to a base material, and apply | coating the aquatic organism adhesion prevention coating material of this invention on an adhesion layer.
本発明の水生生物付着防止パネルは、基材と、基材上に形成されたフッ素樹脂、アミド基含有ポリマー及びＰＡＳを含む液状組成物からなる接着層と、接着層上に形成された本発明の水生生物付着防止塗料からなる塗膜と、からなるものであることがより好ましい。
塗膜の膜厚は、１００〜５０００μｍが好ましい。上記膜厚は、ＪＩＳ Ｋ ５６００の方法により測定して得られる値である。
The aquatic organism adhesion prevention panel of the present invention is a substrate, an adhesive layer made of a liquid composition containing a fluororesin, an amide group-containing polymer and PAS formed on the substrate, and the present invention formed on the adhesive layer. It is more preferable that the coating film comprises an aquatic organism adhesion preventing coating.
As for the film thickness of a coating film, 100-5000 micrometers is preferable. The film thickness is a value obtained by measurement according to the method of JIS K 5600.
本発明は、上述の水生生物付着防止塗料からなる塗膜を備える水中構造物でもある。水中構造物は、既に詳述したとおりである。 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 is as already described in detail.
本発明は、基材又は水中構造物に上述の水生生物付着防止塗料を塗布する工程を含むことを特徴とする、基材又は水中構造物に水生生物が付着することを防止するための方法でもある。 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.
水生生物付着防止塗料を塗布する方法は、特に制限されず、公知の方法により塗布することができる。水生生物付着防止塗料が粉体組成物である場合は、静電塗装法が好適である。 The method for applying the aquatic organism adhesion preventing coating is not particularly limited, and can be applied by a known method. When the aquatic organism adhesion preventing coating is a powder composition, an electrostatic coating method is suitable.
つぎに本発明を実施例をあげて説明するが、本発明はかかる実施例のみに限定されるものではない。 Next, the present invention will be described with reference to examples, but the present invention is not limited to such examples.
調製例１
懸濁重合により得たテトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体（ＴＦＥ／ＰＡＶＥ＝９８／２（モル比）、融点３０４℃）を、新東工業社製のローラーコンパクターＢＳＣ−２５型を用い、得られるシートが真比重の９０％以上となるように圧縮し、次に解砕機で約１０ｍｍ径に解砕したものを、奈良機械製作所社製の粉砕機コスモマイザーＮ−１型を用いて粉砕した。こうして得られた粉砕品Ａの平均粒子径は５６μｍであった。
Preparation Example 1
Using tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (TFE / PAVE = 98/2 (molar ratio), melting point 304 ° C.) obtained by suspension polymerization, a roller compactor BSC-25 type manufactured by Shinto Kogyo Co., Ltd. The resulting sheet is compressed so that it is 90% or more of the true specific gravity, and then crushed to a diameter of about 10 mm with a crusher, using a crusher cosmomizer type N-1 manufactured by Nara Machinery Co., Ltd. Crushed. The average particle size of the pulverized product A thus obtained was 56 μm.
調製例２
懸濁重合により得たテトラフルオロエチレン−ヘキサフルオロプロピレン共重合体（ＴＦＥ／ＨＦＰ＝９３／７（モル比）、融点２６８℃）を、新東工業社製のローラーコンパクターＢＳＣ−２５型を用い、得られるシートが真比重の９０％以上となるように圧縮し、次に解砕機で約１０ｍｍ径に解砕したものを、奈良機械製作所社製の粉砕機コスモマイザーＮ−１型を用いて粉砕した。こうして得られた粉砕品Ｂの平均粒子径は３４μｍであった。
Preparation Example 2
Using tetrafluoroethylene-hexafluoropropylene copolymer (TFE / HFP = 93/7 (molar ratio), melting point 268 ° C.) obtained by suspension polymerization, a roller compactor BSC-25 type manufactured by Shinto Kogyo Co., Ltd. The obtained sheet is compressed to 90% or more of the true specific gravity, and then crushed to a diameter of about 10 mm with a crusher using a crusher Cosmizer N-1 type manufactured by Nara Machinery Co., Ltd. did. The average particle size of the pulverized product B thus obtained was 34 μm.
実施例１
ＳＵＳ３０４のパネル基材上に、テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体、ポリフェニレンサルファイド及びポリアミドイミドからなる液状組成物（ＴＦＥ−ＰＡＶＥ共重合体／ポリフェニレンサルファイド／ポリアミドイミド＝８０／５／１５（質量比））を塗布することにより接着層（乾燥膜厚５２μｍ）を設けた。その上に粉砕品Ａを静電塗装法により３回繰返して塗布することにより塗膜（膜厚２１０μｍ）を設けた。こうして試験パネルＡを作製した。
Example 1
A liquid composition comprising a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polyphenylene sulfide and polyamideimide on a panel substrate of SUS304 (TFE-PAVE copolymer / polyphenylene sulfide / polyamideimide = 80/5/15 ( The adhesive layer (dry film thickness 52 μm) was provided by applying a mass ratio)). A coating film (film thickness: 210 μm) was provided thereon by repeatedly applying the pulverized product A three times by electrostatic coating. Thus, test panel A was produced.
実施例２
ＳＵＳ３０４のパネル基材上に、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体、ポリフェニレンサルファイド及びポリアミドイミドからなる液状組成物（ＴＦＥ−ＨＦＰ共重合体／ポリフェニレンサルファイド／ポリアミドイミド＝８０／５／１５（質量比））を塗布することにより接着層（乾燥膜厚５５μｍ）を設けた。その上に、粉砕品Ｂを静電塗装法により３回繰返して塗布することにより塗膜（膜厚１９６μｍ）を設けた。こうして試験パネルＢを作製した。
Example 2
On a panel substrate of SUS304, a liquid composition comprising tetrafluoroethylene-hexafluoropropylene copolymer, polyphenylene sulfide and polyamideimide (TFE-HFP copolymer / polyphenylene sulfide / polyamideimide = 80/5/15 (mass) Ratio)) was applied to provide an adhesive layer (dry film thickness 55 μm). A coating film (film thickness: 196 μm) was provided thereon by applying the pulverized product B three times by electrostatic coating. Thus, test panel B was produced.
実施例３
コロナ処理が施されたテトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体からなるシート（ＴＦＥ／ＰＡＶＥ＝９８／２（モル比）、厚み０．１ｍｍ）に、アクリル系粘着剤（ＤＡ−４００、商品名、フロント研究所社製）を塗布したものを、スレートのパネル基材上に貼付した。こうして試験パネルＣを作製した。
Example 3
A sheet of a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer that has been subjected to corona treatment (TFE / PAVE = 98/2 (molar ratio), thickness 0.1 mm) and acrylic adhesive (DA-400, product) The name, manufactured by Front Laboratory Co., Ltd., was applied onto a slate panel substrate. Thus, test panel C was produced.
実施例４
コロナ処理が施されたテトラフルオロエチレン−ヘキサフルオロプロピレン共重合体からなるシート（ＴＦＥ／ＨＦＰ＝９３／７（モル比）、厚み０．１ｍｍ）に、アクリル系粘着剤（ＤＡ−４００、商品名、フロント研究所社製）を塗布したものを、スレートのパネル基材上に貼付した。こうして試験パネルＤを作製した。
Example 4
A sheet of a tetrafluoroethylene-hexafluoropropylene copolymer subjected to corona treatment (TFE / HFP = 93/7 (molar ratio), thickness 0.1 mm) and acrylic adhesive (DA-400, trade name) , Manufactured by Front Laboratory Co., Ltd.) was applied on a slate panel substrate. Thus, test panel D was produced.
比較例１
ＳＵＳ３０４のパネル基材上に、まず接着性化合物を含む組成物として、ゼッフル遮熱塗料 下塗り（ダイキン工業社製）を塗布することにより接着層（乾燥膜厚４１μｍ）を設けた。その上に、ＧＫ５７０（ダイキン工業社製 硬化型樹脂ワニス）を塗布することにより塗膜（膜厚３４μｍ）を設けた。こうして試験パネルＥを作製した。
Comparative Example 1
An adhesive layer (dry film thickness 41 μm) was provided on a SUS304 panel substrate by first applying a zefle thermal barrier paint undercoat (manufactured by Daikin Industries) as a composition containing an adhesive compound. A coating film (film thickness 34 μm) was provided thereon by applying GK570 (a curable resin varnish manufactured by Daikin Industries, Ltd.). Thus, test panel E was produced.
比較例２
ＳＵＳ３０４のパネル基材上に、まず接着性化合物を含む組成物として、ゼッフル遮熱塗料 下塗り（ダイキン工業社製）を塗布することにより接着層（乾燥膜厚４７μｍ）を設けた。その上に、ＧＫ５７０（ダイキン工業社製 硬化型樹脂ワニス） １００重量部にジメチルシリコーンオイル ４重量部を添加したものを塗布することにより塗膜（膜厚３２ｍｍ）を設けた。こうして試験パネルＦを作製した。
Comparative Example 2
An adhesive layer (dry film thickness 47 μm) was provided on a SUS304 panel substrate by first applying a zefle thermal barrier paint undercoat (Daikin Kogyo Co., Ltd.) as a composition containing an adhesive compound. On top of that, a coating film (film thickness 32 mm) was provided by applying 100 parts by weight of GK570 (a curable resin varnish manufactured by Daikin Industries, Ltd.) and 4 parts by weight of dimethyl silicone oil. A test panel F was thus prepared.
比較例３
ＳＵＳ３０４のパネル基材上に、まず接着性化合物を含む組成物として、エッチングプライマー Ｈ（中国塗料社製）を塗布することにより接着層（乾燥膜厚３８μｍ）を設けた。その上に、バイオクリンＤ Ｘ（中国塗料社製 シリコーン樹脂系組成物）を塗布することにより塗膜（膜厚８０μｍ）を設けた。こうして試験パネルＧを作製した。
Comparative Example 3
On the panel base material of SUS304, the adhesion layer (dry film thickness of 38 micrometers) was first provided by apply | coating the etching primer H (made by a China paint company) as a composition containing an adhesive compound. A coating film (film thickness of 80 μm) was provided thereon by applying Bioclin DX (a silicone resin composition manufactured by China Paint Co., Ltd.). Thus, a test panel G was produced.
防汚性評価：
ポリスチレン容器の内側へのキプリス幼生（内湾海域の水中構造物に大量付着するタテジマフジツボの付着期幼生）の付着を防止するべく目合い１００μｍのプランクトンネットを設置した上で、ネットの内側に試験パネル、海水、キプリス幼生を投入した。幼生数は一容器当たり２０〜３０固体とし、容器は室温２０℃の晴所に設置した。幼生投入から７日後に試験パネルを容器から取り出し、試験パネルに占める幼生が付着した部分の面積割合を目視で確認した。この結果を表１に示す。
Antifouling evaluation:
In order to prevent adhesion of Cypris larvae (the larvae of the vertical barnacles adhering to the underwater structures in the inner bay sea area) inside the polystyrene container, a plankton net with a mesh size of 100 μm was installed, and a test panel inside the net , Seawater, cypris larvae. The number of larvae was 20 to 30 solids per container, and the container was placed in a sunny place at room temperature of 20 ° C. Seven days after feeding the larvae, the test panel was taken out of the container, and the area ratio of the portion of the test panel where the larvae adhered was visually confirmed. The results are shown in Table 1.
本発明の水生生物付着防止シート、水生生物付着防止塗料、及び、水生生物付着防止パネルは、発電所の導水路管や復水管および取水口や放水口、港湾施設、ブイ、パイプライン、橋梁、海底基地、海底油田掘削設備、船舶などの水中構造物に取り付けることができる。
The aquatic organism adhesion prevention sheet, the aquatic organism adhesion prevention paint, and the aquatic organism adhesion prevention panel of the present invention are a waterway conduit pipe, a condenser pipe, a water intake port, a water discharge port, a port facility, a buoy, a pipeline, a bridge, It can be attached to underwater structures such as submarine bases, subsea oil field drilling equipment, and ships.
Claims (15)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2012069286A JP2012214739A (en) | 2011-03-28 | 2012-03-26 | Sheet for preventing adhesion of aquatic organism and coating material for preventing adhesion of aquatic organism |
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| JP2011070873 | 2011-03-28 | ||
| JP2011070873 | 2011-03-28 | ||
| JP2012069286A JP2012214739A (en) | 2011-03-28 | 2012-03-26 | Sheet for preventing adhesion of aquatic organism and coating material for preventing adhesion of aquatic organism |
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| JP (1) | JP2012214739A (en) |
| CN (1) | CN103443361A (en) |
| WO (1) | WO2012133347A1 (en) |
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| JP2015027291A (en) * | 2013-06-24 | 2015-02-12 | ダイキン工業株式会社 | Fabric for preventing adhesion of aquatic organisms |
| WO2016104602A1 (en) * | 2014-12-26 | 2016-06-30 | ダイキン工業株式会社 | Marine antifouling material, marine antifouling coating, marine antifouling panel, underwater structure and method for preventing adherence of marine microorganisms to underwater structure |
| WO2016121995A1 (en) * | 2015-01-29 | 2016-08-04 | ダイキン工業株式会社 | Base material and application of same |
| EP2902489B1 (en) | 2012-09-27 | 2017-09-13 | Chugai Seiyaku Kabushiki Kaisha | Fgfr3 fusion gene and pharmaceutical drug targeting same |
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| WO2014054685A1 (en) * | 2012-10-03 | 2014-04-10 | ダイキン工業株式会社 | Molded article for preventing adhesion of aquatic organisms |
| US20170158848A1 (en) * | 2014-06-13 | 2017-06-08 | Daikin Industries, Ltd. | Material for preventing adhesion of aquatic organisms |
| ES2882953T3 (en) * | 2014-12-16 | 2021-12-03 | Koninklijke Philips Nv | A marine cable device adapted for fouling prevention |
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| JP2015027291A (en) * | 2013-06-24 | 2015-02-12 | ダイキン工業株式会社 | Fabric for preventing adhesion of aquatic organisms |
| CN105338808A (en) * | 2013-06-24 | 2016-02-17 | 大金工业株式会社 | Fabric for preventing adhesion of aquatic organisms |
| EP3014990A4 (en) * | 2013-06-24 | 2017-03-08 | Daikin Industries, Ltd. | Fabric for preventing adhesion of aquatic organisms |
| CN107090713A (en) * | 2013-06-24 | 2017-08-25 | 大金工业株式会社 | For the manufacture method weaved cotton cloth for preventing aquatile from adhering to |
| TWI636166B (en) * | 2013-06-24 | 2018-09-21 | 大金工業股份有限公司 | Anti-aquatic organism attachment woven fabric |
| WO2016104602A1 (en) * | 2014-12-26 | 2016-06-30 | ダイキン工業株式会社 | Marine antifouling material, marine antifouling coating, marine antifouling panel, underwater structure and method for preventing adherence of marine microorganisms to underwater structure |
| JPWO2016104602A1 (en) * | 2014-12-26 | 2017-10-05 | ダイキン工業株式会社 | 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 |
| WO2016121995A1 (en) * | 2015-01-29 | 2016-08-04 | ダイキン工業株式会社 | Base material and application of same |
| JP2016163988A (en) * | 2015-01-29 | 2016-09-08 | ダイキン工業株式会社 | Substrate and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012133347A1 (en) | 2012-10-04 |
| CN103443361A (en) | 2013-12-11 |
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