JP2006291116A - Ship bottom coating - Google Patents
Ship bottom coating Download PDFInfo
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- JP2006291116A JP2006291116A JP2005116507A JP2005116507A JP2006291116A JP 2006291116 A JP2006291116 A JP 2006291116A JP 2005116507 A JP2005116507 A JP 2005116507A JP 2005116507 A JP2005116507 A JP 2005116507A JP 2006291116 A JP2006291116 A JP 2006291116A
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- ship bottom
- activated carbon
- ship
- carbon powder
- bottom paint
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- 239000011248 coating agent Substances 0.000 title abstract description 14
- 238000000576 coating method Methods 0.000 title abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000000463 material Substances 0.000 claims abstract description 67
- 239000011941 photocatalyst Substances 0.000 claims abstract description 39
- 239000003973 paint Substances 0.000 claims description 68
- 230000001699 photocatalysis Effects 0.000 claims description 29
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 28
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 10
- 238000007740 vapor deposition Methods 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 5
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 4
- 244000060011 Cocos nucifera Species 0.000 claims description 4
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 2
- 229910002367 SrTiO Inorganic materials 0.000 claims description 2
- 230000003373 anti-fouling effect Effects 0.000 abstract description 6
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- 230000001954 sterilising effect Effects 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 241001474374 Blennius Species 0.000 description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 9
- 239000010408 film Substances 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 8
- 241000238586 Cirripedia Species 0.000 description 7
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 7
- -1 alkalis Substances 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000012860 organic pigment Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000010815 organic waste Substances 0.000 description 5
- 238000013032 photocatalytic reaction Methods 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 3
- 229940112669 cuprous oxide Drugs 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000001782 photodegradation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- SXQXMCWCWVCFPC-UHFFFAOYSA-N aluminum;potassium;dioxido(oxo)silane Chemical compound [Al+3].[K+].[O-][Si]([O-])=O.[O-][Si]([O-])=O SXQXMCWCWVCFPC-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- QBLDFAIABQKINO-UHFFFAOYSA-N barium borate Chemical class [Ba+2].[O-]B=O.[O-]B=O QBLDFAIABQKINO-UHFFFAOYSA-N 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- 239000001030 cadmium pigment Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- XJUNRGGMKUAPAP-UHFFFAOYSA-N dioxido(dioxo)molybdenum;lead(2+) Chemical compound [Pb+2].[O-][Mo]([O-])(=O)=O XJUNRGGMKUAPAP-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- UYTPUPDQBNUYGX-UHFFFAOYSA-N guanine Chemical compound O=C1NC(N)=NC2=C1N=CN2 UYTPUPDQBNUYGX-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000001034 iron oxide pigment Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 239000001035 lead pigment Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
本発明は、活性炭の吸着作用と光触媒材料の分解（酸化）・殺菌作用を組み合わせることにより、水棲生物の付着を抑制し、長期間に亘る安定した防汚能力を発現し得る船底塗料に関する。 The present invention relates to a ship bottom coating that can suppress the adhesion of aquatic organisms by combining the adsorption action of activated carbon and the decomposition (oxidation) / sterilization action of a photocatalyst material and can exhibit a stable antifouling ability over a long period of time.
漁船や各種運搬船或いはプレジャーボート等の船舶を海上に係留すると、当該船舶の船底にフジツボや海草、海藻等に代表される水棲生物が徐々に付着し、船底の外観が損なわれるばかりか、船底表面に凹凸が生じることによる推進量の低下及び燃費の悪化が生じる。 When a boat such as a fishing boat, various transport boats or pleasure boats is moored on the sea, aquatic organisms such as barnacles, seaweeds, seaweeds, etc. gradually adhere to the bottom of the vessel and the appearance of the bottom of the vessel is impaired. As a result, the amount of propulsion and fuel consumption deteriorate due to unevenness.
そのため、船底に付着した水棲生物を定期的に除去する作業が必要となるが、この作業は、船舶を一旦陸揚げし、クレーンなどで吊るした後にブラシやサンダなどで擦り落とすといった頓雑な作業であり、又、水棲生物の付着は強固であることから、除去作業に非常に多大な労力が必要となる。 Therefore, it is necessary to periodically remove aquatic organisms attached to the bottom of the ship, but this work is a complicated work such as landing the ship once, hanging it with a crane, etc., and scraping it off with a brush or sander. In addition, since the attachment of aquatic organisms is strong, a great deal of labor is required for the removal operation.
そこで、船底に水棲生物が付着し難くなるようにすべく、亜酸化銅や有機スズ化合物などを含有する塗料を船底に塗布する手段が一般的に採用されている。 Therefore, in order to make it difficult for aquatic organisms to adhere to the ship bottom, means for applying a paint containing cuprous oxide or an organic tin compound to the ship bottom is generally employed.
しかしながら、亜酸化銅や有機スズ化合物には毒性があり、船底に塗布された塗料中の毒性物質が徐々に海水中に溶出して環境汚染を引き起こすことから、その使用には大きな問題が生じており、亜酸化銅や有機スズ化合物に替わる無害な船底塗料の開発が強く要求されている。 However, cuprous oxide and organotin compounds are toxic, and toxic substances in the paint applied to the bottom of the ship gradually elute into seawater, causing environmental pollution. Therefore, there is a strong demand for the development of harmless ship bottom paints that can replace cuprous oxide and organotin compounds.
そこで、最近では、光触媒材料機能を有する酸化チタン等に代表される光触媒材料を利用した船底塗料が開発されている（例えば、特許文献１〜３。）。 Therefore, recently, ship bottom paints using photocatalyst materials typified by titanium oxide having a photocatalyst material function have been developed (for example, Patent Documents 1 to 3).
酸化チタンは、白色顔料として広く使用されているものであり、通常の使用条件では、酸、アルカリ、水、有機溶剤に溶解せず、反応性の強いガスとも反応しない極めて安定な性状を有し、結晶構造として、ルチル、アナターゼ及びブルッカイトの３種の状態をとることができるが、中でもアナターゼ型の結晶構造のものは、太陽光などの紫外線領域の光線が当たることによってスーパーオキサイドアニオン（Ｏ2-）やヒドロキシラジカル（・ＯＨ）などのラジカル基を生成し、その強い酸化力により、微生物を忌避・分解し、有機物を分解する作用を発現する。 Titanium oxide is widely used as a white pigment. Under normal conditions of use, titanium oxide does not dissolve in acids, alkalis, water, or organic solvents, and has extremely stable properties that do not react with highly reactive gases. The crystal structure can take three states: rutile, anatase, and brookite. Among them, the anatase crystal structure has a superoxide anion (O 2 ) when exposed to light in the ultraviolet region such as sunlight. - ) Generates radical groups such as hydroxy radicals (.OH), and by its strong oxidizing power, it repels and decomposes microorganisms and develops the action of decomposing organic substances.
そのため、このような酸化チタンを含有する船底塗料を利用すれば、水棲生物の付着を抑制することが可能となるのである。 Therefore, if such a ship bottom coating containing titanium oxide is used, it is possible to suppress adhesion of aquatic organisms.
しかしながら、上述のように、酸化チタンは、その強い酸化力により接触する有機物を分解するものであるが、この酸化チタンを含有する船底塗料を船底に塗布すると、その強い酸化力により、当該塗料中のバインダー成分がボロボロになってしまい、比較的短期間で塗布した酸化チタンが船底から剥がれ落ちてしまうといった、いわゆる「チョーク現象」の問題がある。 However, as described above, titanium oxide decomposes organic substances that come into contact with its strong oxidizing power. However, when a ship bottom coating containing this titanium oxide is applied to the bottom of the ship, its strong oxidizing power causes the paint to enter the paint. There is a problem of the so-called “choke phenomenon” in which the binder component becomes tattered and the titanium oxide applied in a relatively short period of time is peeled off from the ship bottom.
そこで、この問題に鑑み、本発明者が鋭意検討を重ねた結果、船舶における船底塗装用の塗料として使用する船底塗料であって、該船底塗料は、活性炭粉末及び光触媒材料を含有することを特徴とする本発明の船底塗料を開発するに至ったのである。 Therefore, in view of this problem, as a result of repeated studies by the present inventors, a ship bottom paint used as a ship bottom paint in a ship, wherein the ship bottom paint contains activated carbon powder and a photocatalytic material. As a result, the ship bottom paint of the present invention has been developed.
即ち、本発明者は、船舶における船底塗装用の塗料として使用する船底塗料において、酸化チタンなどの光触媒材料を含有させることにより、水棲生物の付着を抑制することができるのであり、船底の外観及び滑らかさを維持し、推進量の低下及び燃費の悪化を防止することができるとの知見を得たのである。 That is, the present inventor can suppress adhesion of aquatic organisms by adding a photocatalytic material such as titanium oxide in a ship bottom paint used as a ship bottom paint in a ship. They obtained the knowledge that the smoothness can be maintained and the propulsion amount and fuel consumption can be prevented from deteriorating.
特に、本発明者は、船底塗料中に光触媒材料と共に活性炭粉末を含有することにより、活性炭粉末が光触媒材料を吸着し、光触媒材料の剥がれ落ちを抑制するため、長期間にわたって安定した防汚能力を発現し得るとの知見を得たのである。 In particular, the present inventor includes activated carbon powder together with the photocatalyst material in the ship bottom coating so that the activated carbon powder adsorbs the photocatalyst material and suppresses the photocatalyst material from peeling off. The knowledge that it can express was obtained.
又、本発明者は、船底塗料中に光触媒材料と共に活性炭粉末を含有することにより、活性炭粉末が太陽光などの紫外線領域の光線が当たることによってスーパーオキサイドアニオン（Ｏ2-）やヒドロキシラジカル（・ＯＨ）などのラジカル基が生成するが、このスーパーオキサイドアニオン（Ｏ2-）やヒドロキシラジカル（・ＯＨ）などのラジカル基が前記活性炭粉末に吸着されてそれらの拡散、喪失を防止し、これらのラジカル基の有効利用を図ることができると共に、この吸着によって塗料中のバインダー成分がボロボロになるのを防止し得るとの知見も得たのである。 Further, the inventor of the present invention includes the activated carbon powder together with the photocatalyst material in the ship bottom coating, so that the activated carbon powder is exposed to light in the ultraviolet region such as sunlight, thereby superoxide anion (O 2− ) and hydroxy radical (• OH) and other radical groups are produced, and radical groups such as superoxide anion (O 2− ) and hydroxy radical (• OH) are adsorbed on the activated carbon powder to prevent their diffusion and loss. In addition to the effective utilization of radical groups, it has also been found that this adsorption can prevent the binder component in the paint from becoming tattered.
更に、本発明者は、船底に付着する水棲生物や有機性のゴミが活性炭に速やかに吸着されるため、光触媒材料の光分解（酸化）作用によって、非常に効率よく、有機性のゴミを分解することができるとの知見も得たのである。 Furthermore, the present inventor has been able to decompose organic waste very efficiently by the photodegradation (oxidation) action of the photocatalyst material because aquatic organisms and organic waste adhering to the ship bottom are quickly adsorbed to the activated carbon. They also learned that they can do it.
本発明は、上記知見に基づき完成されたものであって、活性炭の吸着作用と光触媒材料の分解（酸化）・殺菌作用を組み合わせることにより、光触媒材料の光分解（酸化）作用によって、水棲生物の付着を抑制し、長期間に亘る安定した防汚能力を発現し得る新規な船底塗料を提供することを目的とする。 The present invention has been completed on the basis of the above knowledge, and by combining the adsorption action of activated carbon and the decomposition (oxidation) / sterilization action of the photocatalyst material, the photodegradation (oxidation) action of the photocatalyst material can An object of the present invention is to provide a novel ship bottom paint that can suppress adhesion and can exhibit a stable antifouling ability over a long period of time.
この目的を達成するため、本発明に係る船底塗料においては、船舶における船底塗装用の塗料として使用する船底塗料であって、該船底塗料は、活性炭粉末及び光触媒材料を含有することを特徴とするものである。
以下、本発明の船底塗料について詳細に説明する。
In order to achieve this object, the ship bottom paint according to the present invention is a ship bottom paint used as a ship bottom paint in a ship, wherein the ship bottom paint contains activated carbon powder and a photocatalytic material. Is.
Hereinafter, the ship bottom paint of the present invention will be described in detail.
本発明に係る船底塗料においては、船舶における船底塗装用の塗料として使用するものであり、漁船や各種運搬船或いはプレジャーボート等の船舶の船底に塗布することにより、フジツボや海草、海藻等に代表される水棲生物の付着を忌避、抑制するものである。 In the ship bottom paint according to the present invention, it is used as a paint for ship bottom paint in ships, and it is represented by barnacles, seaweeds, seaweeds, etc. by applying it to the ship bottoms of fishing ships, various transport ships, pleasure boats and the like. It avoids and suppresses the attachment of aquatic organisms.
ところで、本発明に係る船底塗料は、はけ塗り、スプレー塗装、静電塗装、フローコート及び浸漬塗り等の手段などにより直接船底に塗布したり、この船底塗料をフィルムなどに塗布した後に、当該フィルムを船底に貼り付けたりして、船底に担持され、船底表面を保護するものである。 By the way, the ship bottom paint according to the present invention is applied directly to the ship bottom by means such as brush coating, spray coating, electrostatic coating, flow coating and dip coating, or after applying this ship bottom coating to a film or the like. A film is attached to the bottom of the ship and is carried on the bottom of the ship to protect the bottom surface.
そして、本発明に係る船底塗料においては、活性炭粉末及び光触媒材料を含有させた点、に最も大きな特徴を有するのである。 The ship bottom paint according to the present invention has the greatest feature in that it contains activated carbon powder and a photocatalytic material.
即ち、本発に係る船底塗料においては、酸化チタンなどの光触媒材料を含有させているから、光触媒材料の光分解（酸化）作用によって、水棲生物の付着を抑制することができるので、船底の外観及び滑らかさを維持することができる結果、推進量の低下及び燃費の悪化を防止することができるのである。 That is, since the ship bottom paint according to the present invention contains a photocatalytic material such as titanium oxide, the photodecomposition (oxidation) action of the photocatalyst material can suppress the attachment of aquatic organisms. In addition, as a result of maintaining smoothness, it is possible to prevent a reduction in propulsion amount and a deterioration in fuel consumption.
特に、本発明の船底塗料においては、光触媒材料と共に活性炭粉末が含有されているから、活性炭粉末が光触媒材料を吸着し、塗料中のバインダー成分がボロボロになっても、光触媒材料の剥がれ落ちを抑制することができるので、長期間にわたって安定した防汚能力を発現することができるのである。 In particular, since the ship bottom paint of the present invention contains activated carbon powder together with the photocatalyst material, even if the activated carbon powder adsorbs the photocatalyst material and the binder component in the paint becomes tattered, the photocatalyst material is prevented from peeling off. Therefore, a stable antifouling ability can be expressed over a long period of time.
又、本発明の船底塗料においては、船底塗料中に光触媒材料と共に活性炭粉末を含有することにより、活性炭粉末が太陽光などの紫外線領域の光線が当たることによってスーパーオキサイドアニオン（Ｏ2-）やヒドロキシラジカル（・ＯＨ）などのラジカル基が生成するが、このスーパーオキサイドアニオン（Ｏ2-）やヒドロキシラジカル（・ＯＨ）などのラジカル基が前記活性炭粉末に吸着されてそれらの拡散、喪失を防止し、これらのラジカル基の有効利用を図ることができると共に、この吸着によって塗料中のバインダー成分がボロボロになるのを防止し得るのである。 Further, in the ship bottom paint of the present invention, by containing activated carbon powder together with the photocatalyst material in the ship bottom paint, the activated carbon powder is exposed to light in the ultraviolet region such as sunlight, thereby superoxide anion (O 2− ) and hydroxy. Radical groups such as radicals (.OH) are generated. Radical groups such as superoxide anion (O 2- ) and hydroxy radicals (.OH) are adsorbed on the activated carbon powder to prevent their diffusion and loss. In addition to the effective utilization of these radical groups, it is possible to prevent the binder component in the paint from becoming tattered by this adsorption.
更に、本発明の船底塗料においては、船底に付着する水棲生物や有機性のゴミが活性炭に速やかに吸着されるため、光触媒材料の分解（酸化）作用によって、非常に効率よく、有機物を分解することができるのである。 Furthermore, in the ship bottom paint of the present invention, aquatic organisms and organic waste adhering to the ship bottom are quickly adsorbed by the activated carbon, so that the organic matter is decomposed very efficiently by the decomposition (oxidation) action of the photocatalytic material. It can be done.
本発明の船底塗料において用いられる活性炭粉末としては、特に限定されるものではなく、工業用の触媒担体、脱臭剤、有機溶剤の回収等に用いられる通常の活性炭を粉末状に加工して用いることができる。 The activated carbon powder used in the ship bottom paint of the present invention is not particularly limited, and normal activated carbon used for recovery of industrial catalyst carriers, deodorizers, organic solvents, etc. is processed into powder and used. Can do.
又、本発明の船底塗料において、活性炭粉末の原料としては特に限定されるものではなく、具体的には、例えば木材、おがくず、木材乾留物、木炭、椰子殻又はリグニン等の既知の活性炭原料を好適に用いることができるが、中でも、入手し易く、安価でしかも吸着能力の高い椰子殻を用いることが特に好ましい。 In the ship bottom paint of the present invention, the raw material for the activated carbon powder is not particularly limited. Specifically, for example, a known activated carbon raw material such as wood, sawdust, wood dry matter, charcoal, coconut shell, or lignin is used. Among them, it is particularly preferable to use a coconut shell that is easily available, inexpensive, and has a high adsorption ability.
そして、本発明の船底塗料は、この活性炭粉末と共に光触媒材料を含有させたものであるが、この光触媒材料としては、光吸収によって光触媒反応を起こし、船底にフジツボや海草、海藻等に代表される水棲生物や有機物を分解、忌避し得るものであれば特に制限されるものでない。 The ship bottom paint of the present invention contains a photocatalyst material together with the activated carbon powder. As the photocatalyst material, a photocatalytic reaction is caused by light absorption, and the ship bottom is represented by barnacles, seaweed, seaweed and the like. It is not particularly limited as long as it can decompose and avoid aquatic organisms and organic matter.
なお、光触媒反応は反応系に光エネルギーが加わるので、反応系自身としてはギブスの自由エネルギーが減少する場合と増加する場合の双方があり、一般に後者を光触媒反応とは区別して取り扱う場合もあるが、本発明における光触媒反応は双方の場合を特に区別する必要はないのである。 In addition, since photocatalytic reaction adds light energy to the reaction system, the reaction system itself has both cases where the Gibbs free energy decreases and increases. In general, the latter may be handled separately from the photocatalytic reaction. The photocatalytic reaction in the present invention does not need to be distinguished between the two cases.
具体的な光触媒材料の例としては、例えば、ＴｉＯ2、ＺｎＯ、ＳｒＴｉＯ3、ＣｄＳ、ＣｄＯ、ＣａＰ、ＩｎＰ、Ｉｎ2Ｏ3、ＣａＡｓ、ＢａＴｉＯ3、Ｋ2ＮｂＯ3、Ｆｅ2Ｏ3、Ｔａ2Ｏ5、ＷＯ3、ＳｎＯ2、Ｂｉ2Ｏ3、ＮｉＯ、Ｃｕ2Ｏ、ＳｉＣ、ＳｉＯ2、ＭｏＳ2、ＭｏＳ3、ＩｎＰｂ、ＲｕＯ2及びＣｅＯ2等を挙げることができるのであり、本発明においてはこれらの光触媒材料から選ばれた少なくとも１種以上を用いることができる。 Specific examples of the photocatalytic material include, for example, TiO 2 , ZnO, SrTiO 3 , CdS, CdO, CaP, InP, In 2 O 3 , CaAs, BaTiO 3 , K 2 NbO 3 , Fe 2 O 3 , Ta 2. In the present invention, O 5 , WO 3 , SnO 2 , Bi 2 O 3 , NiO, Cu 2 O, SiC, SiO 2 , MoS 2 , MoS 3 , InPb, RuO 2, and CeO 2 can be mentioned. At least one selected from these photocatalytic materials can be used.
特に、本発明においては、これら光触媒材料のうち、アナターゼ型ＴｉＯ2を必須成分とすることが特に好ましい。 In particular, in the present invention, among these photocatalytic materials, it is particularly preferable to use anatase TiO 2 as an essential component.
この理由としては、光触媒材料としてのアナターゼ型ＴｉＯ2は光り触媒としての活性度が極めて高く、光吸収によって優れた光触媒反応を起こし、船底にフジツボや海草、海藻等に代表される水棲生物や有機物を一層分解、忌避し得るからである。 The reason for this is that anatase-type TiO 2 as a photocatalyst material has a very high activity as a photocatalyst, causes an excellent photocatalytic reaction by light absorption, and aquatic organisms and organic substances typified by barnacles, seaweeds, seaweeds, etc. This is because it can be further decomposed and avoided.
なお、活性炭粉末と光触媒材料の混合割合としては、船舶の使用状況、特に使用海域における水棲生物の発生程度や汚染程度に応じて適宜決定すれば良いから特に限定されるものではないが、一般的には、船底塗料中の活性炭粉末１００重量部に対して、光触媒材料を２０〜２００重量部程度の配合割合とすることが好ましく、特に、船底塗料中に配合する光触媒材料のうち、ＴｉＯ2、特に、アナターゼ型ＴｉＯ2を必須成分とし、光触媒材料全体の２０〜１００重量％をアナターゼ型ＴｉＯ2とすることが好ましく、特に３５〜１００重量％とするのが一層好ましい。 The mixing ratio of the activated carbon powder and the photocatalyst material is not particularly limited because it may be determined as appropriate according to the state of use of the ship, particularly the degree of occurrence of aquatic organisms and the degree of contamination in the sea area of use. Is preferably about 20 to 200 parts by weight of the photocatalyst material with respect to 100 parts by weight of the activated carbon powder in the ship bottom paint. Particularly, among the photocatalyst materials to be blended in the ship bottom paint, TiO 2 , In particular, it is preferable to use anatase TiO 2 as an essential component, and 20 to 100% by weight of the entire photocatalytic material is preferably anatase TiO 2, and more preferably 35 to 100% by weight.
上述の如く、本発明の船底塗料においては、光触媒材料と共に活性炭粉末が含有されているから、活性炭粉末が光触媒材料を吸着し、しかも、前述の理由により、塗料中のバインダー成分がボロボロになり難くなる結果、光触媒材料の剥がれ落ちを抑制し得るのであり、従って、長期間にわたって安定した防汚能力を発現することができる上、船底に付着する水棲生物や有機性のゴミが活性炭に速やかに吸着されるため、非常に効率よく、有機物を分解、忌避することができるのである。 As described above, in the ship bottom paint of the present invention, the activated carbon powder is contained together with the photocatalyst material. Therefore, the activated carbon powder adsorbs the photocatalyst material, and the binder component in the paint does not easily become tattered for the above-described reason. As a result, the photocatalyst material can be prevented from peeling off, so that stable antifouling ability can be expressed over a long period of time, and aquatic organisms and organic waste adhering to the bottom of the ship can be quickly adsorbed to the activated carbon. Therefore, the organic matter can be decomposed and avoided very efficiently.
即ち、本発明の船底塗料においては、前述の理由により、光触媒材料と活性炭粉末が近接した状態で存在すればするほどこの効果が向上するのであり、従って、本発明においては、活性炭粉末の表面に光触媒材料を担持させることが一層好ましい。 That is, in the ship bottom paint of the present invention, for the reasons described above, this effect is improved as the photocatalyst material and the activated carbon powder are in close proximity. Therefore, in the present invention, the surface of the activated carbon powder is improved. It is more preferable to carry a photocatalytic material.
ここで、本発明の船底塗料において、活性炭粉末の表面に光触媒材料を担持させる方法としては、接着剤などのバインダーを用いて活性炭粉末の表面に光触媒材料を担持させても良いが、本発明においては、蒸着手段により、活性炭粉末表面に光触媒材料の被膜を形成・担持させる手段を用いることが特に好ましい。 Here, in the ship bottom paint of the present invention, as a method for supporting the photocatalytic material on the surface of the activated carbon powder, the photocatalytic material may be supported on the surface of the activated carbon powder using a binder such as an adhesive. It is particularly preferable to use means for forming and supporting a film of the photocatalytic material on the surface of the activated carbon powder by vapor deposition means.
即ち、本発明の船底塗料においては、接着剤などのバインダーを用いない手段により光触媒材料を担持させることにより、埋没に起因する光触媒材料の微粒子成分に対する分解作用の減少を防止することができるのであり、更に、光触媒材料の被膜を非常に薄く形成することができるから、係る被膜が活性炭粉末表面の微細孔を覆っても、活性炭粉末の吸着能力を殆ど損ねることがないことから特に好ましいのである。 That is, in the ship bottom paint of the present invention, by supporting the photocatalyst material by means that does not use a binder such as an adhesive, it is possible to prevent a decrease in the decomposition action on the fine particle component of the photocatalyst material due to burial. Furthermore, since the coating film of the photocatalytic material can be formed very thin, even if the coating film covers the fine pores on the surface of the activated carbon powder, it is particularly preferable because the adsorption ability of the activated carbon powder is hardly impaired.
なお、活性炭粉末表面に蒸着手段により光触媒材料を担持させる方法としては、例えば、スパッタリング、グロー放電、熱蒸着、化学蒸着或いはイオンプレーティング等のいわゆる薄膜作成技術を好適に用いることができるのであり、本発明においては、これらの蒸着手段から選ばれた１種或いは２種以上を組み合わせて用いることができるが、特に、本発明においては、簡便で経済的であり、しかも付着速度が速く効率が高い真空熱蒸着の手段を用いることが好ましい。 As a method for supporting the photocatalytic material on the activated carbon powder surface by vapor deposition means, for example, a so-called thin film production technique such as sputtering, glow discharge, thermal vapor deposition, chemical vapor deposition, or ion plating can be suitably used. In the present invention, one or a combination of two or more selected from these vapor deposition means can be used. In particular, in the present invention, it is simple and economical, and has a high deposition rate and high efficiency. It is preferable to use means of vacuum thermal evaporation.
又、本発明における前記蒸着手段において、活性炭粉末表面に形成・担持させる光触媒材料の量は、特に限定されるものではないが、一般的には、活性炭粉末１００重量部に対して、光触媒材料を２０〜２００重量部程度担持させることが好ましい。 In the vapor deposition means of the present invention, the amount of the photocatalyst material formed / supported on the surface of the activated carbon powder is not particularly limited, but in general, the photocatalyst material is added to 100 parts by weight of the activated carbon powder. It is preferable to carry about 20 to 200 parts by weight.
更に、一定量の光触媒材料を一回の蒸着処理で形成・担持させるよりも、２回以上の複数回に分けて形成・担持させるほうが、活性炭粉末表面に光触媒材料がより強固に担持されるため好ましい。 Furthermore, the photocatalyst material is more firmly supported on the activated carbon powder surface by forming and supporting a certain amount of photocatalyst material in two or more times, rather than forming and supporting it in a single vapor deposition process. preferable.
なお、本発明の船底塗料においては、必要に応じて、通常の塗料に使用される各種の顔料、溶剤、各種添加剤などを配合しても良いのである。 In the ship bottom paint of the present invention, various pigments, solvents, various additives and the like used in ordinary paints may be blended as necessary.
具体的な顔料の例としては、二酸化チタン、酸化亜鉛、硫化亜鉛、リトポン、鉛顔料、酸化アンチモン、酸化ジルコニウム又はジルコン等の白色顔料、含水マグネシウムアルミニウムケイ酸塩、炭酸カルシウム、硫酸バリウム、ケイ酸塩、アルミノケイ酸カリウム又は水和アルミナ等の体質顔料、酸化鉄顔料、クロム酸鉛、モリブデン酸鉛、カドミウム顔料、合成金属酸化物混合物又は紺青等の有採無機顔料、ジンクイエロー、塩基性クロム酸亜鉛、クロム酸ストロンチウム、鉛丹、酸化銅（ｌ）、鉛酸カルシウム、塩基性シリコクロム酸鉛、ホワイトモリブデート、変性メタホウ酸バリウム、リン酸亜鉛又はパールエッセンス等の特殊顔料及び金属顔料等を挙げることができるのであり、本発明においては、これらの無機顔料から選ばれた少なくとも１種以上を用いることができる。 Examples of specific pigments include titanium dioxide, zinc oxide, zinc sulfide, lithopone, lead pigments, white pigments such as antimony oxide, zirconium oxide or zircon, hydrous magnesium aluminum silicate, calcium carbonate, barium sulfate, silicic acid. Organic pigments such as salts, potassium aluminosilicate or hydrated alumina, iron oxide pigments, lead chromate, lead molybdate, cadmium pigments, synthetic metal oxide mixtures or bitumen, zinc yellow, basic chromic acid Special pigments and metal pigments such as zinc, strontium chromate, red lead, copper oxide (l), calcium leadate, basic silicochromate, white molybdate, modified barium metaborate, zinc phosphate or pearl essence In the present invention, these inorganic pigments were selected. Even without it is possible to use one or more.
又、具体的な溶剤の例としては、イソプロピルアルコール、ｎ−ブチルアルコール、イソブチルアルコール、ブチルセロソルブ、エチルセロソルブ、メチルエチルケトン、メチルイソブチルケトン、キシレン又はトルエン等を挙げることができるのであり、塗装作業性や塗膜乾燥性などを向上させるために、これらの溶剤から選ばれた少なくとも２種以上を混合して用いても良い。 Specific examples of the solvent include isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, butyl cellosolve, ethyl cellosolve, methyl ethyl ketone, methyl isobutyl ketone, xylene, and toluene. In order to improve the film drying property, at least two selected from these solvents may be mixed and used.
更に、各種添加剤としては、防錆剤、タレ止め剤、湿潤剤、反応促進剤、沈殿防止剤などを必要に応じて適宜配合することができる。 Furthermore, as various additives, a rust preventive agent, an anti-sagging agent, a wetting agent, a reaction accelerator, a precipitation inhibitor and the like can be appropriately blended as necessary.
本発明は、前記構成を有し、活性炭の吸着作用と光触媒材料の分解（酸化）・殺菌作用を組み合わせることにより、光触媒材料の光分解（酸化）作用によって、水棲生物の付着を忌避、抑制し、長期間に亘る安定した防汚能力を発現し得るのである。 The present invention has the above-described configuration, and by combining the adsorption action of activated carbon and the decomposition (oxidation) / sterilization action of the photocatalyst material, the photodegradation (oxidation) action of the photocatalyst material prevents and suppresses the attachment of aquatic organisms. Thus, a stable antifouling ability over a long period of time can be expressed.
即ち、本発明の船底塗料においては、酸化チタンなどの光触媒材料を含有させているから、水棲生物の付着を忌避、抑制することができるのであり、これにより、船底の外観及び滑らかさを維持することができる結果、推進量の低下及び燃費の悪化を防止することができるなどの効果を奏するのである。 In other words, since the ship bottom paint of the present invention contains a photocatalytic material such as titanium oxide, adhesion of aquatic organisms can be avoided and suppressed, thereby maintaining the appearance and smoothness of the ship bottom. As a result, effects such as reduction in propulsion amount and deterioration in fuel consumption can be achieved.
特に、本発明の船底塗料においては、船底塗料中に光触媒材料と共に活性炭粉末を含有することにより、活性炭粉末が太陽光などの紫外線領域の光線が当たることによってスーパーオキサイドアニオン（Ｏ2-）やヒドロキシラジカル（・ＯＨ）などのラジカル基が生成するが、このスーパーオキサイドアニオン（Ｏ2-）やヒドロキシラジカル（・ＯＨ）などのラジカル基が前記活性炭粉末に吸着されてそれらの拡散、喪失を防止し、これらのラジカル基の有効利用を図ることができると共に、この吸着によって塗料中のバインダー成分がボロボロになるのを防止し得るなどの効果を奏するのである。 In particular, in the ship bottom paint of the present invention, by containing activated carbon powder together with a photocatalyst material in the ship bottom paint, the activated carbon powder is exposed to light in the ultraviolet region such as sunlight, thereby superoxide anion (O 2− ) and hydroxy Radical groups such as radicals (.OH) are generated. Radical groups such as superoxide anion (O 2- ) and hydroxy radicals (.OH) are adsorbed on the activated carbon powder to prevent their diffusion and loss. In addition to the effective utilization of these radical groups, the adsorption component can prevent the binder component in the paint from becoming tattered.
更に、本発明の船底塗料においては、船底に付着する水棲生物や有機性のゴミが活性炭に速やかに吸着されるため、光触媒材料の分解（酸化）作用によって、非常に効率よく、有機物を分解することができるなどの効果を奏するのである。 Furthermore, in the ship bottom paint of the present invention, aquatic organisms and organic waste adhering to the ship bottom are quickly adsorbed by the activated carbon, so that the organic matter is decomposed very efficiently by the decomposition (oxidation) action of the photocatalytic material. It has the effect of being able to.
以下、本発明を実施例に基づき詳細に説明するが、本発明はこの実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to this Example.
＜光触媒材料を担持させた活性炭の作成＞
（１） 椰子殻を乾燥して微粉を除いた活性炭原料を焼成炭用ロータリーキルン（８５０〜９５０℃）に入れ、赤熱した状態で水蒸気、炭酸ガス（燃焼ガス中のＣＯ2）及び酸素（燃焼空気中のＯ2）で活性化することにより、粒状の活性炭（ＣＴＣ：５０．４２％）を得た。
（２） この得られた活性炭（１００重量部）を、粉末状に砕いた後、真空容器内に設けられたホルダーに設置して、当該ホルダーに設けられた攪拌棒で攪拌しながら約４２５℃に加温した。
（３） 一方、真空容器内に設けられた基台には、光触媒材料であるアナターゼ型ＴｉＯ2（５０重量部）を設置し、これを蒸発源とした。
（４） 引き続いて、真空容器内に充填されている窒素ガスを真空ポンプを用いて吸引し、真空容器内部を減圧し、３．５×１０-5ｍｍＨｇに達した時点で、基台をヒーターで加熱し、前記酸化チタンを蒸発させ、ホルダー上の活性炭表面に当該酸化チタンの被膜を形成・担持させることにより、光触媒材料が表面に担持された活性炭粉末を得た。
<Creation of activated carbon carrying photocatalytic material>
(1) The activated carbon raw material from which the coconut shell is dried and fine powder is removed is put into a rotary kiln for calcined charcoal (850 to 950 ° C.), and in a red hot state, water vapor, carbon dioxide (CO 2 in the combustion gas) and oxygen (combustion air) By activating with O 2 ) in the middle, granular activated carbon (CTC: 50.42%) was obtained.
(2) After the obtained activated carbon (100 parts by weight) was crushed into a powder, it was placed in a holder provided in a vacuum vessel, and stirred at about 425 ° C. with a stirring rod provided in the holder. Warmed to.
(3) On the other hand, anatase TiO 2 (50 parts by weight), which is a photocatalytic material, was installed on the base provided in the vacuum vessel, and this was used as the evaporation source.
(4) Subsequently, nitrogen gas filled in the vacuum vessel is sucked using a vacuum pump, the inside of the vacuum vessel is depressurized, and when the pressure reaches 3.5 × 10 −5 mmHg, the base is heated. The titanium oxide was evaporated, and the titanium oxide film was formed and supported on the surface of the activated carbon on the holder to obtain activated carbon powder having the photocatalytic material supported on the surface.
（１） プロピレングリコールメチルエーテル８５重量部及び上記アナターゼ型ＴｉＯ2が表面に担持された活性炭粉末４０重量部を仕込み、撹拌しながら７５℃に昇温した。
（２） 続いて、メタクリル酸４５重量部、アクリル酸３５重量部及び水５重量部からなる混合物を３時間で等速滴下した。
（３） 更に、２時間撹拌した後、プロピレングリコールメチルエーテルを３５重量部添加して、アナターゼ型ＴｉＯ2（光触媒材料）が表面に担持された活性炭粉末を含有する本発明の船底塗料を得た。
(1) 85 parts by weight of propylene glycol methyl ether and 40 parts by weight of activated carbon powder on which the anatase TiO 2 was supported were charged and heated to 75 ° C. while stirring.
(2) Subsequently, a mixture composed of 45 parts by weight of methacrylic acid, 35 parts by weight of acrylic acid and 5 parts by weight of water was dropped at a constant rate over 3 hours.
(3) Further, after stirring for 2 hours, 35 parts by weight of propylene glycol methyl ether was added to obtain a ship bottom paint of the present invention containing activated carbon powder having anatase TiO2 (photocatalytic material) supported on the surface.
光触媒材料として実施例１で用いたものと同様のアナターゼ型酸化チタン（ＴｉＯ2）粉末１５重量部を用いた以外は、実施例１と同様にして比較例１に係る船底塗料を得た。 即ち、比較例１に係る船底塗料には、アナターゼ型酸化チタン（ＴｉＯ2）のみからなり、活性炭粉末が全く含有されていないものである。 A ship bottom paint according to Comparative Example 1 was obtained in the same manner as in Example 1, except that 15 parts by weight of anatase-type titanium oxide (TiO2) powder similar to that used in Example 1 was used as the photocatalytic material. That is, the ship bottom paint according to Comparative Example 1 is made of only anatase-type titanium oxide (TiO2) and does not contain any activated carbon powder.
実施例１で用いたものと同様の活性炭粉末１５重量部を用いた以外は、実施例１と同様にして船底塗料を得た。
即ち、比較例２に係る船底塗料には、活性炭粉末のみが配合されたものとなる。
A ship bottom paint was obtained in the same manner as in Example 1 except that 15 parts by weight of activated carbon powder similar to that used in Example 1 was used.
That is, only the activated carbon powder is blended in the ship bottom paint according to Comparative Example 2.
＜テストピースの作成＞
（１） ショットブラスト鋼材（ＪＩＳ Ｇ ３１０１、７０ｍｍ×１５０ｍｍ×３．２ｍｍ）の表面をヘキサンで脱脂し、乾燥させた。
（２） この鋼材の表面に変性エポキシ系下塗塗料（カナエ塗料株式会社 商品名 ＦＲＣプライマー）をエアスプレーを用いて塗装し、乾燥させた（乾燥膜厚２５μｍ）。
（３） 充分に乾燥させた後、上記の実施例１及び比較例１・２に係る船底塗料をそれぞれ個別にエアスプレーを用いて塗装し、乾燥させた（乾燥膜厚４０μｍ）。
<Create test piece>
(1) The surface of shot blast steel (JIS G 3101, 70 mm × 150 mm × 3.2 mm) was degreased with hexane and dried.
(2) The surface of this steel material was coated with a modified epoxy base coat (Kanae Paint Co., Ltd., trade name: FRC primer) using an air spray and dried (dry film thickness 25 μm).
(3) After sufficiently drying, the ship bottom paints according to Example 1 and Comparative Examples 1 and 2 were individually applied using an air spray and dried (dry film thickness 40 μm).
得られた３枚のテストピースの表面に青色の有機性顔料を塗布し、紫外線を２４時間照射した後の表面状態を目視で観察した。 A blue organic pigment was applied to the surface of the obtained three test pieces, and the surface state after irradiation with ultraviolet rays for 24 hours was visually observed.
その結果、実施例１及び比較例１に係る船底塗料を塗布したテストピースにおいては、表面に塗布された有機性顔料を殆ど目視することができず、光触媒機能により、有機性顔料が分解されていることが認められた。 As a result, in the test piece to which the ship bottom paint according to Example 1 and Comparative Example 1 was applied, the organic pigment applied to the surface was hardly visible, and the organic pigment was decomposed by the photocatalytic function. It was recognized that
しかしながら、比較例１に係る船底塗料を塗布したテストピースにおいては、テストピース表面にチョークのような白い粉が吹き出す、いわゆる「チョーキング現象」が発生していることが確認された。 However, in the test piece to which the ship bottom paint according to Comparative Example 1 was applied, it was confirmed that a so-called “choking phenomenon” in which white powder such as chalk blows out on the test piece surface occurred.
一方、比較例２に係る船底塗料を塗布したテストピースにおいては、表面に塗布された有機性顔料が殆ど残存しており、光触媒機能を有していないことが認められたが、活性炭によって僅かに有機性顔料が吸着されていることが認められた。 On the other hand, in the test piece to which the ship bottom paint according to Comparative Example 2 was applied, it was recognized that the organic pigment applied on the surface remained almost and did not have a photocatalytic function. It was observed that the organic pigment was adsorbed.
又、実施例１及び比較例１・２に係る船底塗料を塗布したテストピースを用い、和歌山県串本港沖において、深さ３ｍに沈め、６０日間放置した。 Further, using the test piece coated with the ship bottom paint according to Example 1 and Comparative Examples 1 and 2, it was submerged to a depth of 3 m off Kushimoto Port off Wakayama Prefecture and left for 60 days.
その結果、実施例１のものはフジツボや海草、海藻等の水棲生物の付着は認められなかったが、比較例１のものはその塗料中のバインダー成分が一部ボロボロになって剥がれ落ち、その部位に海草や海藻の付着が認められたが、フジツボの付着は確認されなかった。 一方、比較例２のものについては、フジツボの付着が確認され、又、海草や海藻がかなり生息していることが認められた。 As a result, no adhesion of aquatic organisms such as barnacles, seaweeds, seaweeds, etc. was observed in Example 1, but in Comparative Example 1, the binder component in the paint was partly tattered and peeled off. Although adhesion of seaweed and seaweed was observed at the site, no adhesion of barnacles was confirmed. On the other hand, in the case of Comparative Example 2, adhesion of barnacles was confirmed, and it was recognized that seaweeds and seaweeds were considerably inhabited.
Claims (6)
The ship bottom paint according to claim 5, wherein the photocatalyst material is supported on the surface of the activated carbon powder by vapor deposition means.
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| CN109794268A (en) * | 2019-01-23 | 2019-05-24 | 北京科技大学 | MoSe2Nanometer sheet coats KNbO3The preparation method of nano wire hetero structure catalysis material |
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