KR101670428B1 - Antifouling coating composition, and fishing net, fishing net gear, and underwater structure coated with antifouling coating composition - Google Patents
Antifouling coating composition, and fishing net, fishing net gear, and underwater structure coated with antifouling coating composition Download PDFInfo
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- KR101670428B1 KR101670428B1 KR1020137012933A KR20137012933A KR101670428B1 KR 101670428 B1 KR101670428 B1 KR 101670428B1 KR 1020137012933 A KR1020137012933 A KR 1020137012933A KR 20137012933 A KR20137012933 A KR 20137012933A KR 101670428 B1 KR101670428 B1 KR 101670428B1
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- South Korea
- Prior art keywords
- copper
- antifouling
- mass
- parts
- content
- Prior art date
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- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 105
- 239000008199 coating composition Substances 0.000 title description 9
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- 239000010949 copper Substances 0.000 claims abstract description 81
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 36
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 24
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011701 zinc Substances 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 235000020638 mussel Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Chemical group 0.000 description 1
- 229910052760 oxygen Chemical group 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XNFIRYXKTXAHAC-UHFFFAOYSA-N tralopyril Chemical compound BrC1=C(C(F)(F)F)NC(C=2C=CC(Cl)=CC=2)=C1C#N XNFIRYXKTXAHAC-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000003871 white petrolatum Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229940043810 zinc pyrithione Drugs 0.000 description 1
- HQBBDVUXOOMFQN-UHFFFAOYSA-L zinc;2,2-dimethylpropanoate Chemical compound [Zn+2].CC(C)(C)C([O-])=O.CC(C)(C)C([O-])=O HQBBDVUXOOMFQN-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01K—ANIMAL HUSBANDRY; AVICULTURE; APICULTURE; PISCICULTURE; FISHING; REARING OR BREEDING ANIMALS, NOT OTHERWISE PROVIDED FOR; NEW BREEDS OF ANIMALS
- A01K75/00—Accessories for fishing nets; Details of fishing nets, e.g. structure
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
- A01N59/20—Copper
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/40—Glass
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Environmental Sciences (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- General Health & Medical Sciences (AREA)
- Plant Pathology (AREA)
- Zoology (AREA)
- Agronomy & Crop Science (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Marine Sciences & Fisheries (AREA)
- Inorganic Chemistry (AREA)
- Biodiversity & Conservation Biology (AREA)
- Animal Husbandry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Toxicology (AREA)
- Paints Or Removers (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Farming Of Fish And Shellfish (AREA)
Abstract
따개비나 서관충 등 동물류나 히드로충 등 강장동물의 활성이 강한 해역에 있어서도, 장기간 방오효과를 발휘할 수 있는 방오 도료 조성물을 제공한다. 본 발명에 의하면, (A) 2가의 구리를 포함하는 구리 유리, (B) 금속 피리치온류, 및 (C) 산화 티타늄을 함유하는 방오 도료 조성물로서, 상기 금속 피리치온류의 금속은 구리 또는 아연이며, 전착수지를 더욱 함유하며, 상기 구리 유리(A) 중의 CuO의 함유량은 25~40몰%이며, 상기 구리 유리(A)의 함유량은 고형분 환산으로 상기 방오 도료 조성물의 고형분 중 1~20질량%이며, 상기 금속 피리치온류(B)의 함유량은 고형분 환산으로 상기 구리 유리(A) 100질량부에 대하여 25~150질량부이며, 상기 산화 티타늄(C)의 함유량은 고형분 환산으로 상기 구리 유리(A) 100질량부에 대하여 50~300질량부인 방오 도료 조성물이 제공된다. Provided is an antifouling paint composition capable of exhibiting a long-term antifouling effect even in a marine area having high activity of a tanned animal such as a barnacle or a western shore, such as an animal or a hydrosphere. According to the present invention, there is provided an antifouling paint composition comprising (A) a copper glass containing bivalent copper, (B) a metal pyrite warming agent, and (C) titanium oxide, wherein the metal of the metal pyrite warming agent is copper or zinc The content of CuO in the copper glass (A) is 25 to 40 mol%, and the content of the copper glass (A) is 1 to 20 mass% in terms of solid content of the solid content of the antifouling paint composition (B) is 25 to 150 parts by mass based on 100 parts by mass of the copper glass (A) in terms of solid content, and the content of the titanium oxide (C) And 50 to 300 parts by mass with respect to 100 parts by mass of the antifouling paint composition (A).
Description
본 발명은, 양식용 또는 정치망용(定置網用)의 어망, 상기 어망에 사용되는 낚시찌자, 로프 등 어망용구(이하, 어망류라 칭함) 및 발전소의 냉각 수도관 등 수중 구축물 등에 해양 오염 유기물이 부착되는 것을 오랜 시간에 걸쳐 방지하기 위한 방오 도료 조성물, 및 상기 방오 도료 조성물이 도포된 어망류 및 수중 구축물에 관한 것이다. Industrial Applicability The present invention relates to a method and a device for attaching marine polluted organic matters to fisheries such as fishing nets for aquaculture or settling net, fishing nets used for fishing nets, fishing nets such as ropes (hereinafter referred to as fishing nets) An antifouling coating composition for preventing the antifouling paint composition over a long period of time, and a fishing net and an underwater construction coated with the antifouling paint composition.
어망류 및 수중 구축물 등은 바다 중에 오랜 시간 설치되어 있기 때문에, 방오 도료 조성물을 도포하지 않고 사용하면 해초류, 따개비, 서관충, 이끼 벌레, 연체 동물류 등 여러 가지 해양 오염 유기물이 부착된다. 따라서, 어망의 내측과 외측 사이에서의 바다물의 왕래가 나빠지고, 산소 결핍에 의해 양식 물고기가 대량으로 죽거나, 또한 전염병이 발생하여 출하(出荷)할 수 없게 되는 등 큰 손해가 생긴다. 또한, 양식망이나 정치망 등에 부착생물이 부착되면 그물이 무거워지며, 그물의 침하(沈下)에 의하여 물고기가 도망치거나, 그물 자체가 유출(流出)되는 문제가 존재한다. 때문에 빈번히 그물을 바꿀 필요가 있고, 이것들을 유지하기 위하여 엄청난 노동력과 비용을 쓰지 않으면 안 되는 문제가 존재한다. Since the fishing nets and underwater structures are installed in the sea for a long time, various kinds of marine organic matters such as seaweeds, barnacles, worms, molluscs and other marine animals are attached when they are used without applying the antifouling paint composition. Therefore, the sea water between the inside and the outside of the fishing net deteriorates, and a large amount of fish are killed due to the oxygen deficiency, and the infectious disease is caused and the ship can not be shipped. In addition, there is a problem that if the attached organisms are attached to the aquaculture net or set net, the net becomes heavy, and the fish run away due to settlement of the net or the net itself flows out. Therefore, there is a need to change the net frequently, and there is a problem that requires huge labor and cost to maintain them.
이러한 해양 오염 유기물의 부착 방지 등을 목적으로, 어망류 및 수중 구축물에는 여러 가지 방오 도료 조성물의 도포가 널리 행하여져 왔다. 이러한 방오 도료 조성물 중에서도, 특히, 아산화구리, 구리 유리 및 구리 피리치온(pyrithione) 등 구리계 약제를 함유한 방오 도료 조성물은, 홍합(mussel) 등 조개류, 따개비 및 서관충 등 부착 방지에 일정한 효과를 나타내기 때문에 널리 이용되어 왔다. In order to prevent adhesion of marine polluted organic matter, application of various antifouling paint compositions has been widely carried out on fishing nets and underwater constructions. Among these antifouling paint compositions, antifouling paint compositions containing copper-based agents such as copper oxide, copper glass, and copper pyrithione are particularly effective in preventing adhesion of mussels, shellfish, And thus it has been widely used.
예를 들면, 따개비나 서관충 등 동물류나 히드로충(hydrozoan) 등의 강장동물에 대하여 뛰어난 방오 도료 조성물로서, 아산화구리와 특정 폴리 에테르 변성 실리콘 오일을 배합한 방오제 조성물이 제안되어 있다(특허문헌 1). 또한, 아산화구리와 특정 폴리 에테르 변성 실리콘 오일에, 구리 피리치온을 배합한 방오 도료 조성물도 제안되어 있다(특허문헌 2). For example, there has been proposed an antifouling agent composition in which copper oxide and a specific polyether-modified silicone oil are blended as an excellent antifouling paint composition for a tanning animal such as a barnacle, a horse mackerel, an animal, or a hydrozoan One). Further, an antifouling paint composition in which copper perchlorate is blended with copper oxide and a specific polyether-modified silicone oil has also been proposed (Patent Document 2).
그러나, 이것들의 방오 도료 조성물에 이용되는 아산화구리는, 물에 녹기 어렵고, 이온화되기 어렵기 때문에, 해양 오염 유기물에 대한 충분한 기피(忌避) 효과를 발휘할 수 없으며, 충분한 방오 효과를 발휘하지 못하였다. However, since the copper oxide used in these antifouling paint compositions is difficult to dissolve in water and hardly ionized, it can not exhibit a sufficient repelling effect on marine polluted organic matter, and fails to exhibit a sufficient antifouling effect.
또한, 아산화구리 대신으로 1가 구리를 포함하는 용해성 구리 유리를 이용하여, 금속 피리치온류와 병용하는 것을 특징으로 하는 방오 도료 조성물이 제안되어 있다(특허문헌 3). 그러나, 상기 방오 도료 조성물에 이용되는 1가 구리를 포함하는 용해성 구리 유리는, 아산화구리에 비하여 구리 이온의 용출량은 높지만 아직 해양 오염 유기물에 대한 충분한 기피 효과를 발휘하지 못하였으며, 시장의 수요를 만족시키지 못하였다. Further, an antifouling paint composition is proposed in which a soluble copper glass containing monovalent copper is used instead of copper oxide to be used in combination with a metal pyrite warmer (Patent Document 3). However, the soluble copper glass containing monovalent copper used in the antifouling paint composition has a higher elution amount of copper ion than copper oxide, but has not yet sufficiently exhibited a repelling effect on the marine polluted organic matter and satisfies the market demand I can not.
또한, 2가 구리를 포함하는 구리 유리를 함유하는 방오 도료 조성물도 제안되어 있다 (특허문헌 4). 그러나, 상기 방오 도료 조성물은, 해양 오염 유기물에 대한 기피 효과가 아직 충분하지 않았다. Further, an antifouling paint composition containing copper glass containing divalent copper has also been proposed (Patent Document 4). However, the antifouling paint composition has not yet sufficiently avoided marine polluted organic matters.
때문에, 도막 물성이 좋으며 어망도포시의 작업성이 뛰어나며, 따개비나 서관충 등 동물류나 히드로충 등 강장동물의 활성이 강한 해역에 있어서, 장기간 방오효과를 발휘할 수 있는 어망용 방오 도료 조성물의 개발이 요구되고 있다. Therefore, the development of an antifouling paint composition for fishing nets capable of exhibiting a long-term antifouling effect in a sea area having good physical properties of coating film, excellent workability at the time of application of fishing nets, and strong activity of tanned animals such as barnacles, Is required.
본 발명은, 상기의 점에 비추어 행해진 것이며, 따개비나 서관충 등 동물류나 히드로충 등 강장동물의 활성이 강한 해역에 있어서도, 장기간 방오효과를 발휘할 수 있는 방오 도료 조성물을 제공하는 것이다. An object of the present invention is to provide an antifouling paint composition capable of exhibiting a long-term antifouling effect even in a sea area having a high activity of a tanning animal such as a barnacle,
본 발명에 의하면, (A) 2가의 구리를 포함하는 구리 유리, (B) 금속 피리치온류, 및 (C) 산화 티타늄을 함유하는 방오 도료 조성물로서, 상기 금속 피리치온류의 금속은 구리 또는 아연이며, 전착수지(展着樹脂)를 더 함유하며, 상기 구리 유리(A) 중의 CuO의 함유량은 25~40몰%이며, 상기 구리 유리(A)의 함유량은 고형분 환산으로 상기 방오 도료 조성물의 고형분 중 1~20질량%이며, 상기 금속 피리치온류(B)의 함유량은 고형분 환산으로 상기 구리 유리(A) 100질량부에 대하여 25~150질량부이며, 상기 산화 티타늄(C)의 함유량은 고형분 환산으로 상기 구리 유리(A) 100질량부에 대하여 50~300질량부인 방오 도료 조성물이 제공된다. According to the present invention, there is provided an antifouling paint composition comprising (A) a copper glass containing bivalent copper, (B) a metal pyrite warming agent, and (C) titanium oxide, wherein the metal of the metal pyrite warming agent is copper or zinc Wherein the content of CuO in the copper glass (A) is 25 to 40 mol%, and the content of the copper glass (A) in the copper glass (A) is a solid content of the antifouling paint composition (B) is 25 to 150 parts by mass based on 100 parts by mass of the copper glass (A) in terms of solid content, and the content of the titanium oxide (C) is in the range of 1 to 20% The antifouling paint composition is 50 to 300 parts by mass based on 100 parts by mass of the copper glass (A).
본 발명자들은, 장기간 방오효과를 발휘할 수 있는 방오 도료 조성물을 개발하기 위하여 연구를 거듭한 결과, 방오 도료 조성물이 (A) 2가 구리를 포함하는 구리 유리, (B) 금속 피리치온류, 및 (C) 산화 티타늄의 3성분을 특정 비율로 함유할 경우, 매우 뛰어난 장기방오성을 발휘할 수 있다는 것을 알아내어 본 발명을 완성하였다. The inventors of the present invention have conducted extensive studies to develop an antifouling coating composition capable of exhibiting an antifouling effect over a long period of time. As a result, the inventors have found that an antifouling paint composition comprises (A) copper glass containing bivalent copper, (B) C) titanium oxide is contained at a specific ratio, it is possible to exert a very excellent long-term antifouling property. The present invention has been completed based on this finding.
본 발명의 방오 도료 조성물이 우수한 장기방오성을 발휘하는 작용에 대하여 명확하지는 않지만, 실험적으로는 2가의 구리를 포함하는 구리 유리만을 포함하거나, 2가의 구리를 포함하는 구리 유리와 금속 피리치온류를 포함하는 것은 방오효과가 장기적으로 지속되지 않았고, 상기 3성분을 포함할 경우에 처음으로 우수한 장기방오성을 발휘한다는 것을 알았다. 방오효과를 갖게 되는 유효성분이 구리 유리와 금속 피리치온류인 것으로부터, 산화 티타늄은 구리 유리와 금속 피리치온류의 용출속도를 적당히 컨트롤하며, 긴 기간에 걸쳐 이것들의 유효성분을 안정된 속도로 용출시키는 역할을 할 수 있다고 추측된다. Although the effect of the antifouling paint composition of the present invention exhibiting excellent long-term antifouling properties is not clear, experimentally, it has been experimentally found that the antifouling coating composition contains copper glass containing bivalent copper or copper glass containing bivalent copper , It was found that the antifouling effect did not persist for a long period of time and that the antifouling effect exerted excellent long-term antifouling property for the first time when the antifouling effect was included. Since the active ingredient having an antifouling effect is copper glass and metal pyric oxide, titanium oxide can control the elution rate of the copper glass and the metal pyritic hot water appropriately and elongate these effective ingredients at a stable rate over a long period of time It is assumed that they can play a role.
한편, 1가 구리를 포함하는 구리 유리와 금속 피리치온류와 산화 티타늄의 3성분을 함유하는 도료 조성물이나, 아산화구리와 금속 피리치온류와 산화 티타늄의 3성분을 함유하는 도료 조성물의 장기방오성에 대하여 조사하였지만, 모두 본 발명과 비교하면 장기방오성이 뒤떨어져 있다. 이로부터, 본 발명에 의하여 발휘되는 매우 뛰어난 장기방오성은 방오 도료 조성물이 (A) 2가의 구리를 포함하는 구리 유리, (B) 금속 피리치온류, 및 (C) 산화 티타늄의 3성분을 특정한 비율로 함유함으로써 처음으로 발휘한다는 것이 밝혀져 본 발명을 완성할 수 있었다. On the other hand, a coating composition containing three components of copper glass containing monovalent copper, metallic pyrrichoids and titanium oxide, or a coating composition containing three components of copper oxide, metallic pliichonium and titanium oxide However, as compared with the present invention, the long-term antifouling property is inferior. From this, it can be seen that the antifouling coating composition exhibiting excellent antifouling property exhibited by the present invention is excellent in antifouling paint composition in which the three components of (A) copper glass containing bivalent copper, (B) metallic pyrites, and (C) And thus the present invention can be completed.
본 발명의 방오 도료 조성물에 의하면, 따개비나 서관충 등 동물류나 히드로충 등 강장동물의 활성이 강한 해역에서도, 장기간 방오효과를 발휘할 수 있다. According to the antifouling paint composition of the present invention, the antifouling effect can be exerted for a long period even in a sea area having strong activity of animal such as barnyard and western hallow, and animal such as hydrosphere.
본 발명의 방오 도료 조성물은, (A) 2가의 구리를 포함하는 구리 유리, (B) 금속 피리치온류, 및 (C) 산화 티타늄을 함유하는 방오 도료 조성물로서, 상기 금속 피리치온류의 금속은 구리 또는 아연이며, 전착수지를 더 함유하며, 상기 구리 유리(A) 중의 CuO의 함유량은 25~40몰%이며, 상기 구리 유리(A)의 함유량은 고형분 환산으로 상기 방오 도료 조성물의 고형분 중 1~20질량%이며, 상기 금속 피리치온류 (B)의 함유량은 고형분 환산으로 상기 구리 유리(A) 100질량부에 대하여 25~150질량부이며, 상기 산화 티타늄(C)의 함유량은 고형분 환산으로 상기 구리 유리(A) 100질량부에 대하여 50~300질량부이다.
The antifouling paint composition of the present invention is an antifouling paint composition containing (A) a copper glass containing bivalent copper, (B) a metal pyritic phase, and (C) titanium oxide, wherein the metal of the metal pi- Wherein the content of CuO in the copper glass (A) is 25 to 40 mol%, and the content of the copper glass (A) is 1 to 1 in terms of solid content of the solid content of the antifouling paint composition (B) is contained in an amount of 25 to 150 parts by mass based on 100 parts by mass of the copper glass (A) in terms of solid content, and the content of the titanium oxide (C) Is 50 to 300 parts by mass based on 100 parts by mass of the copper glass (A).
<구리 유리(A)> <Copper Glass (A)>
본 발명에 사용되는 구리 유리(A)는 2가의 구리를 포함하는 유리이며, 상기 구리 유리 중의 CuO의 함유량은 25~40몰%이다. 유리의 조성은, 적당한 속도로 용해하여 구리를 용출시킬 수 있는 것이면 특히 한정되지 않지만, 인산염 유리(P2O5를 주체로 하는 유리)가 바람직하며, P2O5-Na2O-CuO계 유리가 더 바람직하다. 인산염 유리는 실리카 유리에 비하여 유리의 용해량에 대한 구리의 용출량을 많게 할 수 있고, 또한 안정된 용출성능을 쉽게 얻을 수 있다. 따라서, 2가의 구리를 포함하는 인산염 유리를 이용하여 도료 조성물을 제작하였을 경우, 본 발명의 효과는 더 잘 발휘된다. 또한 Na2O는 인산의 인(phosphorus)과 산소의 결합을 분단(分斷)하는 성질을 가지고 있기 때문에, Na2O를 함유시킴으로써, 유리 성분이 물에 용해되기 쉬운 용해성 유리로 된다. P2O5, Na2O, 및 CuO의 함유량은 특히 한정되지 않는다. CuO의 함유량은 30~40몰%인 것이 더 바람직하다. 상기 정도의 함유량일 경우, Cu가 안정적이고 적당히 용출되기 쉬워지게 된다. P2O5와 Na2O의 몰 비율은 실질적으로 서로 동일(즉, P2O5/Na2O=0.8~1.2)하여도 좋고, 서로 달라도 좋다. 유리의 구체적인 조성(몰비)은 예를 들면, P2O5/Na2O/CuO=35/35/30 또는 P2O5/Na2O/CuO=30/30/40이다. The copper glass (A) used in the present invention is glass containing bivalent copper, and the content of CuO in the copper glass is 25 to 40 mol%. The composition of the glass is not particularly limited as long as it can dissolve at an appropriate rate to elute copper, but phosphate glass (glass mainly containing P 2 O 5 ) is preferable, and P 2 O 5 -Na 2 O-CuO Glass is more preferable. The phosphate glass can increase the elution amount of copper with respect to the amount of glass dissolved, and can easily obtain a stable elution performance as compared with silica glass. Therefore, when the coating composition is prepared by using the phosphate glass containing divalent copper, the effect of the present invention is more exerted. Since Na 2 O has a property of separating the phosphorus and oxygen bonds of phosphoric acid, by containing Na 2 O, the glass component becomes a soluble glass which is easily dissolved in water. The content of P 2 O 5 , Na 2 O, and CuO is not particularly limited. The content of CuO is more preferably 30 to 40 mol%. When the content is in the above range, Cu is stable and is liable to elute properly. The molar ratios of P 2 O 5 and Na 2 O may be substantially the same (ie, P 2 O 5 / Na 2 O = 0.8 to 1.2) or may be different from each other. The specific composition (molar ratio) of the glass is, for example, P 2 O 5 / Na 2 O / CuO = 35/35/30 or P 2 O 5 / Na 2 O / CuO = 30/30/40.
상기 구리 유리(A)는 인산 나트륨, 산화 구리(II) 등 조성 원료를 조합, 혼합하여, 1000~1200℃에서 30분~2시간 용융시키며, 용융된 유리를 철판위에 흘려내어, 냉각시킨 후, 유성(遊星) 볼밀(ball mill)등을 이용하여 1~100㎛ 정도로 분쇄하여 제조할 수 있다. The copper glass (A) is prepared by combining and mixing the starting materials such as sodium phosphate and copper (II) oxide, melting the glass at 1000 to 1200 ° C. for 30 minutes to 2 hours, flowing the melted glass over the steel plate, For example, by ball milling using a ball mill or the like.
상기 구리 유리(A)의 함유량은 고형분 환산으로 본 발명의 조성물의 고형분 중 1~20질량%이며, 예를 들면, 1, 2, 5, 10, 15, 20질량%이며, 여기에서 예시된 수치의 임의의 2개 수치의 사이의 범위내여도 좋다.
The content of the copper glass (A) is 1 to 20 mass%, for example, 1, 2, 5, 10, 15 and 20 mass% of the solid content of the composition of the present invention in terms of solid content, May be within a range between any two values of "
<금속 피리치온류(B)> ≪ Metal Pitch Rice Warmer (B) >
본 발명에 이용되는 금속 피리치온류(B)로서는, 비스(2-설파이드 피리딘-1-올라토(2-sulfidepyridine-1-olato))구리(구리 피리치온), 비스(2-설파이드 피리딘-1-올라토)아연(아연 피리치온) 등을 들 수 있으며, 그 중에서, 금속 비스피리치온류(구리 피리치온, 아연 피리치온 등 2가 금속 피리치온)가 바람직하며, 구리 피리치온이 특히 바람직하다. 금속 피리치온류는 시판품(市販品)을 이용할 수 있다. 시판품으로서는, 예를 들면, 카퍼 오마딘 파워(Copper Omadine Powder), 징크 오마딘 파워(Zinc Omadine Powder)(전부 아치 케미칼 재팬(주)(Arch Chemicals Japan, Inc)제) 등을 들 수 있다. Examples of the metal pyrite type (B) used in the present invention include bis (2-sulfide pyridine-1-olato) copper (copper pyrrityone), bis (2-sulfide pyridine- Among them, preferred are metal non-spirits (copper-pivalate, zinc-pivalate, and other divalent metal-pivalic ions) Rich on is particularly preferred. Commercially available metal products (commercially available) can be used. Commercially available products include, for example, Copper Omadine Powder and Zinc Omadine Powder (all manufactured by Arch Chemicals Japan, Inc).
상기 금속 피리치온류(B)의 함유량은 고형분 환산으로 상기 구리 유리(A) 100질량부에 대하여 25~150질량부이며, 예를 들면, 25, 50, 100, 150, 200, 250질량부이며, 여기에서 예시된 수치의 임의의 2개 사이의 범위내여도 좋다. 이런 범위에 있으면, 따개비나 서관충 등 동물류나 히드로충 등 강장동물 등에 대한 방오 효과가 특별히 좋다.
The content of the metal pyrite-free stream (B) is 25 to 150 parts by mass, for example, 25, 50, 100, 150, 200, and 250 parts by mass based on 100 parts by mass of the copper glass (A) , But may be in the range between any two of the values exemplified herein. In such a range, antifouling effect is particularly good against animal such as barnyard grass and western shrubbery, and animal such as hydroponics.
<산화 티타늄(C)> <Titanium oxide (C)>
본 발명에 이용되는 산화 티타늄(C)은, 루틸형, 아나타제(anatase)형 또는 브루카이트(brookite)형 등 산화 티타늄을 들 수 있으며, 이것들의 산화 티타늄은 단독으로 사용해도 좋고, 혹은 2종 이상을 조합시켜 사용해도 좋다. The titanium oxide (C) to be used in the present invention may be rutile, anatase or brookite type titanium oxide. These titanium oxide may be used singly or two or more kinds May be used in combination.
상기 산화 티타늄 중에서, 소위 초킹현상(도장 표면이 폭로 상태일 경우에, 자외선, 열, 수분, 바람 등에 의해 도장면의 표면수지가 열화되고, 도료의 색성분의 안료가 초킹과 같은 분말 형상이 되어 나타내는 현상이나 상태를 말함)을 일으키기 어렵다는 점에서, 루틸형의 산화 티타늄을 이용하는 것이 특히 바람직하다. Among the titanium oxides, the so-called chalking phenomenon (when the coating surface is in an exposed state, the surface resin of the coating surface is deteriorated by ultraviolet ray, heat, moisture, wind, etc. and the pigment of the color component of the coating becomes powdery It is particularly preferable to use rutile type titanium oxide in view of difficulty in causing a phenomenon or state.
본 발명의 산화 티타늄으로서는, 평균 입경이 0.001㎛~10㎛의 것이 바람직하고, 특히 0.1~3㎛의 것이 바람직하다. The titanium oxide of the present invention preferably has an average particle diameter of 0.001 탆 to 10 탆, particularly preferably 0.1 to 3 탆.
한편, 상기 산화 티타늄의 평균 입경은, 레이저 회절·산란법에 의해 측정되는 체적평균 직경으로부터 산출된 중위직경(50% 누계(累計) 입경)의 값을 말한다. 구체적으로, 니끼소(주)(Nikkiso Co., Ltd.)제의 레이저 회절·산란법 입도(粒度) 분석계, 광학장치 MT3300을 이용하고, 입경 측정용 분산매로서 메탄올을 이용하여, 측정 온도 25℃에서 측정된 값을 말한다. On the other hand, the average particle diameter of the titanium oxide refers to the value of the median diameter (50% accumulated particle diameter) calculated from the volume average diameter measured by the laser diffraction / scattering method. Specifically, a laser diffraction / scattering method particle size analyzer, an optical device MT3300 manufactured by Nikkiso Co., Ltd. was used, and methanol was used as a dispersion medium for particle size measurement at a measurement temperature of 25 占 폚 .
본 발명의 산화 티타늄으로서는 흡유량(吸油量)이 1ml/100g~1000ml/100g인 것이 바람직하며, 특히 3ml/100g~50ml/100g인 것이 바람직하다. The titanium oxide of the present invention preferably has an oil absorption amount (oil absorption amount) of 1 ml / 100g to 1000ml / 100g, and more preferably 3ml / 100g to 50ml / 100g.
본 발명의 산화 티타늄은, 표면처리되어 있어도 좋고, 예를 들면, Al, Si, Zr, Sb, Cr 및 Ti의 1종 이상 원소의 산화물이나 유기 규소화합물로 이루어지는 피막으로 표면처리된 것을 사용할 수도 있다. The titanium oxide of the present invention may be subjected to a surface treatment or may be surface treated with a coating of an oxide of at least one element of Al, Si, Zr, Sb, Cr and Ti or an organic silicon compound .
산화 티타늄으로서는, 시판품을 이용할 수 있다. 시판품으로서는, 예를 들면, 「FR-41」(후루카와 케미칼(주)(FURUKAWA CHEMICALS CO., LTD)제), 「R-5N」(사카이 화학공업(주)( SAKAI CHEMICAL INDUSTRY CO., LTD)제), 「R-820」「」(이시하라 산업(주)(ISHIHARA SANGYO KAISHA, LTD.)제) 등을 들 수 있다. As the titanium oxide, a commercially available product can be used. R-5N "(manufactured by SAKAI CHEMICAL INDUSTRY CO., LTD.)," FR-41 "(manufactured by FURUKAWA CHEMICALS CO., LTD.), R-820 "" (manufactured by ISHIHARA SANGYO KAISHA, LTD.), And the like.
상기 산화 티타늄(C)의 함유량은 고형분 환산으로 상기 구리 유리(A) 100질량부에 대하여, 상기 산화 티타늄(C)가 50~300질량부이며, 예를 들면, 50, 100, 150, 200, 250, 300질량부이며, 여기에서 예시된 수치의 임의의 2개 사이의 범위내여도 좋다. 이러한 범위일 경우에 본 발명의 효과가 더 잘 발휘된다. The content of the titanium oxide (C) is 50 to 300 parts by mass, for example, 50 to 100 parts by mass, 150 to 200 parts by mass based on 100 parts by mass of the copper glass (A) 250, and 300 parts by mass, and may be within a range between any two of the values exemplified herein. In the case of such a range, the effect of the present invention is more exerted.
<그 외의 첨가 성분> <Other components added>
본 발명에 이용되는 방오 도료 조성물은, 전착수지를 포함하고, 더욱이 용출조제, 기타 방오약제, 침강 방지제, 흐름 방지제, 가소제, 계면 활성제, 소포제, 염료, 안료, 유기용제 및 물 등을, 본 발명의 목적에 손상을 주지 않는 범위내에서 임의의 배합 비율로 함유할 수 있다.
The antifouling paint composition used in the present invention is a composition containing an electrodeposition resin and further containing an elution assistant, other antifouling agent, antisettling agent, flow inhibitor, plasticizer, surfactant, defoaming agent, dye, pigment, organic solvent, May be contained in an arbitrary compounding ratio within a range that does not impair the purpose of the composition.
(용출조제) (Dissolution preparation)
용출조제로서는, 실리콘 오일, 에틸렌·α-올레핀 공중합체, 폴리부텐류, 파라핀류, 바셀린류, 디알킬 황화 화합물 등을 들 수 있으며, 상기 용출조제를 함유시키는 것으로써, 도막의 용출속도를 적합하게 억제할 수 있으며, 장기간 방오효과를 발휘시킬 수 있다. Examples of the dissolution aid include silicone oil, ethylene /? - olefin copolymer, polybutene, paraffins, vaseline and dialkyl sulfide compounds. By including the elution assistant, , And can exhibit an antifouling effect for a long period of time.
용출조제의 함유량은, 특히 한정되지 않지만 고형분 환산으로 본 발명의 조성물의 고형분 중에서 보통 0.1~35질량%이며, 바람직하게는 1~30질량%이다. The content of the dissolution aid is not particularly limited, but is usually 0.1 to 35% by mass, preferably 1 to 30% by mass, in terms of solid content, in the solid content of the composition of the present invention.
상기 실리콘 오일로서는, 예를 들면, 폴리디메틸실록산(polydimethylsiloxane), 폴리메틸페닐실록산(Polymethylphenylsiloxane), 메틸페닐실록산-디메틸실록산 공중합체(methylphenylsiloxane-dimethylsiloxane copolymer), 폴리에테르 변성 폴리디메틸실록산 (Polyether modified polydimethylsiloxane), 폴리 에테르 변성 폴리 알킬(메틸)실록산(polyether modified polyalkyl(methyl)siloxane), 폴리에테르 변성 폴리디메틸실록산(polyester modified polydimethylsiloxane), 장쇄 알킬 변성 폴리디메틸실록산(long-chain alkyl modified polydimethylsiloxane), 아랄킬 변성 폴리디메틸실록산(aralkyl modified polydimethylsiloxane), 폴리 에테르 장쇄 알킬 아랄킬 변성 디메틸 실리콘 오일(polyether long-chain alkyl aralkyl modified dimethyl silicone oil), 플루오르실리콘 오일(fluorosilicone oil), 아미노 변성 실리콘 오일(amino modified silicone oil), 기타 각종 관능기에 의한 변성 실리콘 오일 등을 들 수 있다. 특히, 친수 친유 밸런스(HLB값)가 0.5~9인 폴리 에테르 변성 실리콘 오일이 바람직하며, 구체적으로는 0.5~9인 폴리 에테르 변성 폴리디메틸실록산 또는 폴리 에테르 장쇄 알킬 아랄킬 변성 디메틸 실리콘 오일이 바람직하다. 또한 바람직한 것으로는, 친수 친유 밸런스(HLB값)가 1~5 범위에 있는 폴리 에테르 변성 폴리디메틸실록산 또는 폴리 에테르 장쇄 알킬 아랄킬 변성 디메틸 실리콘 오일을 들 수 있다. Examples of the silicone oil include polydimethylsiloxane, polymethylphenylsiloxane, methylphenylsiloxane-dimethylsiloxane copolymer, polyether-modified polydimethylsiloxane, poly Polyether modified polydimethylsiloxane, long-chain alkyl modified polydimethylsiloxane, polyether modified polydimethylsiloxane, polyether modified polydimethylsiloxane, polyether modified polydimethylsiloxane, Polyether long-chain alkylaralkyl modified dimethyl silicone oil, fluorosilicone oil, amino-modified silicone oil, and the like. To various functional groups And a modified silicone oil. In particular, a polyether-modified silicone oil having a hydrophilic-lipophilic balance (HLB value) of 0.5 to 9 is preferable, and a polyether-modified polydimethylsiloxane or polyether long-chain alkyl aralkyl-modified dimethyl silicone oil having a ratio of 0.5 to 9 is preferable . Also preferred are polyether-modified polydimethylsiloxane or polyether long-chain alkyl aralkyl-modified dimethyl silicone oil having a hydrophilic lipophilic balance (HLB value) in the range of 1 to 5.
본 발명에서는, 이러한 실리콘 오일을 단독으로 이용해도 좋고, 2종 이상을 조합시켜 이용해도 좋다. In the present invention, these silicone oils may be used singly or in combination of two or more kinds.
실리콘 오일의 점도는, 도공 성능 및 도막 물성의 관점에서, 1000포아즈(poise) 이하가 바람직하며, 100포아즈 이하가 더 바람직하다. The viscosity of the silicone oil is preferably 1000 poise or less, more preferably 100 poise or less, from the viewpoints of coating performance and coating film properties.
상기 에틸렌·α-올레핀 공중합체로서는, 예를 들면, 일반식 (I)로 나타내는 에틸렌·α-올레핀 공중합체를 들 수 있다.: Examples of the ethylene /? - olefin copolymer include an ethylene /? - olefin copolymer represented by the general formula (I):
[화학식 1][Chemical Formula 1]
(식 중, R1은 탄소수 1~10인 직쇄(直鎖) 혹은 분지쇄(分技鎖) 형상의 알킬기를 나타내며, x, y 및 p는 각각 동일 또는 다른 1 이상의 정수를 나타낸다)(Wherein R 1 represents an alkyl group in the form of a straight chain or branched chain having 1 to 10 carbon atoms, and each of x, y and p represents the same or different integer of 1 or more)
R1로 표현되는 탄소수 1~10인 직쇄 혹은 분지쇄 형상의 알킬기로서는, 특히, 메틸기, 에틸기, 프로필기, 이소프로필기, 부틸기, 이소부틸기 등 탄소원자수 1~4인 알킬기가 바람직하며, 메틸기가 보다 바람직하다. As the linear or branched alkyl group having 1 to 10 carbon atoms represented by R 1 , an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and an isobutyl group is preferable, More preferred is a methyl group.
일반식 (I)로 표현되는 에틸렌·α-올레핀 공중합체는, 에틸렌과 α-올레핀을 공중합시켜 얻을 수 있는 공중합체이다. 상기 에틸렌·α-올레핀 공중합체는, 랜덤 공중합체(random copolymer), 블록 공중합체 또는 그라프트 공중합체 중의 임의의 하나여도 좋다. The ethylene /? - olefin copolymer represented by the general formula (I) is a copolymer obtainable by copolymerizing ethylene and an? -Olefin. The ethylene /? - olefin copolymer may be any one of a random copolymer, a block copolymer and a graft copolymer.
상기 에틸렌·α-올레핀 공중합체로서는 시판품을 이용할 수 있다. 시판품으로서는, 예를 들면, 루칸트(LUCANT)HC-10, 루칸트HC-20, 루칸트HC-40, 루칸트HC-100, 루칸트HC-150, 루칸트HC-600, 루칸트HC-2000(모두 등록상표, 미쓰이 케미칼(주)(Mitsui Chemicals, Inc)제) 등을 들 수 있다. 이것들의 에틸렌·α-올레핀 공중합체는, 단독으로 이용하여도 좋고, 2종 이상을 조합시켜 이용하여도 좋다. As the ethylene /? - olefin copolymer, commercially available products can be used. Examples of commercially available products include LUCANT HC-10, Lukant HC-20, Lukant HC-40, Lukant HC-100, Lukant HC-150, Lukant HC- 2000 (all registered trademarks, manufactured by Mitsui Chemicals, Inc). These ethylene /? - olefin copolymers may be used alone, or two or more of them may be used in combination.
상기 에틸렌·α-올레핀 공중합체의 수평균분자량(Mn)은, 도공 성능 및 도막물성의 관점에서 보면 10,000 이하가 바람직하고, 1,000~3,000이 보다 바람직하다. 상기 에틸렌·α-올레핀 공중합체는, 0℃에서의 점도가 20,000PaS 이하인 것이 바람직하며, 500PaS 이하인 것이 보다 바람직하다. The number average molecular weight (Mn) of the ethylene /? - olefin copolymer is preferably 10,000 or less, more preferably 1,000 to 3,000 from the viewpoints of coating performance and coating film properties. The ethylene /? - olefin copolymer preferably has a viscosity at 0 ° C of 20,000 Pa s or less, more preferably 500 Pa s or less.
상기 폴리부텐류로서는, 폴리부텐, 폴리이소부텐 등을 들 수 있다. 폴리부텐류로서는 시판품을 이용할 수 있다. 시판품으로서는 예를 들면, 폴리부텐LV-7, 폴리부텐LV-10, 폴리부텐LV-25, 폴리부텐LV-50, 폴리부텐LV-100, 폴리부텐HV-35, 폴리부텐HV-100, 폴리부텐HV-300, 폴리부텐HV-1900(모두 일본석유화학(주)(Nisseki Chemical Inc.)제); 폴리부텐0H, 폴리부텐5H, 폴리부텐10H, 폴리부텐300H, 폴리부텐2000H, 폴리부텐0R, 폴리부텐15R, 폴리부텐35R, 폴리부텐100R, 폴리부텐350R (모두 이데미쓰석유화학 주식 회사제); 폴리부텐0N, 폴리부텐06N, 폴리부텐3N, 폴리부텐10SH, 폴리부텐200N (전부 니치유(주)(NOF CORPORATION)제) 등을 들 수 있다. Examples of the polybutene include polybutene, polyisobutene, and the like. As polybutene, commercially available products can be used. Examples of commercially available products include polybutene LV-7, polybutene LV-10, polybutene LV-25, polybutene LV-50, polybutene LV-100, polybutene HV-35, polybutene HV- HV-300 and Polybutene HV-1900 (all manufactured by Nisseki Chemical Inc.); Polybutene 0H, polybutene 5H, polybutene 10H, polybutene 300H, polybutene 2000H, polybutene 0R, polybutene 15R, polybutene 35R, polybutene 100R and polybutene 350R (all manufactured by Idemitsu Petrochemical Co., Ltd.); Polybutene 0N, polybutene 06N, polybutene 3N, polybutene 10SH, and polybutene 200N (all manufactured by NOF CORPORATION).
상기 파라핀류로서는, 예를 들면, n-파라핀, 고형 파라핀, 유동 파라핀, 염소화 파라핀 등을 들 수 있다. The paraffins include, for example, n-paraffin, solid paraffin, liquid paraffin, chlorinated paraffin and the like.
상기 바셀린류로서는, 예를 들면, 백색 바셀린, 황색 바셀린 등을 들 수 있다. Examples of the petrolatum include white petrolatum and yellow petrolatum.
상기 디알킬 황화 화합물로서는, 디-tert-부틸데카설파이드(di-tert-butyl decasulfide), 디펜틸테트라설파이드(dipentyl tetrasulfide), 디펜틸펜타설파이드(dipentyl pentasulfide), 디펜틸데카설파이드(dipentyl decasulfide), 디옥틸테트라설파이드(dioctyl tetrasulfide), 디옥틸펜타설파이드(dioctyl pentasulfide), 디노닐테트라설파이드(dinonyl tetrasulfide), 디노닐펜타설파이드(dinonyl pentasulfide), 디-tert-노닐테트라설파이드(di-tert-nonyl tetrasulfide), 디-tert-노닐펜타설피드, 디데실테트라설파이드(didecyl tetrasulfide), 디도데실테트라설파이드(didodecyl tetrasulfide), 디옥타데실테트라설파이드(dioctadecyl tetrasulfide), 디노나데실테트라설파이드(dinonadecyl tetrasulfide) 등을 들 수 있다. Examples of the dialkyl sulfide compound include di-tert-butyl decasulfide, dipentyl tetrasulfide, dipentyl pentasulfide, dipentyl decasulfide, But are not limited to, dioctyl tetrasulfide, dioctyl pentasulfide, dinonyl tetrasulfide, dinonyl pentasulfide, di-tert-nonyl tetrasulfide, ), Di-tert-nonylpentasulfide, didecyl tetrasulfide, didodecyl tetrasulfide, dioctadecyl tetrasulfide, and dinonadecyl tetrasulfide. .
(전착수지) (Electrodeposited resin)
전착수지로서는, 합성수지 및 천연수지를 이용할 수 있으며, 전착수지를 함유시킴으로써, 도막형성에 대한 작업성이 향상된다. 또한, 피도막 형성물과의 밀착성이 뛰어난 도막을 형성할 수 있다. As the electrodeposition resin, synthetic resin and natural resin can be used, and workability for forming a coating film is improved by containing an electrodeposition resin. Further, it is possible to form a coating film having excellent adhesion with the coating film formation product.
상기 합성수지로는, 예를 들면, 비닐 수지, 알키드 수지, 아크릴 수지, 우레탄 수지, 폴리에스테르 수지, 합성 고무, 염소화 폴리에틸렌 등을 사용할 수 있다. 상기 비닐 수지로서는, 염화 비닐-아세트산 비닐 공중합체, 염화 비닐-알킬 비닐 에테르 공중합체, 염화 비닐 수지 등을 예시할 수 있다. As the synthetic resin, for example, a vinyl resin, an alkyd resin, an acrylic resin, a urethane resin, a polyester resin, a synthetic rubber, chlorinated polyethylene and the like can be used. Examples of the vinyl resin include a vinyl chloride-vinyl acetate copolymer, a vinyl chloride-alkyl vinyl ether copolymer, and a vinyl chloride resin.
또한, 상기 천연수지로서는, 예를 들면, 우드 로진, 껌 로진, 변성 로진 등을 들 수 있다. Examples of the natural resin include wood rosin, gum rosin, and modified rosin.
상기 전착 수지로서는, 특히 아크릴 수지를 함유하는 것이 바람직하다. As the electrodeposition resin, it is particularly preferable to contain an acrylic resin.
상기 전착 수지의 유리 전이온도(Tg)는 -100~100℃가 바람직하고, -50~80℃가 보다 바람직하다. 상기 전착 수지의 중량 평균 분자량(Mw)은, 5,000~1,000,000이 바람직하며, 10,000~500,000이 보다 바람직하다. 상기 전착 수지의 함유량은, 특히 한정되지 않지만, 고형분 환산으로 본 발명의 조성물의 고형분 중 보통 0.1~80질량%이며, 바람직하게는 1~45질량%이다.
The glass transition temperature (Tg) of the electrodeposited resin is preferably -100 to 100 ° C, more preferably -50 to 80 ° C. The weight average molecular weight (Mw) of the electrodeposited resin is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000. The content of the electrodeposited resin is not particularly limited, but is usually 0.1 to 80% by mass, preferably 1 to 45% by mass, in terms of solid content in the solid content of the composition of the present invention.
(다른 방오약제) (Other antifouling agents)
본 발명에 이용되는 2가 구리를 포함하는 구리 유리(A)나 금속 피리치온류 (B) 이외의 방오약제로서, 이하의 방오약제를 함유시킬 수 있다. 따라서, 형성된 도막이 더욱 좋은 방오효과를 발휘시킬 수 있다. As the antifouling agent other than the copper glass (A) or the metallic antifreeze (B) containing divalent copper used in the present invention, the following antifouling agent can be contained. Therefore, the formed coating film can exhibit a better antifouling effect.
다른 방오약제로는, 예를 들면, 테트라메틸티우람 디설파이드(tetramethylthiuram disulfide), 테트라에틸티우람 디설파이드(tetraethylthiuram disulfide)등의 테트라알킬티우람 디설파이드(tetraalkylthiuram disulfide)화합물 등을 들 수 있다. 그 외, 클로로 메틸-n-옥틸디설파이드(chloromethyl-n-octyl disulfide), N, N-디메틸디클로로페닐 요소(N,N-dimethyldichlorophenyl urea), N- (플루오로디클로로메틸티오)프탈이미드(N-(fluorodichloromethylthio)phthalimide), N, N'- 디메틸 -N'-페닐-(N-플루오로디클로로메틸티오)설파미드(N,N'-dimethyl-N'-phenyl-(N-fluorodichloromethylthio)sulfamide), N,N'-디메틸-N'-톨릴-(N-플루오로디클로로메틸티오)설파미드(N,N'- dimethyl -N'-tolyl-(N-fluorodichloromethylthio)sulfamide), 4,5-디클로로-2-n-옥틸-4-이소티아졸린-3-온(4,5-dichloro-2-n-octyl-4-isothiazoline-3-one), 2,3-디클로로-N- (2,6-디에틸 페닐)말레이미드(2,3-dichloro-N-(2,6-diethylphenyl) maleimide), 2,3-디클로로-N- (2'-에틸, 6'-메틸 페닐)말레이미드(2,3-dichloro-N-(2'- ethyl, 6'-methylphenyl)maleimide), 3-벤조 [b]티엔-2-일-5,6-디히드로-1,4,2-옥사티아진-4-옥사이드(3-benzo[b]thiene-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide), 2- (p-클로로페닐)-3-시아노-4-브로모-5-트리플루오로메틸피롤(2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole), 테트라클로로이소프탈로니트릴(tetrachloro-isophthalonitrile) 등을 사용할 수도 있다. Examples of other antifouling agents include tetraalkylthiuram disulfide compounds such as tetramethylthiuram disulfide and tetraethylthiuram disulfide. In addition, chloromethyl-n-octyl disulfide, N, N-dimethyldichlorophenyl urea, N- (fluorodichloromethylthio) phthalimide (N - (fluorodichloromethylthio) phthalimide, N, N'-dimethyl-N'-phenyl- (N-dimethyldinomethylthio) sulfamide, , N, N'-dimethyl-N'-tolyl- (N-fluorodichloromethylthio) sulfamide, 4,5-dichloro 2-n-octyl-4-isothiazoline-3-one, 2,3-dichloro-N- (2,6 2,6-diethylphenyl) maleimide), 2,3-dichloro-N- (2'-ethyl, 6'-methylphenyl) maleimide , 3-dichloro-N- (2'-ethyl, 6'-methylphenyl) maleimide), 3-benzo [b] thien- 3-benzo [b] thiene-2-yl-5,6-dihydro-1,4,2-oxathiazin e-4-oxide, 2- (p-chlorophenyl) -3-cyano-4-bromo- 5-trifluoromethylpyrrole, tetrachloro-isophthalonitrile, or the like may be used.
상기 구리 유리(A)나 금속 피리치온류(B)와 병용되는 다른 방오약제로서, 특히, 4,5-디클로로-2-n-옥틸-4-이소티아졸린-3-온이 바람직하다. As other antifouling agents to be used in combination with the copper glass (A) or the metal frit-on stream (B), 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one is particularly preferable.
상기 다른 방오약제의 함유량은, 특히 한정되지 않지만, 고형분 환산으로 본 발명의 조성물의 고형분 중 보통 0.1~80질량%, 바람직하게는 1~50질량%이다.
The content of the other antifouling agent is not particularly limited, but is usually 0.1 to 80% by mass, preferably 1 to 50% by mass, in terms of solid content, in the solid content of the composition of the present invention.
(침강 방지제·흐름방지제(Sagging agent)) (Sedimentation agent, sagging agent)
침강 방지제·흐름방지제로서는 예를 들면, 폴리에틸렌 왁스, 수소 첨가 아주까리기름 왁스계, 폴리아마이드 왁스계, 아마이드 왁스계, 산화 폴리에틸렌계 왁스 등을 들 수 있으며, 바람직하게는 수소 첨가 아주까리기름 왁스계, 폴리아마이드 왁스계, 아마이드 왁스계, 산화 폴리에틸렌계 왁스이다. 상기 침강 방지제·흐름방지제는 단독으로 이용해도 되고, 혹은 2종 이상을 조합시켜 이용해도 된다.
Examples of the anti-settling agent and anti-flow agent include polyethylene wax, hydrogenated castor oil wax, polyamide wax, amide wax, and oxidized polyethylene wax, preferably hydrogenated castor oil wax, poly Amide wax, amide wax, and oxidized polyethylene wax. The anti-settling agent and anti-flow agent may be used alone or in combination of two or more.
(가소제) (Plasticizer)
가소제로는 예를 들면, 프탈산 에스테르, 아디핀산 에스테르, 인산 에스테르 등을 들 수 있다. 상기 프탈산 에스테르로서는, 프탈산 디부틸, 프탈산 디옥틸, 프탈산디2-에틸헥실을 들 수 있으며, 상기 아디핀산 에스테르로는, 아디핀산 디부틸, 아디핀산 디옥틸, 아디핀산 2-에틸헥실을 들 수 있으며, 상기 인산 에스테르로는, 인산 트리크레실, 인산 트리옥틸 등을 들 수 있다. 상기 가소제는, 단독으로 이용해도 되고, 혹은 2종 이상을 조합시켜 이용해도 된다.
Examples of plasticizers include phthalic acid esters, adipic acid esters, phosphoric acid esters and the like. Examples of the phthalic acid esters include dibutyl phthalate, dioctyl phthalate and di-2-ethylhexyl phthalate. Examples of the adipic acid esters include dibutyl adipate, dioctyl adipate, and 2-ethylhexyl adipate. And examples of the phosphate ester include tricresyl phosphate, trioctyl phosphate and the like. These plasticizers may be used alone or in combination of two or more.
(유기용제) (Organic solvent)
유기용제로서는 예를 들면, 크실렌, 토루엔, 솔베소(Solvesso)100, 솔베소150(전부 등록상표, 엑손 모빌(Exxon Mobil Corporation)제) 등 방향족계 용제; 이소부틸 메틸 케톤(ISOBUTYL METHYL KETONE)(MIBK), 디이소부틸 케톤(DIISOBUTYL KETONE)(DIBK) 등 케톤계 용제; 초산 부틸, 초산 이소부틸, 초산이소아밀 등 에스테르계 용제를 사용할 수 있다. Examples of the organic solvent include aromatic solvents such as xylene, toluene, Solvesso 100 and Solvesso 150 (all of which are manufactured by Exxon Mobil Corporation); Ketone solvents such as ISOBUTYL METHYL KETONE (MIBK) and DIISOBUTYL KETONE (DIBK); Ester solvents such as butyl acetate, isobutyl acetate, and isoamyl acetate can be used.
또한, 저독·저취·저환경부하를 고려한 유기용제도 사용할 수 있으며, 예를 들면, 페가소(Pegasol)AN45, 페가소AS100(전부 등록상표, 엑손 모빌(Exxon Mobil Corporation)제), LAWS, HAWS(전부 셀 케미컬(Shell Chemicals)제) 등 방향족·지환식·지방족 탄화수소 혼합 용제; 프로필렌 글리콜 모노메틸 에테르 아세테이트, 프로필렌글리콜 모노에틸 에테르 아세테이트 등 글리콜계 에스테르 용제; 에틸 시클로헥산, 디메틸 시클로헥산, 리카솔부(RIKASOLV)(등록상표) 900(C9방향족수첨체), 리카솔부(등록상표) 1000(C10방향족수첨체) 등 지환식 탄화수소계 용제; 쉘졸(ShellSol)D40(등록상표, 셀 케미컬(Shell Chemicals)제), 엑솔(Exol)D30, 엑솔D40(모두 등록상표, 엑손 모빌(Exxon Mobil Corporation)제) 등 지환식·지방족 혼합 용제; 아이소파(Isopar)G, 아이소파H(모두 등록상표, 엑손 모빌제) 등 지방족 탄화수소 혼합 용제 등도 사용할 수 있다. For example, organic solvents such as Pegasol AN45 and Pegaso AS100 (all of which are manufactured by Exxon Mobil Corporation), LAWS, HAWS (All manufactured by Shell Chemicals); aromatic / alicyclic / aliphatic hydrocarbon mixed solvents; Glycol-based ester solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; Alicyclic hydrocarbon solvents such as ethyl cyclohexane, dimethyl cyclohexane, RIKASOLV (registered trademark) 900 (C9 aromatic hydrocolloid), Riccovu (registered trademark) 1000 (C10 aromatic hydrocolloid); Alicyclic / aliphatic mixed solvents such as ShellSol D40 (registered trademark, manufactured by Shell Chemicals), Exol D30, Exol D40 (all registered trademark, manufactured by Exxon Mobil Corporation); And aliphatic hydrocarbon mixed solvents such as Isopar G and Isopar H (all registered trademarks, exxon Mobil) may be used.
이러한 유기용제는 단독 또는 2종 이상을 혼합하여 이용할 수 있다. These organic solvents may be used alone or in combination of two or more.
본 발명의 조성물은, 여러 가지 어업도구, 수중 구조물 등 방오 도막의 형성에 사용될 수 있다. 특히, 본 발명의 조성물은, 어망용 방오 도료 조성물로서 적합하게 사용될 수 있다. The composition of the present invention can be used to form antifouling coatings such as various fishing tools and underwater structures. In particular, the composition of the present invention can be suitably used as an antifouling paint composition for fishing nets.
본 발명의 어망방오 도료 조성물은 상기 [A]~[C]성분, 및 필요에 따라서 상기 각 성분을 혼합함으로써 조제할 수 있다. 혼합시의 각 성분의 첨가량에 대하여서는 상기 배합량 및 함유량이 되도록 적당히 조정하면 좋다. 각 성분을 혼합하는 순서에 대하여서는 특히 제한되지 않는다. 혼합 방법에 대하여서는 교반 장치를 이용하여 혼합하는 등 공지된 방법을 이용하면 된다.
The antifouling paint composition of the present invention can be prepared by mixing the components [A] to [C] and, if necessary, the components described above. The addition amount of each component at the time of mixing may be appropriately adjusted so as to be the above mixing amount and content. The order of mixing the components is not particularly limited. For the mixing method, a known method such as mixing by using a stirring device may be used.
어망방오 도막의 형성 방법, 방오 도막, 및 도장물 Method of forming antifouling antifouling coating film, antifouling coating film, and coating material
본 발명의 어망방오 도막의 형성 방법은, 상기 어망방오 도료 조성물을 이용하여 피도막 형성물의 표면에 방오 도막을 형성하는 것을 특징으로 한다. 본 발명의 형성 방법에 의해 얻어진 방오 도막은, 표면에서 서서히 용해되어 도막표면이 늘 갱신됨으로써, 해양 오염 유기물의 부착 방지를 도모할 수 있다. 또한, 도막을 용해시킨 후, 상기 조성물을 덧칠하는 것으로써, 계속적으로 방오효과를 발휘할 수 있다. The method for forming a fishing net antifouling coating film of the present invention is characterized in that an antifouling coating film is formed on the surface of a coating film formation using the fishing net antifouling paint composition. The antifouling coating film obtained by the forming method of the present invention gradually dissolves on the surface and the surface of the coating film is always renewed, so that adhesion of marine contaminated organic matter can be prevented. Further, by dissolving the coating film and then applying the composition, the antifouling effect can be continuously exhibited.
피도막 형성물로서는, 예를 들면, 어업도구, 수중 구조물 등을 들 수 있다. 어업도구로서는, 예를 들면, 양식용 또는 정치(定置)용의 어망, 상기 어망에 사용되는 낚시찌자, 로프 등 어망부속 도구 등을 들 수 있다. 수중 구조물로서는, 예를 들면, 발전소 도수관, 교량, 항만(港p) 설비 등을 들 수 있다. Examples of the coated film formation include fishery tools and underwater structures. Examples of the fishery tool include fishing nets for aquaculture or stationary use, fishing nets for fishing nets, and fishing nets such as ropes. The underwater structure includes, for example, a power plant water pipe, a bridge, and a harbor (p) facility.
본 발명의 어망방오 도막은, 상기 어망방오 도료 조성물을 피도막 형성물의 표면(전체 또는 일부)에 도포하는 것으로써 형성될 수 있다. The fishing net antifouling coating film of the present invention can be formed by applying the fishing net antifouling paint composition to the surface (all or a part) of the coating film formation.
도포 방법으로서는, 예를 들면, 브러시 코팅, 스프레이법, 디핑법, 플로우 코트법, 스핀 코트법 등을 들 수 있다. 이것들은, 1종 또는 2종 이상을 병용할 수 있다. 예를 들면, 본 발명의 어망방오 도료 조성물을 어망에 도포할 경우, 도포 방법으로서는 디핑법을 이용하는 것이 바람직하다. Examples of the application method include brush coating, spraying, dipping, flow coating, spin coating and the like. These may be used alone or in combination of two or more. For example, when the fishing net antifouling paint composition of the present invention is applied to a fishing net, it is preferable to use a dipping method as a coating method.
도포 후 건조시킨다. 건조 온도는 실온이면 된다. 건조 시간은 어망방오 도료의 부착량에 따라 적당히 설정할 수 있다. After application, it is dried. The drying temperature may be room temperature. The drying time can be set appropriately according to the adhered amount of the fishing net antifouling paint.
상기 어망방오 도료의 부착량은, 피도막 형성물의 종류 등에 따라 적당히 설정하면 된다. 예를 들면, 피도막 형성물이 어망일 경우, 건조 도막의 부착량이 어망 100질량부에 대하여 바람직하게는 1~35질량부, 더욱 바람직하게는 4~20질량부이다. The adhesion amount of the fishing net antifouling paint may be suitably set in accordance with the kind of the coating film formation or the like. For example, when the coated film is a fishing net, the amount of the dried coating applied is preferably 1 to 35 parts by mass, more preferably 4 to 20 parts by mass, based on 100 parts by mass of the fishing net.
본 발명의 도장물은 상기 방오 도막을 표면에 갖는다. 본 발명의 도장물은 상기 방오 도막을 표면 전체에 갖고 있어도 좋고, 일부에 갖고 있어도 좋다.
The coating material of the present invention has the antifouling coating film on its surface. The coating material of the present invention may have the above-described antifouling coating film on the whole surface or a part thereof.
실시예Example
이하에, 실시예 등을 이용하여 본 발명의 특징을 더 명확하게 나타낸다. 그러나, 본 발명은 이러한 실시예 등에 한정되는 것이 아니다.
Hereinafter, the features of the present invention will be more clearly shown using examples and the like. However, the present invention is not limited to these embodiments and the like.
비교 제조예 1 (1가의 구리를 포함하는 구리 유리H-1의 제조) COMPARATIVE PREPARATION EXAMPLE 1 (Preparation of copper glass H-1 containing univalent copper)
하기 조성비의 유리 성분재료와 구리 화합물을 균일하게 혼합하여, 1100~1300℃의 가스 화로를 이용하여 60분간 용융시킨 후, 급냉시켜 1가의 구리를 함유하는 용해성 유리를 제조하며, 그 후, 상기 용해성 유리를 볼 밀에서 분쇄하여 1가의 구리를 포함하는 구리 유리 분말을 얻는다.
A glass component material having the following composition ratio and a copper compound are uniformly mixed and melted for 60 minutes using a gas furnace at 1100 to 1300 DEG C and then quenched to prepare a soluble glass containing monovalent copper, The glass is pulverized in a ball mill to obtain a copper glass powder containing monovalent copper.
<조성> <Composition>
SiO2: 7.7질량부 SiO 2: 7.7 parts by weight
Al2O3: 0.1질량부 Al 2 O 3 : 0.1 parts by mass
Na2O: 5.9질량부 Na 2 O: 5.9 parts by mass
B2O3: 28.8질량부 B 2 O 3 : 28.8 parts by mass
Cu2O: 53.3질량부 Cu 2 O: 53.3 parts by mass
ZnO: 4.2질량부
ZnO: 4.2 parts by mass
실시예 1~6 및 비교예 1~12 Examples 1 to 6 and Comparative Examples 1 to 12
표1에 기재된 배합 성분을 표1에 기재된 비율(질량%)로 혼합함으로써 방오 도료 조성물을 얻는다. An antifouling paint composition is obtained by mixing the compounding ingredients shown in Table 1 at a ratio (mass%) shown in Table 1.
상품명 「PNU-40」: 2가의 구리를 포함하는 구리 유리(P2O5/Na2O/CuO=30/30/40(몰%), 평균 입경 3μ, (도요 가라스(주)(TOYO GLASS CO., LTD.)제) (P 2 O 5 / Na 2 O / CuO = 30/30/40 (mol%), average particle diameter 3 μ, (TOYO (trade name) GLASS CO., LTD.))
상품명 「PNU-30」: 2가의 구리를 포함하는 구리 유리(P2O5/Na2O/CuO=35/35/30(몰%), 평균 입경 3μ, (도요 가라스(주)제) (P 2 O 5 / Na 2 O / CuO = 35/35/30 (mol%), average particle size 3 μ, (manufactured by Toyo Garas Co., Ltd.)
상품명 「NC-301」: 아산화구리(닛신 켐코(주)(NISSIN CHEMCO Co., Ltd.)제) NC-301 ": copper oxide (manufactured by NISSIN CHEMCO Co., Ltd.)
상품명 「산화 아연2종」: 산화 아연(세도화학공업(주)(Seido Chemical Industry Co., Ltd.)제) Trade name " Zinc oxide ": zinc oxide (manufactured by Seido Chemical Industry Co., Ltd.)
상품명 「Nocceler PZ」:디메틸디티오카르바메이트아연(오우치신흥화학 공업(주)(OUCHI SHINKO CHEMICAL INDUSTRIAL)제) Trade name " Nocceler PZ ": dimethyldithiocarbamate zinc (manufactured by OUCHI SHINKO CHEMICAL INDUSTRIAL CO., LTD.)
상품명 「Nocceler TET-G」:테트라에틸티우람 디설파이드(오우치신흥화학 공업(주)제) Trade name " Nocceler TET-G ": tetraethylthiuram disulfide (manufactured by Ouchi New Chemical Industry Co., Ltd.)
상품명 「Copper Omadine Powder」:비스(2-술피드 피리딘-1-올라토)구리(bis(2-sulfidepyridin-1-olato)copper)(아치·케미컬·저팬(주)(Arch Chemicals Japan)제) Copper Omadine Powder: Bis (2-sulfide pyridin-1-olato) copper (manufactured by Arch Chemicals Japan)
상품명 「Zinc Omadine Powder」:비스(2-술피드 피리딘-1-올라토)아연(bis(2-sulfidepyridin-1-olato)zinc)(아치·케미컬·저팬(주)제) Zinc Omadine Powder "bis (2-sulfide pyridin-1-olato) zinc (manufactured by Arch Chemical Co., Ltd.)
상품명 「FR-41」:산화 티타늄(루틸형 산화 티타늄, 후루카와 케미컬(주)(FURUKAWA CHEMICALS CO., LTD)제) Trade name " FR-41 ": titanium oxide (rutile type titanium oxide, manufactured by FURUKAWA CHEMICALS CO., LTD)
상품명 「산화 아연2종」:산화 아연(세도화학공업(주)제) Trade name " zinc oxide ": zinc oxide (manufactured by Sedo Chemical Industry Co., Ltd.)
상품명 「티누빈(TINUVIN)P」:2-(5-메틸-2-히드록시 페닐)벤조트리아졸(나가세 산업(주)(Nagase & Co., Ltd.)제) (Trade name: TINUVIN P): 2- (5-methyl-2-hydroxyphenyl) benzotriazole (manufactured by Nagase & Co.,
상품명 「NITTOL HN」:아크릴 수지 크실렌 용액(고형분 40%, Tg= 약20도, Mw= 약230000, 닛토 카세이(주)(NITTO KASEI CO., LTD.)제) Trade name " NITTOL HN ": acrylic resin xylene solution (solid content 40%, Tg = about 20 degrees, Mw = about 230000, manufactured by NITTO KASEI CO., LTD.
상품명 「KF-6020」:폴리 에테르 변성디메틸 실리콘 오일 (신에츠 화학공업(주)(Shin-Etsu Chemical Co, Ltd)제) Trade name " KF-6020 ": polyether-modified dimethyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.)
상품명 「X-22-2516」:폴리 에테르장 쇠사슬알킬 아랄킬변성디메틸 실리콘 오일 (신에츠 화학공업(주)제) Trade name " X-22-2516 ": polyether long-chain alkyl aralkyl-modified dimethyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.)
상품명 「루칸트 HC-40」:에틸렌료-올레핀 공중합체(미쓰이 케미칼(주)(Mitsui Chemicals, Inc)제) Quot; Lucent HC-40 ": an ethylene-olefin copolymer (manufactured by Mitsui Chemicals, Inc)
상품명 「폴리부텐 0N」:폴리부텐(일본 유지(주)(NOF CORPORATION)제) &Quot; Polybutene 0N ": polybutene (manufactured by NOF CORPORATION)
상품명 「디스파론 4200-20」:산화 폴리에틸렌계 왁스(고형분 20%, 구스모토 케미칼(주)(Kusumoto Chemicals, Ltd.)제) Trade name " DIPARON 4200-20 ": oxidized polyethylene wax (solid content 20%, manufactured by Kusumoto Chemicals, Ltd.)
상품명 「디스파론(Disparlon) A630-20X」:폴리 아마이드계 왁스(고형분 20%, 구스모토 케미칼(주)제) (Trade name: Disparlon A630-20X): polyamide wax (solid content 20%, manufactured by Goosumoto Chemical Co., Ltd.)
크실렌: 키시다 케미칼(주)(Kishida Chemical Co., Ltd.)제, 1급 시약 Xylene: manufactured by Kishida Chemical Co., Ltd., a first-grade reagent
[표 1] [Table 1]
시험예 1(방오 효과 확인 시험) Test Example 1 (Antifouling effect confirmation test)
폴리에틸렌제의 어망(400데니어, 40개, 8절)을, 실시예 1~6 및 비교예 1~12에서 얻은 각 방오 도료 조성물에, 건조 도막의 부착량이 어망 100질량부에 대하여 15질량부가 되도록 침지 도포하여 건조시켰다. 도막이 형성된 어망을 40×60cmSUS의 테두리에 고정하여, 해양 오염 유기물의 활성이 강한 해역인 미에현(三重縣) 오와세(尾鷲)의 뗏목에서 흘수부(喫水部)에 침지하여, 그 방오 평가를 12개월간에 걸쳐 정기적으로 관찰하였다. Each of the antifouling paint compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 12 was applied to a fishing net (400 denier, 40 pieces, 8 segments) made of polyethylene so that the adhered amount of the dried coating film was 15 parts by mass per 100 parts by mass of the fishing net Immersed and dried. The fishing net with the coated film was fixed to the rim of 40 × 60 cm SUS and immersed in the draft part of the raft of Owase, Mie Prefecture, where the activity of marine contaminated organic matter was strong, They were observed regularly for 12 months.
평가는 이하의 방법으로 행했다. 한편, 수생(水棲) 생물의 부착 면적(%)은, 시험 기간(2, 4, 6, 8, 10 또는 12개월) 후에 위에서 어망의 사진을 촬영하여, 어망에 있어서의 수생 생물의 점유 면적을 목시(目視)로 평가하였다. Evaluation was conducted in the following manner. On the other hand, the area of attachment (%) of aquatic organisms can be determined by photographing the fish net from above after the test period (2, 4, 6, 8, 10 or 12 months) And evaluated by visual observation.
◎: 수생 생물의 부착 면적이 0% ◎: The attachment area of aquatic organisms is 0%
○: 수생 생물의 부착 면적이 0% 초과 10%미만 ○: the attachment area of aquatic organisms is more than 0% and less than 10%
△: 수생 생물의 부착 면적이 10% 이상 50%미만 △: the attachment area of aquatic organisms is 10% or more and less than 50%
×: 수생 생물의 부착 면적이 50%이상 X: An area of attachment of aquatic organisms is 50% or more
결과를 표2에 나타낸다. The results are shown in Table 2.
[표 2] [Table 2]
표2에 있어서, 본 발명의 실시예 1~6의 방오 도료 조성물은, 비교예 1~12의 방오 도료 조성물의 임의의 하나보다 장기 방오성에 뛰어나다는 것을 알았다. In Table 2, it was found that the antifouling paint compositions of Examples 1 to 6 of the present invention are superior in antifouling performance to any one of the antifouling paint compositions of Comparative Examples 1 to 12.
실시예 1~6은, 2가의 구리를 포함하는 구리 유리, 금속 피리치온류, 및 산화 티타늄의 3성분을 함유한다. 이것에 대하여, 비교예 1은 2가의 구리를 포함하는 구리 유리만을 함유하며, 비교예 2 및 3은 2가의 구리를 포함하는 구리 유리와 금속 피리치온류만을 함유하며, 비교예 4는 2가의 구리를 포함하는 구리 유리와 산화 티타늄을 함유하지만, 비교예 1~4의 장기방오성은 실시예 1~6보다 훨씬 낮았다. 상기 결과는 방오 도료 조성물이 훌륭한 장기방오성을 발휘하기 위하여 상기 3성분을 모두 함유하는 것이 필수적이며, 3성분 중의 임의의 하나라도 빠지면 장기 방오성이 극단적으로 저하된다는 것을 알았다. Examples 1 to 6 contain three components, copper glass containing bivalent copper, metal pyrites, and titanium oxide. On the contrary, Comparative Example 1 contained only copper glass containing divalent copper, Comparative Examples 2 and 3 contained only copper glass containing divalent copper and metallic pyrite manganese, Comparative Example 4 contained divalent copper , But the long-term antifouling properties of Comparative Examples 1 to 4 were much lower than those of Examples 1 to 6. The results show that it is essential that the antifouling paint composition contains all of the above three components in order to exhibit excellent long-term antifouling properties, and that if any one of the three components is omitted, the long-term antifouling property is extremely lowered.
또한, 비교예 5~8에서는, 1가의 구리를 포함하는 구리 유리, 금속 피리치온류, 및 산화 티타늄의 3성분, 또는 아산화구리, 금속 피리치온류, 및 산화 티타늄의 3성분을 함유하는 방오 도료 조성물의 장기 방오성을 조사했지만, 비교예 5~8의 임의의 하나에 있어서도, 장기 방오성은 실시예 1~6보다 훨씬 낮았다. 따라서, 금속 피리치온류 및 산화 티타늄을 첨가함으로써 장기 방오성이 크게 향상되는 효과는, 2가 구리를 포함하는 구리 유리의 특유한 것이며, 1가 구리를 포함하는 구리 유리나 아산화구리를 이용하였을 경우에는, 같은 결과가 얻어질 수 없다는 것을 알았다. In addition, in Comparative Examples 5 to 8, an antifouling paint containing three components of copper glass containing monovalent copper, metallic pyrites, and titanium oxide, or three components of copper oxide, metallic pyrites, and titanium oxide The long-term antifouling property of the composition was examined, but in any one of Comparative Examples 5 to 8, the long-term antifouling property was much lower than those of Examples 1 to 6. [ Therefore, the effect of greatly improving the long-term antifouling property by adding the metallic pyrite hot-air stream and the titanium oxide is peculiar to copper glass including divalent copper, and when copper glass or copper oxide containing monovalent copper is used, The results could not be obtained.
더욱이, 비교예 9는 피리치온과 산화 티타늄을 포함하지만 1가 구리를 포함하는 구리 유리를 포함하지 않은 방오 도료 조성물에 관한 것이다. 방오 평가의 결과에 의하면, 비교예 9에서는 4개월 때의 관찰시에 수생 생물이 부착되어 있으며, 장기 방오성은 실시예보다도 훨씬 떨어졌다. Further, Comparative Example 9 relates to an antifouling paint composition that does not contain copper glass containing piri-rich and titanium oxide but containing monovalent copper. According to the results of the antifouling evaluation, in Comparative Example 9, aquatic organisms adhered at the time of observation at 4 months, and the long-term antifouling property was much lower than those of Examples.
비교예 10은 비교예 9에 산화 아연을 첨가한 것이다. 방오 평가의 결과에 의하면 비교예 10에도 4개월 때의 관찰시에 수생 생물이 부착되어 있었으며, 산화 아연을 첨가하여도, 장기 방오성은 개선되지 않는다는 것을 알았다. In Comparative Example 10, zinc oxide was added to Comparative Example 9. According to the results of the antifouling evaluation, the aquatic organisms adhered to Comparative Example 10 at the time of observation at 4 months, and it was found that even if zinc oxide was added, the long-term antifouling property was not improved.
비교예 11은 비교예 9에 디메틸디티오카르바메이트 아연을 첨가한 것이다. 방오 평가의 결과에 의하면 비교예 11에서는 장기 방오성은 조금 개선되었지만, 4개월 때의 관찰시에 수생 생물이 부착되어 있었으며, 디메틸디티오카르바메이트 아연을 첨가하여도 장기 방오성은 대폭적으로 개선되지 않는다는 것을 알았다. In Comparative Example 11, dimethyldithiocarbamate zinc was added to Comparative Example 9. According to the results of the antifouling evaluation, although the long-term antifouling property was slightly improved in Comparative Example 11, aquatic organisms were attached at the observation at 4 months, and even if the addition of dimethyldithiocarbamate zinc did not significantly improve the long term antifouling property .
비교예 12는 비교예 9에 테트라에틸티우람 디설파이드를 첨가한 것이다. 방오 평가의 결과에 의하면 비교예 12에서는, 4개월 때의 관찰시에 수생 생물이 부착되어 있었으며, 테트라에틸티우람 디설파이드를 첨가하여도, 장기 방오성은 대부분 개선되지 않는다는 것을 알았다. Comparative Example 12 is obtained by adding tetraethylthiuram disulfide to Comparative Example 9. According to the results of the antifouling evaluation, in Comparative Example 12, aquatic organisms adhered at the time of observation at 4 months, and it was found that even if tetraethylthiuram disulfide was added, most of the long-term antifouling property was not improved.
더욱이, 구리 피리치온을 함유하는 실시예 1, 2 및 5는, 아연 피리치온을 함유하는 실시예 3, 4 및 6에 비하여 장기 방오성이 뛰어나다는 것을 알았다. Moreover, it was found that Examples 1, 2 and 5 containing copper pyrithione are superior in long-term antifouling property to Examples 3, 4 and 6 containing zinc pyrithione.
Claims (7)
상기 금속 피리치온류의 금속은 구리 또는 아연이며,
전착수지 및 용출조제를 더 함유하고,
상기 구리 유리(A) 중의 CuO의 함유량은 25~40몰%이며,
상기 구리 유리(A)의 함유량은 고형분 환산으로 상기 방오 도료 조성물의 고형분 중 1~20질량%이고,
상기 금속 피리치온류(B)의 함유량은 고형분 환산으로 상기 구리 유리(A) 100질량부에 대하여 25~150질량부이며,
상기 산화 티타늄(C)의 함유량은, 고형분 환산으로 상기 구리 유리(A) 100질량부에 대하여 50~300질량부이고,
상기 용출조제는 실리콘 오일, 에틸렌·α-올레핀 공중합체 및 폴리부텐류로 이루어진 군에서 선택되는 1종 이상인 방오 도료 조성물.
(A) a copper glass containing bivalent copper, (B) a metal pyritic oxide, and (C) a rutile type titanium oxide,
Wherein the metal of the metal pi-rich metal is copper or zinc,
An electrodeposition resin and an elution aid,
The content of CuO in the copper glass (A) is 25 to 40 mol%
The content of the copper glass (A) is 1 to 20% by mass based on the solid content of the solid content of the antifouling paint composition,
The content of the metallic pyrite-free stream (B) is 25 to 150 parts by mass based on 100 parts by mass of the copper glass (A) in terms of solid content,
The content of the titanium oxide (C) is 50 to 300 parts by mass based on 100 parts by mass of the copper glass (A) in terms of solid content,
Wherein the elution assistant is at least one selected from the group consisting of silicone oil, ethylene /? - olefin copolymer, and polybutene.
상기 금속 피리치온은 금속 비스피리치온류인 방오 도료 조성물.
The method according to claim 1,
Wherein the metal pyricion is a metal non-spichielite.
An antifouling coating film formed on the surface of an antifouling coating film formed using the antifouling paint composition according to any one of claims 1 to 3.
A fishing net tool having an antifouling coating film formed on the surface thereof using the antifouling paint composition according to claim 1 or 2.
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| JP2010251848A JP4812895B1 (en) | 2010-11-10 | 2010-11-10 | Antifouling paint composition, fishing net to which the paint composition is applied, fishing net equipment and underwater construction |
| JPJP-P-2010-251848 | 2010-11-10 | ||
| PCT/JP2011/075164 WO2012063679A1 (en) | 2010-11-10 | 2011-11-01 | Antifouling coating composition, and fishing net, fishing net gear, and underwater structure coated with antifouling coating composition |
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| JP6186199B2 (en) * | 2013-07-30 | 2017-08-23 | 日東化成株式会社 | A fishing net antifouling paint composition, a fishing net having an antifouling coating film formed using the composition, a fishing net tool, or an underwater structure. |
| KR101514455B1 (en) * | 2014-09-03 | 2015-04-28 | 대한민국 | Sub-plate for mussel aquaculture and suspended type rearing rope using thererof |
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| KR102455511B1 (en) | 2021-06-04 | 2022-10-14 | 신용자 | Oil-repellant and antifouling coating composition for fishing net and fishing net coated with the coating composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103370385B (en) | 2015-08-12 |
| JP4812895B1 (en) | 2011-11-09 |
| JP2012102233A (en) | 2012-05-31 |
| WO2012063679A1 (en) | 2012-05-18 |
| AU2011327409A1 (en) | 2013-05-02 |
| KR20130084675A (en) | 2013-07-25 |
| TW201224083A (en) | 2012-06-16 |
| TWI431079B (en) | 2014-03-21 |
| CN103370385A (en) | 2013-10-23 |
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