KR20130084675A - 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 compositionDownload PDFInfo
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- 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
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- A—HUMAN NECESSITIES
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- 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
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- 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
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- 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
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C08K3/00—Use of inorganic substances as compounding ingredients
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Abstract
Translated fromKoreanDescription
Translated fromKorean본 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.The present invention is a marine pollutant organic matter is attached to aquaculture or fixed nets, such as fishing nets, ropes, fishing nets (hereinafter referred to as fishing nets) used in the fishing nets, underwater constructions such as cooling water pipes of power plants And antifouling paint compositions for preventing them over time, and to fishnets and underwater constructs to which the antifouling paint compositions have been applied.
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 fish nets and underwater constructs have been installed in the sea for a long time, various marine pollutant organic matters such as seaweeds, barnacles, corpus worms, moss worms, and mollusks adhere to them when the antifouling coating composition is used without application. Therefore, the marine water between the inner side and the outer side of the fishing net worsens, and a large amount of damage occurs, such as a large number of aquaculture fish dies due to oxygen deficiency, or an infectious disease occurs and cannot be shipped. In addition, when attached organisms are attached to aquaculture nets or political networks, the net becomes heavy, and there is a problem that the fish escape due to the settlement of the net, or the net itself flows out. Because of this, the nets need to be changed frequently, and there is a problem that a huge amount of labor and money must be used 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. Application of various antifouling coating compositions has been widely applied to fish nets and underwater constructs for the purpose of preventing adhesion of such marine polluted organic matters. Among these antifouling coating compositions, in particular, antifouling coating compositions containing copper-based chemical agents such as copper nitrous oxide, copper glass and copper pyrithione have a constant effect on the prevention of adhesion such as shellfish such as mussels, barnacles and corpus callosum. It has been widely used because it represents.
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, as an antifouling coating composition excellent for animals such as barnacles and cochlea and tonic animals such as hydrozoan, an antifouling agent composition comprising copper oxide and a specific polyether-modified silicone oil has been proposed (patent document). One). Moreover, the antifouling coating composition which mix | blended copper pyrithione with copper nitrous oxide and a specific polyether modified silicone oil is also 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 cuprous oxide used in these antifouling coating compositions is hard to dissolve in water and hardly ionized, it cannot exhibit a sufficient repelling effect on marine polluting organic matters and has not exhibited 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.Moreover, the antifouling coating composition which uses together with metal pyrithione using the soluble copper glass containing monovalent copper instead of cuprous oxide is proposed (patent document 3). However, the soluble copper glass containing monovalent copper used in the antifouling coating composition has a higher elution amount of copper ions than copper nitrite, but has not yet exhibited sufficient avoiding effects on marine pollutant organic matters, and satisfies the market demand. I could not let you.
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.Moreover, the antifouling coating composition containing the copper glass containing bivalent copper is also proposed (patent document 4). However, the antifouling coating composition has not yet had sufficient repelling effects on marine polluting organics.
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, it has good coating properties and excellent workability when applying fish nets, and the development of antifouling coating composition for fishing nets that can exert long-term antifouling effect in the sea area with strong activity of animals such as barnacles and copeworms and tonic animals such as hydroworms. It 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.The present invention has been made in view of the above, and provides an antifouling coating composition capable of exhibiting an antifouling effect for a long time even in an area of strong activity of animals such as barnacles and cochlea, and tonic animals such as hydroworms.
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 coating composition containing (A) a copper glass containing bivalent copper, (B) metal pyrithiones, and (C) titanium oxide, wherein the metal of the metal pyrithione is copper or zinc. It further contains electrodeposition resin, the content of CuO in the copper glass (A) is 25 to 40 mol%, the content of the copper glass (A) is a solid content of the antifouling coating composition in terms of solid content It is 1-20 mass% in content, content of the said metal pyrithione (B) is 25-150 mass parts with respect to 100 mass parts of said copper glasses (A) in solid content conversion, and content of the said titanium oxide (C) is solid content The antifouling coating composition which is 50-300 mass parts with respect to 100 mass parts of said copper glasses (A) in conversion is provided.
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.MEANS TO SOLVE THE PROBLEM The present inventors conducted research in order to develop the antifouling coating composition which can exhibit an antifouling effect for a long time, As a result, the antifouling coating composition contains (A) copper glass containing bivalent copper, (B) metal pyrithiones, and ( C) When it contained three components of titanium oxide in a specific ratio, it discovered that the outstanding long-term antifouling property was exhibited, and completed this invention.
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 antifouling coating composition of the present invention is not clear about the effect of exhibiting excellent long-term antifouling properties, experimentally includes only copper glass containing divalent copper, or copper glass and metal pyrithione containing divalent copper. It was found that the antifouling effect did not last long term, and exhibited excellent long-term antifouling properties when the three components were included. Since the active ingredient having an antifouling effect is copper glass and metal pyrithione, titanium oxide moderately controls the dissolution rate of copper glass and metal pyrithione and elutes these effective ingredients at a stable rate over a long period of time. It is assumed that it 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, in the long-term antifouling property of a coating composition containing copper glass, metal pyrithione containing monovalent copper, and three components of metal oxide and titanium oxide, or a coating composition containing copper oxide, metal pyrithione, and titanium oxide. Although it investigated, all are inferior to long-term antifouling property compared with this invention. From this, the excellent long-term antifouling property exhibited by the present invention is characterized in that the antifouling coating composition has a specific ratio of three components of (A) copper glass containing bivalent copper, (B) metal pyrithiones, and (C) titanium oxide. It turned out to exhibit for the first time by containing and was able to complete this invention.
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 coating composition of the present invention, an antifouling effect can be exhibited for a long time even in an area of strong activity of tonic animals such as barnacles and cochlea, and tonic animals such as hydroworms.
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 coating composition of the present invention is an antifouling coating composition containing (A) a copper glass containing bivalent copper, (B) metal pyrithiones, and (C) titanium oxide, wherein the metal of the metal pyrithione It is copper or zinc, and further contains electrodeposition resin, Content of CuO in the said copper glass (A) is 25-40 mol%, Content of the said copper glass (A) is 1 in solid content of the said antifouling coating composition in solid content conversion. It is -20 mass%, content of the said metal pyrithione (B) is 25-150 mass parts with respect to 100 mass parts of said copper glass (A) in solid content conversion, and content of the said titanium oxide (C) is solid content conversion It is 50-300 mass parts with respect to 100 mass parts of said 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.Copper glass (A) used for this invention is glass containing bivalent copper, and content of CuO in the said copper glass is 25-40 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 composed of P2 O5 ) is preferable, and P2 O5 —Na2 O—CuO-based Glass is more preferred. Phosphate glass can increase the elution amount of copper with respect to the dissolution amount of glass compared with a silica glass, and also can obtain the stable elution performance easily. Therefore, when the coating composition is produced using phosphate glass containing divalent copper, the effect of the present invention is more exerted. In addition, since Na2 O has a property of dividing the bond between phosphorus and phosphorus of phosphoric acid, by containing Na2 O, the glass component is easily soluble in water. The content of P2 O5, Na2 O, CuO, and are not particularly limited. As for content of CuO, it is more preferable that it is 30-40 mol%. When content of the said grade, Cu becomes stable and it is easy to elute suitably. The molar ratio of P2 O5 and Na2 O may be substantially the same (ie, P2 O5 / Na2 O = 0.8 to 1.2) or may be different from each other. Specific composition (molar ratio) of the glass is, forexample, P 2 O 5 / Na 2 O / CuO = 35/35/30 orP 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 said copper glass (A) mixes and mixes raw materials, such as sodium phosphate and copper (II) oxide, melts at 1000-1200 degreeC for 30 minutes-2 hours, and flows a molten glass on an iron plate, and it cools, It can be manufactured by grinding about 1 to 100 µm using a planetary 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.
Content of the said copper glass (A) is 1-20 mass% in solid content of the composition of this invention in conversion of solid content, For example, it is 1, 2, 5, 10, 15, 20 mass%, The numerical value illustrated here The range between any two numerical values of may be sufficient.
<금속 피리치온류(B)> Metal pyrithiones (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.As metal pyrithione (B) used for this invention, bis (2-sulfide pyridine-1-olato) copper (copper pyridion), bis (2-sulfide pyridine-) 1-olato) zinc (zinc pyrithione) and the like, among which metal bispyrithiones (divalent metal pyrithione such as copper pyrithione and zinc pyrithione) are preferred, and copper Richons are particularly preferred. Commercially available products can be used for the metal pyrithione. Examples of commercially available products include 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.
Content of the said metal pyrithione (B) is 25-150 mass parts with respect to 100 mass parts of said copper glass (A) in solid content conversion, For example, it is 25, 50, 100, 150, 200, 250 mass parts It may be in the range between any two of the numerical values exemplified herein. If it is in this range, the antifouling effect with respect to animals, such as barnacles and ankylosworms, and tonic animals, such as a hydroworm, is especially good.
<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.Titanium oxide (C) used for this invention can mention titanium oxide, such as a rutile type, an anatase type, or a brookite type, These titanium oxides may be used independently, or 2 or more types You may use 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 choking phenomenon (when the surface of the coating is exposed, the surface resin of the coating surface is deteriorated by ultraviolet rays, heat, moisture, wind, etc., and the pigment of the color component of the paint becomes powdery like chalking. It is particularly preferable to use a rutile titanium oxide in that it is difficult to cause development).
본 발명의 산화 티타늄으로서는, 평균 입경이 0.001㎛~10㎛의 것이 바람직하고, 특히 0.1~3㎛의 것이 바람직하다.As titanium oxide of this invention, that whose average particle diameter is 0.001 micrometer-10 micrometers is preferable, and the thing of 0.1-3 micrometers is especially preferable.
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. In addition, the average particle diameter of the said titanium oxide means the value of the median diameter (50% cumulative particle diameter) computed from the volume average diameter measured by the laser diffraction and the scattering method. Specifically, measurement temperature 25 degreeC using methanol as a dispersion medium for particle size measurement using the laser diffraction and scattering method particle size analyzer and the optical apparatus MT3300 by Nikkiso Co., Ltd. Refers to the measured value.
본 발명의 산화 티타늄으로서는 흡유량(吸油量)이 1ml/100g~1000ml/100g인 것이 바람직하며, 특히 3ml/100g~50ml/100g인 것이 바람직하다.As titanium oxide of this invention, it is preferable that oil absorptions are 1 ml / 100g-1000 ml / 100g, and it is especially preferable that they are 3 ml / 100g-50 ml / 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 this invention may be surface-treated, For example, the surface-treated with the film | membrane which consists of oxides or organosilicon compounds of 1 or more types of elements of Al, Si, Zr, Sb, Cr, and Ti can also be used. .
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 titanium oxide, a commercial item can be used. As a commercial item, it is, for example, "FR-41" (made by Furukawa Chemical Co., Ltd. (FURUKAWA CHEMICALS CO., LTD)), "R-5N" (SAKAI CHEMICAL INDUSTRY CO., LTD.) "R-820" "" (made by ISHIHARA SANGYO KAISHA, LTD.), Etc. are mentioned.
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.Content of the said titanium oxide (C) is 50-300 mass parts of said titanium oxide (C) with respect to 100 mass parts of said copper glasses (A) in solid content conversion, For example, 50, 100, 150, 200, It is 250 and 300 mass parts, and may be in the range between any two of the numerical values illustrated here. Within this range, the effects of the present invention are better exhibited.
<그 외의 첨가 성분> <Other additive components>
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 coating composition used in the present invention includes an electrodeposition resin, and further, an elution aid, another antifouling agent, an antisettling agent, a flow inhibitor, a plasticizer, a surfactant, an antifoaming agent, a dye, a pigment, an organic solvent, water, and the like. It may be contained in any blending ratio within a range that does not impair the purpose of.
(용출조제) (Elution aid)
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 elution aid include silicone oils, ethylene-α-olefin copolymers, polybutenes, paraffins, petrolatum, dialkyl sulfide compounds, and the like. It can be suppressed and it can exert an antifouling effect for a long time.
용출조제의 함유량은, 특히 한정되지 않지만 고형분 환산으로 본 발명의 조성물의 고형분 중에서 보통 0.1~35질량%이며, 바람직하게는 1~30질량%이다.Although content of an elution aid is not specifically limited, Usually, it is 0.1-35 mass% in solid content of the composition of this invention in conversion of solid content, Preferably it is 1-30 mass%.
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.As the silicone oil, for example, polydimethylsiloxane, polymethylphenylsiloxane, methylphenylsiloxane-dimethylsiloxane copolymer, polyether modified polydimethylsiloxane, poly Ether modified polyalkyl (methyl) siloxane, polyether modified polydimethylsiloxane, long-chain alkyl modified polydimethylsiloxane, aralkyl modified polydimethyl Aralkyl modified polydimethylsiloxane, polyether long-chain alkyl aralkyl modified dimethyl silicone oil, fluorosilicone oil, amino modified silicone oil, other On various functional groups Modified silicone oils and the like. In particular, polyether modified silicone oils having a hydrophilic lipophilic balance (HLB value) of 0.5 to 9 are preferable, and polyether modified polydimethylsiloxane or polyether long-chain alkyl aralkyl modified dimethyl silicone oil having 0.5 to 9 is particularly preferable. . Moreover, as a preferable thing, the polyether modified polydimethylsiloxane or polyether long chain alkyl aralkyl modified dimethyl silicone oil whose hydrophilic lipophilic balance (HLB value) exists in the range of 1-5 is mentioned.
본 발명에서는, 이러한 실리콘 오일을 단독으로 이용해도 좋고, 2종 이상을 조합시켜 이용해도 좋다.In this invention, such silicone oil may be used independently and may be used in combination of 2 or more type.
실리콘 오일의 점도는, 도공 성능 및 도막 물성의 관점에서, 1000포아즈(poise) 이하가 바람직하며, 100포아즈 이하가 더 바람직하다.From the viewpoint of coating performance and coating film properties, the viscosity of the silicone oil is preferably 1000 poise or less, and more preferably 100 poise or less.
상기 에틸렌·α-올레핀 공중합체로서는, 예를 들면, 일반식 (I)로 나타내는 에틸렌·α-올레핀 공중합체를 들 수 있다.:As said ethylene-alpha-olefin copolymer, the ethylene-alpha-olefin copolymer represented by general formula (I) is mentioned, for example:
[화학식 1][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)(In formula, R <1> represents the C1-C10 linear or branched alkyl group, and x, y, and p represent the same or another integer of 1 or more, respectively.)
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.Especially as a C1-C10 linear or branched alkyl group represented by R <1> , a C1-C4 alkyl group, such as a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group and an isobutyl group, is preferable, Methyl group is more preferable.
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-alpha-olefin copolymer represented by general formula (I) is a copolymer obtained by copolymerizing ethylene and alpha-olefin. The ethylene-α-olefin copolymer may be any one of a random copolymer, a block copolymer or 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.A commercial item can be used as said ethylene-alpha-olefin copolymer. As a commercial item, for example, LUCANT HC-10, LUKANT HC-20, LUKANT HC-40, LUKANT HC-100, LUKANT HC-150, LUKANT HC-600, LUKANT HC- 2000 (all are registered trademarks, manufactured by Mitsui Chemicals, Inc.) and the like. These ethylene-alpha-olefin copolymers may be used independently and may be used in combination of 2 or more type.
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.From the viewpoint of coating performance and coating film properties, the number average molecular weight (Mn) of the ethylene-α-olefin copolymer is preferably 10,000 or less, and more preferably 1,000 to 3,000. It is preferable that the viscosity in 0 degreeC of the said ethylene-alpha-olefin copolymer is 20,000 PaS or less, and it is more preferable that it is 500 PaS 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 polybutenes include polybutene and polyisobutene. A commercial item can be used as polybutenes. As a commercial item, for example, polybutene LV-7, polybutene LV-10, polybutene LV-25, polybutene LV-50, polybutene LV-100, polybutene HV-35, polybutene HV-100, polybutene HV-300 and Polybutene HV-1900 (all manufactured by Nissei Chemical Inc.); Polybutene 0H, polybutene 5H, polybutene 10H, polybutene 300H, polybutene 2000H, polybutene 0R, polybutene 15R, polybutene 35R, polybutene 100R, polybutene 350R (all manufactured by Idemitsu Petrochemical Co., Ltd.); Polybutene 0N, Polybutene 06N, Polybutene 3N, Polybutene 10SH, Polybutene 200N (all Nippon Oil Corporation make), etc. are mentioned.
상기 파라핀류로서는, 예를 들면, n-파라핀, 고형 파라핀, 유동 파라핀, 염소화 파라핀 등을 들 수 있다.Examples of the paraffins include n-paraffins, solid paraffins, liquid paraffins, chlorinated paraffins, and the like.
상기 바셀린류로서는, 예를 들면, 백색 바셀린, 황색 바셀린 등을 들 수 있다.As said petrolatum, white petrolatum, yellow petrolatum, etc. are mentioned, for example.
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 compounds include di-tert-butyl decasulfide, dipentyl tetrasulfide, dipentyl pentasulfide, and dipentyl decasulfide. Dioctyl tetrasulfide, dioctyl pentasulfide, dinonyl tetrasulfide, dinonyl pentasulfide, di-tert-nonyl tetrasulfide ), Di-tert-nonylpentasulfide, didecyl tetrasulfide, didodecyl tetrasulfide, dioctadecyl tetrasulfide, dinonadecyl tetrasulfide, and the like. Can be mentioned.
(전착수지)Electrodeposition 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 resins and natural resins can be used. By containing the electrodeposition resins, workability for forming a coating film is improved. Moreover, the coating film excellent in adhesiveness with a to-be-coated film formation can be formed.
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, vinyl resin, alkyd resin, acrylic resin, urethane resin, polyester resin, synthetic rubber, chlorinated polyethylene, or the like can be used. As said vinyl resin, a vinyl chloride-vinyl acetate copolymer, a vinyl chloride- alkyl vinyl ether copolymer, a vinyl chloride resin, etc. can be illustrated.
또한, 상기 천연수지로서는, 예를 들면, 우드 로진, 껌 로진, 변성 로진 등을 들 수 있다.Moreover, as said natural resin, wood rosin, gum rosin, modified rosin, etc. are mentioned, for example.
상기 전착 수지로서는, 특히 아크릴 수지를 함유하는 것이 바람직하다.Especially as said electrodeposition resin, what contains an acrylic resin is preferable.
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.
-100-100 degreeC is preferable and, as for the glass transition temperature (Tg) of the said electrodeposition resin, -50-80 degreeC is more preferable. 5,000-1,000,000 are preferable and, as for the weight average molecular weight (Mw) of the said electrodeposition resin, 10,000-500,000 are more preferable. Although content of the said electrodeposition resin is not specifically limited, Usually, it is 0.1-80 mass% in solid content of the composition of this invention in conversion of solid content, Preferably it is 1-45 mass%.
(다른 방오약제)(Other antifouling medicines)
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.The following antifouling agents can be contained as antifouling agents other than copper glass (A) and metal pyrithione (B) containing bivalent copper used for this invention. Therefore, the formed coating film can exhibit more favorable 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-fluorodichloromethylthio) sulfamide (N, N'-dimethyl-N'-phenyl- (N-fluorodichloromethylthio) sulfamide) , N, N'-dimethyl-N'-tolyl- (N-fluorodichloromethylthio) sulfamide (N, N'-dimethyl-N'-tolyl- (N-fluorodichloromethylthio) sulfamide), 4,5-dichloro 2-n-octyl-4-isothiazolin-3-one (4,5-dichloro-2-n-octyl-4-isothiazoline-3-one), 2,3-dichloro-N- (2,6 -Diethyl phenyl) maleimide (2,3-dichloro-N- (2,6-diethylphenyl) maleimide), 2,3-dichloro-N- (2'-ethyl, 6'-methyl phenyl) maleimide (2 , 3-dichloro-N- (2'-ethyl, 6'-methylphenyl) maleimide), 3-benzo [b] thien-2-yl-5,6-dihydro-1,4,2-oxathiazine- 4-oxide (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 (2- (p-chlorophenyl) -3-cyano-4-bromo- 5-trifluoromethylpyrrole), tetrachloro-isophthalonitrile and the like can also 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 another antifouling agent used together with the said copper glass (A) and metal pyrithiones (B), 4, 5- dichloro- 2-n-octyl- 4-isothiazolin-3-one is especially preferable.
상기 다른 방오약제의 함유량은, 특히 한정되지 않지만, 고형분 환산으로 본 발명의 조성물의 고형분 중 보통 0.1~80질량%, 바람직하게는 1~50질량%이다.
Although content of the said other antifouling agent is not specifically limited, Usually, it is 0.1-80 mass% in solid content of the composition of this invention in conversion of solid content, Preferably it is 1-50 mass%.
(침강 방지제·흐름방지제(Sagging agent)) (Sagging 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 the anti-flow agent include polyethylene wax, hydrogenated castor oil wax, polyamide wax, amide wax, polyethylene oxide wax, and the like, and preferably hydrogenated castor oil wax and poly Amide waxes, amide waxes, and oxidized polyethylene waxes. The sedimentation inhibitor and the flow inhibitor may be used alone or in combination of two or more thereof.
(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.
As a plasticizer, a phthalic acid ester, adipic acid ester, a phosphate ester, etc. are mentioned, for example. Examples of the phthalic acid esters include dibutyl phthalate, dioctyl phthalate and diethyl ethyl phthalate. Examples of the adipic acid ester include dibutyl adipic acid, dioctyl adipic acid and 2-ethylhexyl adipic acid. Examples of the phosphate ester include tricresyl phosphate and trioctyl phosphate. The said plasticizers may be used independently, or may be used in combination of 2 or more type.
(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.As an organic solvent, For example, aromatic solvents, such as xylene, toluene, Solvesso 100, and Solvesso 150 (all are a trademark of 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.In addition, organic solvents considering low toxicity, low odor and low environmental load can be used. For example, Pegasol AN45, Pegaso AS100 (all trademarks, manufactured by Exxon Mobil Corporation), LAWS, HAWS Aromatic, alicyclic, aliphatic hydrocarbon mixed solvents, such as (all from Shell Chemicals); Glycol 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® 900 (C9 aromatic hydrogenated body) and Rikasol portion (registered trademark) 1000 (C10 aromatic hydrogenated body); Alicyclic / aliphatic mixed solvents such as ShellSol D40 (trademark, manufactured by Shell Chemicals), Exol D30, and Exsol D40 (all trademarks, manufactured by Exxon Mobil Corporation); Aliphatic hydrocarbon mixed solvents, such as Isopar G and Isopar H (all are trademarks of Exxon Mobil) can also be used.
이러한 유기용제는 단독 또는 2종 이상을 혼합하여 이용할 수 있다. These organic solvents can be used individually or in mixture of 2 or more types.
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 for forming antifouling coating films such as various fishing tools and underwater structures. In particular, the composition of the present invention can be suitably used as an antifouling coating 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 fishnet antifouling coating composition of this invention can be prepared by mixing the said [A]-[C] component and each said component as needed. About the addition amount of each component at the time of mixing, it may adjust suitably so that it may become the said compounding quantity and content. There is no restriction | limiting in particular about the order which mixes each component. About a mixing method, you may use a well-known method, such as mixing using a stirring apparatus.
어망방오 도막의 형성 방법, 방오 도막, 및 도장물Formation method of a fishing net 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 formation method of the fish-eye antifouling coating film of this invention is characterized by forming an antifouling coating film on the surface of a to-be-coated film formation using the said fish-eye antifouling coating composition. The antifouling coating film obtained by the forming method of the present invention is gradually dissolved on the surface and the surface of the coating film is constantly updated, thereby preventing the adhesion of marine pollutant organic matter. Moreover, after dissolving a coating film, by coating the said composition, an antifouling effect can be exhibited continuously.
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?) 설비 등을 들 수 있다.As a to-be-coated film formation, a fishing tool, an underwater structure, etc. are mentioned, for example. As a fishing tool, the fishing net for aquaculture or stationary, the fishing bobber used for the said fishing net, a fishing net attachment tool, such as a rope, etc. are mentioned, for example. As an underwater structure, a power plant water pipe, a bridge, a harbor facility, etc. are mentioned, for example.
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 this invention can be formed by apply | coating the said fishing net antifouling coating composition to the surface (all or part) of a to-be-coated 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.As a coating method, the brush coating, the spray method, the dipping method, the flow coat method, the spin coat method, etc. are mentioned, for example. These can use together 1 type (s) or 2 or more types. For example, when apply | coating the fishing net antifouling coating composition of this invention to a fishing net, it is preferable to use the dipping method as a coating method.
도포 후 건조시킨다. 건조 온도는 실온이면 된다. 건조 시간은 어망방오 도료의 부착량에 따라 적당히 설정할 수 있다.Dry after application. The drying temperature should just be room temperature. Drying time can be suitably set according to the adhesion amount of a fish 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.What is necessary is just to set the adhesion amount of the said fishnet antifouling paint suitably according to the kind etc. of to-be-coated film formation. For example, when a to-be-coated film formation is a fishing net, the adhesion amount of a dry coating film becomes like this. Preferably it is 1-35 mass parts, More preferably, it is 4-20 mass parts with respect to 100 mass parts of fishing nets.
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 this invention has the said antifouling coating film on the surface. The coating material of this invention may have the said antifouling coating film in the whole surface, and may have it in part.
실시예Example
이하에, 실시예 등을 이용하여 본 발명의 특징을 더 명확하게 나타낸다. 그러나, 본 발명은 이러한 실시예 등에 한정되는 것이 아니다.
Below, the characteristic of this invention is shown more clearly using an Example etc. However, the present invention is not limited to these examples and the like.
비교 제조예 1 (1가의 구리를 포함하는 구리 유리H-1의 제조)Comparative Production Example 1 (Preparation of Copper Glass H-1 Containing Monovalent 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.
The glass component material and the copper compound of the following composition ratio are mixed uniformly, melt | dissolved for 60 minutes using the gas furnace of 1100-1300 degreeC, and then quenched to produce the soluble glass containing monovalent copper, and the said solubility. The glass is ground in a ball mill to obtain a copper glass powder containing monovalent copper.
<조성> <Composition>
SiO2: 7.7질량부SiO2 : 7.7 parts by mass
Al2O3: 0.1질량부Al2 O3 : 0.1 parts by mass
Na2O: 5.9질량부Na2 O: 5.9 parts by mass
B2O3: 28.8질량부B2 O3 : 28.8 parts by mass
Cu2O: 53.3질량부Cu2 O: 53.3 parts by mass
ZnO: 4.2질량부
ZnO: 4.2 parts by mass
실시예 1~6 및 비교예 1~12Examples 1-6 and Comparative Examples 1-12
표1에 기재된 배합 성분을 표1에 기재된 비율(질량%)로 혼합함으로써 방오 도료 조성물을 얻는다.The antifouling coating composition is obtained by mixing the compounding component of Table 1 in the ratio (mass%) of 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)Product name "PNU-40": Copper glass (P2 O5 / Na2 O / CuO = 30/30/40 (mol%)) containing divalent copper, average particle diameter 3μ, (Toyo Glass Co., Ltd. (TOYO) 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)Trade name "PNU-30": Copper Glass(P 2 O 5 / Na 2 O / CuO = 35/35/30 (% by mole) including a second copper-valent, an average particle diameter of 3μ, (Toyobo sink switch (Ltd.))
상품명 「NC-301」: 아산화구리(닛신 켐코(주)(NISSIN CHEMCO Co., Ltd.)제)Product name "NC-301": Copper oxide (made by Nissin Chemco Co., Ltd.)
상품명 「산화 아연2종」: 산화 아연(세도화학공업(주)(Seido Chemical Industry Co., Ltd.)제)Product name "two kinds of zinc oxide": zinc oxide (made by Seido Chemical Industry Co., Ltd.)
상품명 「Nocceler PZ」:디메틸디티오카르바메이트아연(오우치신흥화학 공업(주)(OUCHI SHINKO CHEMICAL INDUSTRIAL)제)`` Nocceler PZ '': Dimethyldithiocarbamate zinc (product made in Ouchi Shinsei Chemical Co., Ltd. (OUCHI SHINKO CHEMICAL INDUSTRIAL))
상품명 「Nocceler TET-G」:테트라에틸티우람 디설파이드(오우치신흥화학 공업(주)제)"Nocceler TET-G": Tetraethyl thiuram disulfide (product made in Ouchi emerging chemical industry)
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 pyridine-1-olato) copper (bis (2-sulfidepyridin-1-olato) copper) (product made in Arch Chemical Japan (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 pyridine-1-olato) zinc (bis (2-sulfidepyridin-1-olato) zinc) (product made in Achi Chemical Japan Co., Ltd.)
상품명 「FR-41」:산화 티타늄(루틸형 산화 티타늄, 후루카와 케미컬(주)(FURUKAWA CHEMICALS CO., LTD)제)`` FR-41 '': Titanium oxide (rutile type titanium oxide, product made by Furukawa Chemical Co., Ltd. (FURUKAWA CHEMICALS CO., LTD))
상품명 「산화 아연2종」:산화 아연(세도화학공업(주)제)"Two kinds of zinc oxide": Zinc oxide (made by Sedo Chemical Co., Ltd.)
상품명 「티누빈(TINUVIN)P」:2-(5-메틸-2-히드록시 페닐)벤조트리아졸(나가세 산업(주)(Nagase & Co., Ltd.)제)"Tinuvin (TINUVIN) P": 2- (5-methyl-2-hydroxy phenyl) benzotriazole (made by Nagase Industries Co., Ltd.) (Nagase & Co., Ltd.)
상품명 「NITTOL HN」:아크릴 수지 크실렌 용액(고형분 40%, Tg= 약20도, Mw= 약230000, 닛토 카세이(주)(NITTO KASEI CO., LTD.)제)"NITTOL HN": Acrylic resin xylene solution (40% of solid content, Tg = approximately 20 degrees, Mw = approximately 230000, product made by NITTO KASEI CO., LTD.)
상품명 「KF-6020」:폴리 에테르 변성디메틸 실리콘 오일 (신에츠 화학공업(주)(Shin-Etsu Chemical Co, Ltd)제)`` 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)`` X-22-2516 '': Polyether long chain alkyl aralkyl modified dimethyl silicone oil (made by Shin-Etsu Chemical Co., Ltd.)
상품명 「루칸트 HC-40」:에틸렌료-올레핀 공중합체(미쓰이 케미칼(주)(Mitsui Chemicals, Inc)제)"Lucant HC-40": Ethylene pigment-olefin copolymer (made by Mitsui Chemicals, Inc.)
상품명 「폴리부텐 0N」:폴리부텐(일본 유지(주)(NOF CORPORATION)제)`` Polybutene 0N '': Polybutene (product made in Nippon Oil Holdings Co., Ltd. (NOF CORPORATION))
상품명 「디스파론 4200-20」:산화 폴리에틸렌계 왁스(고형분 20%, 구스모토 케미칼(주)(Kusumoto Chemicals, Ltd.)제)"Disparon 4200-20": Oxidized polyethylene-based wax (20% of solid content, product of Kusumoto Chemical Co., Ltd.)
상품명 「디스파론(Disparlon) A630-20X」:폴리 아마이드계 왁스(고형분 20%, 구스모토 케미칼(주)제)"Disparlon (Disparlon) A630-20X": Polyamide-based wax (20% of solid content, product of Kusumoto Chemical Co., Ltd.)
크실렌: 키시다 케미칼(주)(Kishida Chemical Co., Ltd.)제, 1급 시약Xylene: made by Kishida Chemical Co., Ltd., first-class 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.Polyethylene fishing nets (400 deniers, 40 pieces, 8 sections) were applied to the antifouling paint compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 12 so that the adhesion amount of the dry coating film was 15 parts by mass relative to 100 parts by mass of the fishing net. Dipping applied and dried. A fishing net with a coating film is fixed to a rim of 40 × 60 cmSUS, immersed in a draft on a raft in Owase, Mie Prefecture, where the active area of marine pollutants is strongly active. Observations were periodically made over 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 performed by the following method. On the other hand, the attachment area (%) of aquatic organisms takes a photograph of the fishing net from above after the test period (2, 4, 6, 8, 10 or 12 months) to determine the occupied area of the aquatic organism in the fishing net. Visual evaluation was performed.
◎: 수생 생물의 부착 면적이 0%(Double-circle): 0% of attachment area of aquatic organisms
○: 수생 생물의 부착 면적이 0% 초과 10%미만○: adhesion area of aquatic organisms is greater than 0% and less than 10%
△: 수생 생물의 부착 면적이 10% 이상 50%미만(Triangle | delta): The attachment area of aquatic organisms is 10% or more and less than 50%.
×: 수생 생물의 부착 면적이 50%이상X: The attachment area 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 turned out that the antifouling coating composition of Examples 1-6 of this invention is excellent in long-term antifouling property more than any one of the antifouling coating compositions of Comparative Examples 1-12.
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 1-6 contain the three components of copper glass containing bivalent copper, metal pyrithiones, and titanium oxide. On the other hand, Comparative Example 1 contains only copper glass containing divalent copper, Comparative Examples 2 and 3 contain only copper glass and metal pyrithione containing divalent copper, and Comparative Example 4 contains divalent copper Although containing copper glass and titanium oxide, the long-term antifouling property of Comparative Examples 1-4 was much lower than Examples 1-6. The results show that the antifouling coating composition contains all three components in order to exhibit excellent long-term antifouling properties, and when any one of the three components is omitted, the long-term antifouling property is extremely reduced.
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.Moreover, in Comparative Examples 5-8, the antifouling paint containing the three components of copper glass, metal pyrithione, and titanium oxide containing monovalent copper, or three components of copper oxide, metal pyrithione, and titanium oxide. Although the long-term antifouling property of the composition was investigated, the long-term antifouling property was much lower than Examples 1-6 also in any one of Comparative Examples 5-8. Therefore, the effect of greatly improving long-term antifouling properties by adding metal pyrithiones and titanium oxide is unique to copper glass containing divalent copper, and when copper glass or cuprous oxide containing monovalent copper is used, It was found that the result 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.Moreover, Comparative Example 9 relates to an antifouling coating composition comprising pyrithione and titanium oxide but not containing copper glass comprising monovalent copper. According to the results of the antifouling evaluation, in Comparative Example 9, aquatic organisms were attached at the time of observation at 4 months, and the long-term antifouling property was much lower than that of the 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, it was found that the aquatic organisms adhered to the comparative example 10 at the time of 4 months of observation, and even when 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, long-term antifouling property was slightly improved in Comparative Example 11, but aquatic organisms were attached at the time of observation at 4 months, and long-term antifouling property was not significantly improved even if dimethyldithiocarbamate zinc was added. I knew that.
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.In Comparative Example 12, tetraethylthiuram disulfide was added to Comparative Example 9. According to the results of the antifouling evaluation, it was found that in Comparative Example 12, aquatic organisms were attached at the time of 4 months of observation, and even if tetraethylthiuram disulfide was added, long-term antifouling properties were 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.Furthermore, it was found that Examples 1, 2 and 5 containing copper pyrithione were superior in long-term antifouling properties as compared to Examples 3, 4 and 6 containing zinc pyrithione.
Claims (5)
Translated fromKorean상기 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 50~300질량부인 방오 도료 조성물.
As an antifouling coating composition containing (A) copper glass containing bivalent copper, (B) metal pyrithiones, and (C) titanium oxide,
The metal of the said metal pyrithione is copper or zinc,
It contains more electrodeposition resin,
Content of CuO in the said copper glass (A) is 25-40 mol%,
Content of the said copper glass (A) is 1-20 mass% in solid content of the said antifouling coating composition in solid content conversion,
Content of the said metal pyrithione (B) is 25-150 mass parts with respect to 100 mass parts of said copper glass (A) in solid content conversion,
Content of the said titanium oxide (C) is 50-300 mass parts with respect to 100 mass parts of said copper glasses (A) in solid content conversion.
상기 금속 피리치온은 금속 비스피리치온류인 방오 도료 조성물.
The method of claim 1,
An antifouling coating composition wherein the metal pyrithione is metal bispyrithione.
상기 산화 티타늄이 루틸형인 방오 도료 조성물.
The method according to claim 1 or 2,
The antifouling coating composition wherein the titanium oxide is rutile type.
용출조제를 더 함유하는 방오 도료 조성물.
4. The method according to any one of claims 1 to 3,
An antifouling coating composition further comprising an elution aid.
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| PCT/JP2011/075164WO2012063679A1 (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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Also Published As
| Publication number | Publication date |
|---|---|
| JP2012102233A (en) | 2012-05-31 |
| WO2012063679A1 (en) | 2012-05-18 |
| CN103370385A (en) | 2013-10-23 |
| TWI431079B (en) | 2014-03-21 |
| KR101670428B1 (en) | 2016-10-28 |
| CN103370385B (en) | 2015-08-12 |
| JP4812895B1 (en) | 2011-11-09 |
| AU2011327409A1 (en) | 2013-05-02 |
| TW201224083A (en) | 2012-06-16 |
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