TW201224083A

TW201224083A - Coating composition for preventing an object from being dirtied; fishing net, fishing device, and structure immersed in water coated with the same

Info

Publication number: TW201224083A
Application number: TW100140049A
Authority: TW
Inventors: Toshiyuki Takezawa
Original assignee: Nitto Kasei Co Ltd
Priority date: 2010-11-10
Filing date: 2011-11-03
Publication date: 2012-06-16
Also published as: JP2012102233A; AU2011327409A1; CN103370385B; JP4812895B1; KR20130084675A; CN103370385A; KR101670428B1; TWI431079B; WO2012063679A1

Abstract

Provided is an antifouling coating composition capable of exhibiting an antifouling effect for a long period of time even in ocean water containing highly active barnacles, serpula, and other animal species, as well as hydrozoans and other coelenterates. This antifouling coating composition comprises (A) copper glass containing divalent copper, (B) metal pyrithiones, and (C) titanium oxide, wherein the metal of the metal pyrithiones is copper or zinc; the composition further contains a spreading resin; the content of copper in the copper glass (A) is 24-40 mol%; the content of the copper glass (A), in terms of solid content, is 1-20 mass% of the solid content of the antifouling coating composition; the content of the metal pyrithiones (B), in terms of solid content, is 25-150 parts by mass per 100 parts by mass of the copper glass (A); and the content of the titanium oxide (C), in terms of solid content, is 50-300 parts by mass per 100 parts by mass of the copper glass (A).

Description

201224083 六、發明說明：【發明所屬之技術領域】本發明係關於一種用於長期地防止水生污損生物附著於養殖用或固定網用漁網、在它們中使用的浮標和繩索等漁網用具（以下，有時也將它們合併稱為漁網類）以及發電站的冷卻水導管等之水中建築結構等上的防污塗料組成物；以及塗布有該防污塗料組成物的漁網類及水中建築結構。【先前技術】漁網類及水中建築結構等由於長期設置於海中，因此在未塗佈防污塗料組成物而使用時，會附著海蕩類、藤壺、龍介蟲、苔蟲、軟體動物類等多種水生污損生物。由此，海水在漁網的内側與外側之間的流通變差，產生由缺氧導致養殖魚大量死亡、因發生傳染病而導致無法上市等較大損失。此外’養殖漁網和固定漁網等上附著有附著生物時，漁網變重，還存在由於漁網的下沉而導致魚逃脫、漁網自身流失的問題。因此需要頻繁地更換漁網，存在必須花費極大的勞力和費用來保養漁網的問題。以防止這些水生污損生物的附著等為目的，一直以來廣泛進行著在漁網類及水中建築結構上塗布多種防污塗料組成物。這些防污塗料組成物中，特別是含有氧化亞銅、 201224083 銅玻璃及吨啶硫酮銅等銅系藥劑的防污塗料組成物’表現出一定的防止厚殼胎貝等貝類、藤壺和龍介蟲等附著的效果’因此得到廣泛使用。例如’作為對於藤壺和龍介蟲等動物類、水螅蟲等腔腸動物效果優良的防污塗料組成物，提出了配合有氧化亞銅和特定的聚醚改質矽油的防污劑組成物（專利文獻此外’還提出了在氧化亞銅和特定的聚醚改質矽油的基礎上配合。比啶硫鲷銅的防污塗料組成物（專利文獻2 )。然而’這些防污塗料組成物令使用的氧化亞銅難溶于水’難以進行離子化，因此無法發揮對水生污損生物的充分的迴避（avoidance)效果，並非屬於發揮充分的防污效果的物質。 · . 此外’提出了特徵在於使用含有一價銅的溶解性銅玻璃代替氧化亞銅’並且並用金屬吡啶硫酮類的防污塗料組成物（專利文獻3)。但是，對於該防污塗料組成物中使用的含有一價銅的溶解性銅玻璃而言’雖然與氧化亞銅相比銅離子的溶出量較高，但仍然不是發揮出對水生污損生物的充分的迴避效果的物質，並不能滿足市場的需求。進而，提出了含有包含二價銅的銅玻璃的防污塗料組成物（專利文獻4)。但是，該防污塗料組成物的對水生污損生物的迴避效果仍然不充分。因此，渴望開發出塗膜物性良好 '漁網塗布時的操作 201224083 性優良、且在藤壺或龍介蟲等動物類、水螅蟲等腔腸動物的活性較強的海域能夠長期發揮防污效果的漁網用防污塗料組成物。 [現有技術文獻] [專利文獻] 專利文獻1:日本特開平8-252533號公報專利文獻2 ··日本特開2002-265849號公報專利文獻3:日本特開2000-264804號公報專利文獻4 :日本特開2004-203774號公報【發明内容】 [發明所要解決的問題] 本發明蓉於上述問題而完成，提供一種防污塗料組成物’其即使是在藤壺或龍介蟲等動物類、水總蟲等腔腸動物的活性較強的海域’也能夠長期發揮防污效果。 [用於解決問題的方法] 根據本發明能夠提供一種防污塗料組成物，含有（A)含有二價銅的銅玻璃、（B)金屬吡啶硫酮類以及（〇氧化鈦，其中，所述金屬吡啶硫酮類的金屬為銅或鋅，還含有擴散用（spreading )樹脂，所述銅玻璃（A)中的CuO的含量為 25〜40摩爾％;以固體成分換算，所述銅玻璃（A)的含量占所述防污塗料組成物的固體成分中的1〜20質量％;以固體成 201224083 分換算’所述金屬吡啶硫酮類（B)的含量相對於所述銅玻璃 (A) 100質量份為254 5〇質量份；以固體成分換算，所述氧化鈦（C)的含量相對於所述銅玻璃（A)l〇〇質量份為50〜300 質量份。本發明人為了開發出能夠長期發揮防污效果的防污塗料組成物進行了深入研究，結果發現防污塗料組成物在以特定的比例含有（A)含有二價銅的銅玻璃、（B )金屬吡啶硫酿I類以及（C)氧化鈦這三種成分的情況下，發揮出極為優良的長期防污性，從而完成了本發明。雖然對於本發明的防污塗料組成物發揮優良的長期防污性的作用尚不明確，但在實驗上可知，對於僅含有包含二價銅的銅玻璃的情況、或者含有.包含二價銅的銅玻.璃和金屬吡啶硫酮類的情況而言，均不能長期持續防污效果，只有在含有上述三種成分的情況下才能夠發揮出優良的長期防污性。帶來防污效果的有效成分為銅玻璃和金屬吡咬破酿I類，由此推測氧化鈦起到藉由適度控制銅玻璃和金屬比咬硫酮類的浴出速度’從而使上述有效成分長期以穩定的速度溶出的作用。另外，對於含有包含一價銅的銅玻璃、金屬吼啶硫酮類和氧化鈦這三種成分的塗料組成物、和含有氧化亞銅、金屬吡啶硫酮類和氧化鈦這三種成分的塗料組成物的長期防污性也進行了研究，但與本發明相比，其長期防污性均 201224083 較差。由此表明，由本發明發揮的極為優良的長期防污性是藉由使防污組成物以特定的比例含有（A)含有二價銅的銅玻璃、（B)金屬吡啶硫酮類以及（c)氧化鈦這三種成分才夠發揮出來的，從而完成了本發明。 [发明效果] 利用本發明的防污塗料組成物，即使是在藤壺或龍介蟲等動物類、水媳蟲等腔腸動物的活性較強的海域，也能夠長期發揮防污效果。【實施方式】本發明的防污塗料組成物’含有U)含有二價鋼的鋼玻璃、（B)金屬吡啶硫酮類以及（c)氧化鈦，其中，所述金屬吡啶硫酮類的金屬為銅或辞，還含有擴散用樹脂，所述鋼玻璃（A)中的CuO的含量為25~4〇摩爾％;以固體成分換算，所述銅玻璃（A)的含量為所述防污塗料組成物的固體成分中的卜20質量％ ;以固體成分換算，所述金屬吡啶硫酮類 (B)的含量相對於所述銅玻璃（A)1〇〇質量份為25〜15〇質量份；以固體成分換算，所述氧化鈦（c)的含量相對於所述銅玻璃（A)100質量份為50〜300質量份。〈銅玻璃（A)> 本發明中使用的銅玻螭（A)為含有二價銅的玻璃，該銅玻璃中的CuO的含量為25~40摩爾％。對於玻璃的組成而 201224083 言’只要能夠以適度的速度溶解而使銅溶出，則沒有特別限制，優選磷酸鹽玻璃（以pz〇s為主體的玻璃），進一步優選P2〇s-Na2〇-CuO系玻璃。就磷酸鹽玻璃而言，與二氧化石夕 (silica)玻璃相比，能夠增加相對於玻璃的溶解量的銅的溶出量’並且，容易得到穩定的溶出性能。因此，使用含有二價銅的磷酸鹽玻璃製作塗料組成物時，本發明的效果能夠更好的發揮。此外，由於NaaO具有切斷磷酸的碟與氧的鍵的性質’因此藉由含有NhO，玻璃成分成為容易溶解於水的本解性玻璃。pz〇5、Na2〇以及CuO的含量不受特別限定。CuO的含量更加優選為30〜40摩爾％。這是因為，在這種程度的含量的情況下，Cu容易穩定地適度溶出。p2〇s 與Naz〇的摩爾比率可以實質上·相同（即， P2〇5/Na2〇 = 0_8~1.2)’也可以不同。玻璃的具體組成（摩爾比）例如為 ’ P2〇s/Na2〇/CuO=35/35/30、或者 P2〇s/Na2〇/Cii0 = 30/30/40 〇配製並混上述銅玻璃（A)可以按照如下方法進行製造：合磷酸納、氧化銅⑴）等組成原料，在丨刚、副。c下進行炫化30分鐘~2小時，將該炫化的玻璃繞到鐵板上放冷後，利用行星式球磨機等粉碎至約1〇〇以肌。以固體成分換算成物的固體成分中占上述鋼玻璃A的含量在本發明的組，2° 質量例如為 1'2、5、10、15 別質量％，可的數值的任意兩個之間的 8 201224083 〈金屬吡啶硫酮類（Β)> 作為本發明中使用的金屬吡啶硫酮類（Β)，可以列舉：雙（2-硫代-1-氧化吡啶）銅（吡啶硫酮銅）、雙（2-硫代-卜氧化°比啶）鋅（吡啶硫酮鋅）等，其中，優選金屬雙吡啶硫酮類 (°比啶硫輞銅、吡啶硫酮鋅等二價金屬的吡啶硫酮），特別優選吡啶硫酮銅。對於金屬吡啶硫酮類而言，可以使用市售品。作為市售品，可以列舉例如：C〇ppe]r Omadine201224083 VI. Description of the Invention: [Technical Field] The present invention relates to a fishing net appliance for use in a long-term prevention of attachment of aquatic fouling organisms to fishing nets for breeding or fixed nets, and buoys and ropes used therein (hereinafter And sometimes they are combined as a fishing net type) and an antifouling coating composition on a water building structure or the like of a cooling water pipe of a power station; and a fishing net type and a water building structure coated with the antifouling paint composition. [Prior Art] Since fishing nets and underwater structures are installed in the sea for a long time, when they are not coated with antifouling paint composition, they will be attached to the sea, barnacle, dragon worm, moss, mollusc, etc. A variety of aquatic fouling organisms. As a result, the flow of seawater between the inside and the outside of the fishing net is deteriorated, resulting in a large loss of a large number of dead fish caused by lack of oxygen, and the inability to market due to infectious diseases. In addition, when attached organisms are attached to farmed fishing nets and fixed fishing nets, the fishing nets become heavier, and there is also the problem that the fish escapes and the fishing nets are lost due to the sinking of the fishing nets. Therefore, it is necessary to frequently change the fishing net, and there is a problem that it is necessary to spend a great deal of labor and expense to maintain the fishing net. In order to prevent the adhesion of these aquatic fouling organisms, various antifouling coating compositions have been widely applied to fishing nets and underwater building structures. In these antifouling coating compositions, in particular, an antifouling coating composition containing a copper-based agent such as cuprous oxide, 201224083 copper glass, and ton acesulfame copper exhibits certain shellfish, barnacles, and the like to prevent thick-shelled fetuses and the like. The effect of attachment of dragon worms and the like 'is therefore widely used. For example, as an antifouling coating composition which is excellent for animals such as barnacles and dragon worms, and watery mites, etc., an antifouling composition containing cuprous oxide and a specific polyether modified eucalyptus oil is proposed ( In addition, the patent document also proposes an antifouling coating composition based on cuprous oxide and a specific polyether modified eucalyptus oil (patent document 2). However, these antifouling coating composition orders Since the used cuprous oxide is hardly soluble in water, it is difficult to ionize, and thus it is not possible to exhibit a sufficient avoidance effect on aquatic fouling organisms, and it is not a substance that exhibits a sufficient antifouling effect. An antifouling coating composition using a molten copper glass containing monovalent copper instead of cuprous oxide and using a metal pyrithione (Patent Document 3). However, a monovalent content is used for the antifouling coating composition. In the case of copper-soluble copper glass, although the amount of copper ions eluted is higher than that of cuprous oxide, it does not exert sufficient avoidance effect on aquatic fouling organisms. Further, an antifouling coating composition containing copper glass containing divalent copper has been proposed (Patent Document 4). However, the antifouling coating composition avoids aquatic fouling organisms. The effect is still insufficient. Therefore, it is eager to develop a good coating film property. The operation of the fishnet coating is excellent in 201224083, and it can be used for a long time in the sea where the activity of coelenteans such as barnacles or dragon worms and watery aphids is strong. The antifouling coating composition for the anti-fouling effect of the anti-fouling effect. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei 8-252533. [Problem to be Solved by the Invention] The present invention has been accomplished in view of the above problems, and provides an antifouling coating composition 'even It is also a long-term antifouling effect in animals such as barnacles or dragon worms, such as animals and watery worms, which have strong activity. [Methods for solving problems] According to the present invention, it is possible to provide an antifouling coating composition comprising (A) copper glass containing divalent copper, (B) metal pyrithione, and (titanium oxide, wherein the metal pyrithione metal a copper or zinc, further comprising a spreading resin, wherein the content of CuO in the copper glass (A) is 25 to 40 mol%; and the content of the copper glass (A) is in terms of solid content. 1 to 20% by mass of the solid content of the antifouling coating composition; the content of the metal pyrithione (B) in terms of solids in 201224083 minutes is 254 5 parts by mass based on 100 parts by mass of the copper glass (A). The content of the titanium oxide (C) is 50 to 300 parts by mass based on the mass of the copper glass (A). In order to develop an antifouling coating composition capable of exhibiting an antifouling effect for a long period of time, the present inventors have found that the antifouling coating composition contains (A) copper glass containing divalent copper in a specific ratio, (B) In the case of the three components of the metal pyrithione type I and (C) titanium oxide, the extremely long-term antifouling property is exhibited, and the present invention has been completed. Although it is not clear that the antifouling coating composition of the present invention exhibits excellent long-term antifouling properties, it is experimentally known that it contains copper copper containing only divalent copper or contains divalent copper. In the case of copper glass and metal pyrithione, the antifouling effect cannot be sustained for a long period of time, and excellent long-term antifouling properties can be exhibited only when the above three components are contained. The effective ingredients for the antifouling effect are copper glass and metal thief bite type I, and it is presumed that titanium oxide acts as a bathing speed by moderately controlling copper glass and metal thizones to make the above active ingredients Long-term dissolution at a steady rate. Further, a coating composition containing three components of copper glass, metal acridine thione, and titanium oxide containing monovalent copper, and a coating composition containing three components of cuprous oxide, metal pyrithione, and titanium oxide The long-term antifouling property was also studied, but compared with the present invention, the long-term antifouling property was poor in 201224083. This shows that the extremely excellent long-term antifouling property exerted by the present invention is obtained by containing the antifouling composition in a specific ratio (A) copper glass containing divalent copper, (B) metal pyrithione, and (c). The three components of titanium oxide are sufficient to complete the present invention. [Effect of the Invention] The antifouling coating composition of the present invention can exhibit an antifouling effect for a long period of time even in a sea area where the activity of an animal such as barnacle or dragon worm or a coelenter such as water mites is strong. [Embodiment] The antifouling paint composition of the present invention 'containing U) steel glass containing divalent steel, (B) metal pyrithione, and (c) titanium oxide, wherein the metal pyrithione metal Further, in the case of copper, the resin for diffusion is further contained, and the content of CuO in the steel glass (A) is 25 to 4 mol%; and the content of the copper glass (A) is the antifouling in terms of solid content. 20% by mass of the solid content of the coating composition; the content of the metal pyrithione (B) in terms of solid content is 25 to 15 Å by mass based on 1 part by mass of the copper glass (A) 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. <Copper Glass (A)> The copper glass (A) used in the present invention is a glass containing divalent copper, and the content of CuO in the copper glass is 25 to 40% by mole. In the case of the composition of the glass, 201224083 is not particularly limited as long as it can be dissolved at a moderate rate, and phosphate glass (glass mainly composed of pz〇s) is preferable, and P2〇s-Na2〇-CuO is further preferable. Glass. In the case of the phosphate glass, the amount of eluted copper of the amount of dissolution relative to the glass can be increased as compared with the silica glass, and stable dissolution performance can be easily obtained. Therefore, when a coating composition is prepared using phosphate glass containing divalent copper, the effects of the present invention can be better exerted. Further, since NaaO has a property of cutting off the bond between the disc and the phosphoric acid of phosphoric acid, the glass component becomes a water-soluble glass which is easily dissolved in water by containing NhO. The content of pz〇5, Na2〇, and CuO is not particularly limited. The content of CuO is more preferably from 30 to 40% by mole. This is because, in the case of such a content, Cu is easily and stably eluted moderately. The molar ratio of p2〇s to Naz〇 may be substantially the same (i.e., P2〇5/Na2〇 = 0_8~1.2)' may be different. The specific composition (molar ratio) of the glass is, for example, 'P2〇s/Na2〇/CuO=35/35/30, or P2〇s/Na2〇/Cii0 = 30/30/40 〇 formulated and mixed with the above copper glass (A ) It can be manufactured as follows: raw materials such as sodium phosphite, copper oxide (1)), etc. After squeezing for 30 minutes to 2 hours, the glazed glass is wound on an iron plate and allowed to cool, and then pulverized to about 1 〇〇 muscle by a planetary ball mill or the like. The content of the steel glass A in the solid content of the solid content is in the group of the present invention, and the mass of 2° is, for example, 1'2, 5, 10, 15% by mass, and any two of the numerical values 8 201224083 <Metal pyrithione (Β)> As the metal pyrithione (Β) used in the present invention, bis(2-thio-1-oxidized pyridine) copper (copper thiophene copper) , bis (2-thio-bu oxidized pyridine) zinc (zinc pyrithione), etc., among which metal bipyridyl thiones (° compared to divalent metals such as acridine sulfonium or zinc pyrithione) Pyrithione) is particularly preferably copper pyrithione. For metal pyrithiones, commercially available products can be used. As a commercial item, for example, C〇ppe]r Omadine can be cited.

Powder、Zinc Omadine Powder(均為 Arch Chemicals Japan, Inc.製）等。以固體成分換算’上述金屬吡啶硫酮類（B)的含量相對於上述銅玻璃（A)l00質量份為25〜150質量份，例如為25、 50、100、150、200、250質量份，可以在此處例示出的數值的任意兩個之間的範圍内。在上述範圍内時，對藤壺和龍介蟲等動物類、水螅蟲等腔腸動物等的防污效果特別優良。〈氧化鈦（C)> 對於本發明中使用的氧化鈦（C)而言，可以列舉為金紅石型、銳鈦礦型或板鈦礦型等的氧化鈦，這些氧化鈦可以單獨使用’或者也可以組合兩種以上來使用。上述氧化鈦中’從難以發生所謂的粉筆（Chalking)現象（係指塗裝表面在暴露狀態時，表現出由紫外線 '熱、水 201224083 分、風等導致塗裝面的表面樹脂劣化，塗料的顏色成分的顏料成為如粉筆那樣的粉狀的現象和狀態）的方面出發，特別優選使用金紅石型的氧化鈇。作為本發明的氧化銳，優選平均粒徑為 0. 001 e m~10 e m，特別優選為 ο. 1~3 Θ m » 需要說明的是，上述氧化欽的平均粒徑係指，由藉由鐳射衍射散射法測定的體積平均粒徑計算出的令值粒徑 (median diameter) (50%累積粒徑）的值。具體而言，係才曰使用日機裝（股）製的錯射衍射散射法粒度分析儀、光學裝置MT3300，使用曱醇作為粒徑測定用分散劑，在測定溫度25°C下測定的值。作為本發明的氧化鈦.，優選吸油量為 lml/100g~l〇〇〇mi/i〇0g，特別優選為 3ml/1〇〇g 5〇mi/i〇〇g。對於本發明的氧化鈦而言，可以進行過表面處理，例如’可以使用由A卜Si、Zr、Sb、Cr以及Ti中的1種以上的元素的氧化物、有機矽化合物形成的被膜進行表面處理後的氧化鈦。作為氧化鈦，可以使用市售„。口。作為市售品，可以列舉例如：“FR-41”（古河化學(股)製），“R，”（堺化學: 業（股）製），“R-820” “R_830,，（石原產業（股）製）等。相對於上述銅 5〇、100、150 ' 以固體成分換算’上述氧化鈦（c)的含量玻璃（A)l〇〇質量份為5〇〜3〇〇質量份，例如為 201224083 200、250、300質量份’可以在此處例示出的數值的任意兩個之間的範圍内。在這種範圍内的情況下，本發明的效果能夠更好的發揮。〈其他添加成分〉本發明中使用的防污塗料組成物含有擴散用樹脂，進而’還可以在不損害本發明的目的的範圍内，以任意的配合比例任意地含有溶出助劑、其他防污藥劑、防沉降劑、防局部塗料垂掛劑（anhrunn丨ng agents、流打止办剤）、增塑劑、表面活性劑、消泡劑、染料、顏料、有機溶劑及水等。 (溶出助劑） -作為溶出助劑，可·以列舉：矽油、乙烯_ α -烯烴共聚物、聚丁烯類、石蠟類、凡士林類、二烷基硫醚化合物等，藉由含有該溶出助劑，能夠適當地抑制塗膜的溶出速度，從而能夠長期發揮防污效果。溶出助劑的含量不受特別限定，以固體成分換算，在本發明的組成物的固體成分中，通常為〇.丨~35質量％，優選為1〜30質量％。作為上述矽油’可以列舉例如：聚二曱基矽氧烷、聚甲基苯基石夕氧烷、曱基苯基矽氧烷-二甲基矽氧烷共聚物、聚謎改質聚二甲基矽氧烷、聚醚改質聚烷基（甲基）矽氧烷、聚醋改質聚二甲基矽氧烷、長鏈烷基改質聚二甲基矽氧 11 201224083 烷、芳炫基改質聚二曱基矽氧烷、聚醚長鏈烷基芳烧基改質二甲基矽油、氟矽油、氨基改質矽油、利用其他各種官能團的改質矽油等。特別優選親水親油平衡（HLB值）為 0.5~9的聚醚改質矽油，具體而言，優選〇·5~9的聚醚改質聚二曱基矽氧烷或聚醚長鏈烷基芳烷基改質二曱基矽油。作為更加優選的矽油，為親水親油平衡（HLB值）為1 ~ 5的範圍内的聚醚改質聚二曱基矽氧烷或聚醚長鏈烷基芳烷基改質二甲基矽油。本發明中，可以單獨使用這些矽油，也可以組合兩種以上使用。從塗覆性能及塗膜物性的觀點出發，矽油的黏度優選為1 0 0 0泊（po i se ).以下，更加優選為· 1 〇〇泊以下。 -作為上述乙烯-α -烯烴共聚物，可以列舉例如通式（I ) 表示的乙烯-α-烯烴共聚物（式中，R1表示碳原子數ι~ι〇的直鏈或支鏈狀烷基，x、y和Ρ相同或不同，分別表示1 以上的整數）。化1 R1 ch2-ch2 f-1 CH2-CH |— Ρ ⑴ 作為R1表示的碳原子數1~10的直鏈或支鏈狀烷基特別優選甲基、乙基、丙基、異丙基、丁基、異丁基等碳原子數1〜4的烧基，更加優選曱基。 12 201224083 由通式（i)表示的乙烯- 〇：-烯烴共聚物是藉由使乙稀和α —烯烴共聚而得到的共聚物。上述乙烯-α -稀烴共聚物可以是無規共聚物 '嵌段共聚物或接枝共聚物中的任意一種。上述乙烯-α -烯烴共聚物可以使用市售品。作為市售品’可以列舉例如：Lucant (;—力 > 卜）HC-10、Lucant HC-2G 、 Lucant HC-40 ' Lucant HC-100 、 Lucant HC-150 、Powder, Zinc Omadine Powder (all manufactured by Arch Chemicals Japan, Inc.) and the like. The content of the metal pyrithione (B) in terms of the solid content 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). It can be within the range between any two of the numerical values exemplified herein. In the above range, the antifouling effect on animals such as barnacles and worms, and coelenterates such as water mites is particularly excellent. <Titanium oxide (C)> The titanium oxide (C) used in the present invention may be a titanium oxide such as a rutile type, an anatase type or a brookite type, and these titanium oxides may be used alone. Alternatively, two or more types may be used in combination. In the above-mentioned titanium oxide, it is difficult to cause a so-called "Chalking" phenomenon (meaning that the surface of the coating surface is deteriorated by ultraviolet rays 'heat, water 201224083 minutes, wind, etc. when the coated surface is exposed, the coating material In view of the fact that the pigment of the color component is in a powdery state and state like chalk, it is particularly preferable to use rutile-type cerium oxide. The oxidized sharpness of the present invention preferably has an average particle diameter of 0.001 em~10 em, particularly preferably ο. 1~3 Θ m » It should be noted that the average particle diameter of the above oxidized chin is indicated by laser The value of the median diameter (50% cumulative particle diameter) calculated from the volume average particle diameter measured by the diffraction scattering method. Specifically, the erroneous diffraction scattering particle size analyzer and the optical device MT3300 manufactured by Nikkiso Co., Ltd. are used, and decyl alcohol is used as a dispersing agent for particle diameter measurement, and the value measured at a measurement temperature of 25 ° C is used. . The titanium oxide of the present invention preferably has an oil absorption of 1 ml/100 g to 10 〇〇〇mi/i 〇 0 g, and particularly preferably 3 ml / 1 〇〇 g 5 〇 mi / i 〇〇 g. The titanium oxide of the present invention may be subjected to a surface treatment, for example, a surface formed of an oxide of an element or more of an element of A, Si, Zr, Sb, Cr, and Ti may be used. Treated titanium oxide. For the titanium oxide, a commercially available product can be used. For example, "FR-41" (Furukawa Chemical Co., Ltd.), "R," (堺Chemistry: Industrial Co., Ltd.), "R-820" "R_830,, (Ishihara Industry Co., Ltd.), etc. The content of the titanium oxide (c) in terms of the solid content of the above-mentioned copper 5 〇, 100, 150 'glass (A) is 5 〇 to 3 〇〇 parts by mass, for example, 201224083 200, 250, 300 parts by mass 'may be in the range between any two of the numerical values exemplified herein. In the case of such a range, the effects of the present invention can be exerted better. <Other Additive Components> The antifouling paint composition used in the present invention contains a resin for diffusion, and further can optionally contain a dissolution aid and other antifouling at an arbitrary mixing ratio within a range not impairing the object of the present invention. Pharmacy, anti-settling agent, anti-local paint sag (anhrunn丨ng agents, flow stop), plasticizers, surfactants, defoamers, dyes, pigments, organic solvents and water. (Dissolution aid) - Examples of the dissolution aid include: eucalyptus oil, ethylene_α-olefin copolymer, polybutene, paraffin, petrolatum, dialkyl sulfide compound, etc., by containing the dissolution The auxiliary agent can appropriately suppress the elution speed of the coating film, and can exhibit the antifouling effect for a long period of time. The content of the dissolution aid is not particularly limited, and is usually 5% to 5% by mass, preferably 1 to 30% by mass, based on the solid content of the solid content of the composition of the present invention. Examples of the above-mentioned eucalyptus oil include polydidecyl fluorene oxide, polymethyl phenyl oxalyl, decyl phenyl oxa oxane-dimethyl decane copolymer, and polymylon modified polydimethyl. Oxane, polyether modified polyalkyl (meth) decane, polyacetate modified polydimethyl siloxane, long chain alkyl modified polydimethyl oxime 11 201224083 alkane, aromatic Modified polydimercapto oxime, polyether long-chain alkyl aryl-based modified dimethyl hydrazine oil, fluoroindole oil, amino-modified eucalyptus oil, modified eucalyptus oil using various other functional groups, and the like. Particularly preferred is a polyether modified eucalyptus oil having a hydrophilic-lipophilic balance (HLB value) of 0.5 to 9. Specifically, a polyether modified polydidecyl fluorene oxide or a polyether long-chain alkyl group of 〇·5-9 is preferred. Aralkyl modified dimethyl sulfonium oil. As a more preferable eucalyptus oil, a polyether modified polydidecyl fluorene oxide or a polyether long-chain alkyl aralkyl modified dimethyl oxime oil having a hydrophilic-lipophilic balance (HLB value) of 1 to 5 . In the present invention, these eucalyptus oils may be used singly or in combination of two or more. The viscosity of the eucalyptus oil is preferably 100 poise (po i se ) or less, and more preferably 1 〇〇 or less from the viewpoint of coating performance and coating physical properties. The above-mentioned ethylene-α-olefin copolymer may, for example, be an ethylene-α-olefin copolymer represented by the formula (I) (wherein R1 represents a linear or branched alkyl group having a carbon number of from 1 to 10) , x, y, and Ρ are the same or different, respectively representing an integer of 1 or more). 1 R1 ch2-ch2 f-1 CH2-CH |— Ρ (1) A linear or branched alkyl group having 1 to 10 carbon atoms represented by R1 is particularly preferably a methyl group, an ethyl group, a propyl group or an isopropyl group. An alkyl group having 1 to 4 carbon atoms such as a butyl group or an isobutyl group is more preferably a mercapto group. 12 201224083 The ethylene-ruthenium-olefin copolymer represented by the general formula (i) is a copolymer obtained by copolymerizing ethylene and an α-olefin. The above ethylene-α-dilute hydrocarbon copolymer may be any of a random copolymer 'block copolymer or graft copolymer. A commercially available product can be used for the above ethylene-α-olefin copolymer. As a commercial item, for example, Lucant (; - force > Bu) HC-10, Lucant HC-2G, Lucant HC-40 'Lucant HC-100, Lucant HC-150,

Lucant HC-600、Lucant HC-2000(均為註冊商標，三井化學（股）製）等。這些乙烯-α-稀烴共聚物可以單獨使用，也可以組合兩種以上使用。從塗覆性能及塗膜物性的觀點出發，上述乙稀_ α _稀煙共t物的數均分.子量（Μη)優選為1〇, 〇〇〇以下，更加優選為1，000~3, 000。上述乙烯-α -烯烴共聚物優選下的黏度為20, OOOPaS以下，更加優選為500PaS以下。作為上述聚丁烯類’可以列舉聚丁烯、聚異丁稀等。作為聚丁稀類’可以使用市售品。作為市售品，可以列舉例如：聚丁烯LV-7、聚丁烯LV-10、聚丁烯LV-25、聚丁烯 LV-50、聚丁烯 LV-100、聚丁烯 HV-35、聚丁稀 HV-100、聚丁烯HV-300、聚丁烯HV-1 900(均為日本石油化學（股）製）；聚丁烯0H、聚丁烯5H、聚丁烯10H、聚丁烯300H、聚丁烯 2000H' 聚丁烯 0R、聚丁烯 15R、聚丁烯 35R' 聚丁烯 100R、聚丁烯350R(均為出光石油化學股份會社製）；聚丁稀〇N、 13 201224083 聚丁烯10SH、聚丁烯200Ν(均為聚丁烯06N、聚丁烯3N、曰油（股）製）等。作為上述石躐類，可以列舉例如：η_石蠟 '固體石蠟' 液體石蠟、氯化石蠟等。可以列舉例如：白色凡士林、黃色作為上述凡士林類，凡士林等。作為上述二烷基硫醚化合物、可以列舉：二叔丁基十硫醚、二戊基四硫醚、二戊基五硫醚'二戊基十硫醚、二辛基四硫喊、二辛基五硫_ ' 二壬基四硫醚、二壬基五硫醚' 一叔壬基四硫醚、二叔壬基五硫醚、二癸基四硫醚、二十二烷基四硫醚、二十八烷基四硫醚、二十九烷基四硫醚等。 (擴散用樹脂）作為擴散用樹脂’可以使用合成樹脂及天然樹脂，藉由含有擴散用樹脂’塗膜形成的操作性提高。此外，能夠形成與被塗膜形成物的密合性優良的塗膜。作為上述合成樹脂，可以使用例如：乙烯樹脂、醇酸樹脂、丙烯酸樹脂、聚氨酯樹脂、聚酯樹脂、合成橡膠、氯化聚乙烯等。作為上述乙烯樹脂，可以例示：氣乙烯—乙酸乙烯共聚物、氣乙烯-烷基乙烯醚共聚物、氣化乙烯樹脂等。另外，作為上述天然樹脂’可以列舉例如：木松香、脂松香、改質松香等。作為上述擴散用樹脂，特別優選含有丙烯酸樹脂。 14 201224083 上述擴散用樹脂的玻璃化轉變溫度（Tg)優選為 -100〜100°c，更加優選為-50〜8(rc。上述擴散用樹脂的重均分子量（Mw)優選為5, 〇〇〇〜1，〇〇〇,〇〇〇，更加優選為 10, 000〜500, 000。上述擴散用樹脂的含量不受特別限定，以固體成分換算，在本發明的組成物的固體成分中通常占 0. 1-80質量％，優選占1〜45質量％。 (其他防污藥劑）作為本發明中使用的含有二價銅的銅玻璃（A)和金屬 0比咬硫辆類（B )以外的防污藥劑，可以含有以下的防污藥劑。由此’能夠使形成的塗膜進一步發揮出適當的防污效果》作為其他的防污藥劑’也可以使用例如：二硫化四曱基秋蘭姆，二硫化四乙基秋蘭姆等二硫化四烷基秋蘭姆化合物等。另外’也可以使用：氣曱基—正辛基二硫醚、N，1二曱基二氣苯基脲、N-(氟二氯甲硫基）鄰苯二甲醯亞胺、N， N 一二甲基-Ν’ -笨基-(N-氟二氣甲硫基）磺醯胺、n，n，-二甲基-Ν -甲苯基-(Ν-氟二氣甲硫基）磺醯胺、4，5_二氯_2一正辛基-4-異噻唑啉-3-酮，2 , 3-二氣-Ν-(2 , 6-二乙基笨基）馬來醯亞胺、2，3-二氯-Ν-(2，-乙基-6，-甲基笨基）馬來酿亞胺、3 -笨並[b]°塞吩-2-基-5，6 -二氫-1，4，2-。惡。塞嗪-4-氧化物、2-(鄰氣笨基）-3-氰基_4_溴三氟甲基吡咯、四氣間苯二氰等。 15 201224083 作為與上述銅玻璃（A)和金屬吡啶硫酮類（B)並用的其他防污藥劑，特別優選4, 5-二氣-2-正辛基-4-異噻唑啉-3-_。上述其他防污藥劑的含量不受特別限定，以固體成分換算，在本發明的組成物的固體成分中，通常為〇卜8〇質量％，優選為1〜50質量？^ (防沉降劑和防局部塗料垂掛劑）作為防沉降劑和防局部塗料垂掛劑，可以列舉例如：聚乙稀蠟、氫化蓖麻油蠟系、聚醯胺蠟系、醯胺蠟系、氧化聚乙烯系蠟等，優選為氫化蓖麻油蠟系、聚醯胺壤系、醯胺環系、氧化聚乙稀系螺ι »這些防沉降劑和防局部塗料垂掛劑可以單獨使用，或者也可以組合兩種以上使用。 (增塑劑）作為增塑劑，可以列舉例如：鄰苯二甲酸酯、己二酸醋，磷酸酯等。作為上述鄰苯二甲酸酯，可以列舉：鄰苯二甲酸二丁酯、鄰笨二曱酸二辛酯、鄰笨二甲酸二_2_乙基己赌’作為上述己二酸酯’可以列舉：己二酸二丁醋、己二酸二辛酯、己二酸_2-乙基己酯’作為上述磷酸酯，可以列舉. 碟酸三曱笨酯、磷酸三辛酯等。這些增塑劑可以單獨使用，或者也可以組合兩種以上來使用。 (有機溶劑）Lucant HC-600, Lucant HC-2000 (all registered trademarks, Mitsui Chemicals Co., Ltd.). These ethylene-α-dilute hydrocarbon copolymers may be used singly or in combination of two or more. From the viewpoint of the coating property and the physical properties of the coating film, the number average sub-quantity (Μη) of the above-mentioned ethylene_α_稀烟共物物 is preferably 1 〇, 〇〇〇 or less, more preferably 1,000 Å. 3,000. The ethylene-α-olefin copolymer preferably has a viscosity of 20, OOO PaS or less, and more preferably 500 PaS or less. Examples of the polybutenes' include polybutene and polyisobutylene. Commercially available products can be used as the polybutylene. As a commercial item, a polybutene LV-7, polybutene LV-10, polybutene LV-25, polybutene LV-50, polybutene LV-100, polybutene HV-35 are mentioned, for example. , polybutylene HV-100, polybutene HV-300, polybutene HV-1 900 (both manufactured by Nippon Petrochemical Co., Ltd.); polybutene 0H, polybutene 5H, polybutene 10H, poly Butene 300H, polybutene 2000H' polybutene 0R, polybutene 15R, polybutene 35R' polybutene 100R, polybutene 350R (all manufactured by Idemitsu Petrochemical Co., Ltd.); polybutylene N, 13 201224083 Polybutene 10SH, polybutene 200 Ν (both polybutene 06N, polybutene 3N, eucalyptus oil). Examples of the sarcophagus include η_paraffin 'solid paraffin', liquid paraffin, chlorinated paraffin, and the like. For example, white petrolatum and yellow are used as the above Vaseline, Vaseline, and the like. Examples of the above dialkyl sulfide compound include di-tert-butyl decasulfide, dipentyl tetrasulfide, dipentyl pentasulfide 'dipentyl decasulfide, dioctyl tetrasulfide, and dioctyl. Pentasulfuryl-'didecyltetrasulfide, dimercaptopentasulfide'-tert-decyltetrasulfide, di-tert-decylpentanesulfide, dimercaptotetrasulfide, behenyltetrasulfide , octadecyl tetrasulfide, dinonyl tetrasulfide, and the like. (Resin for diffusion) As the resin for diffusion, a synthetic resin and a natural resin can be used, and workability by forming a coating film containing a resin for diffusion is improved. Further, it is possible to form a coating film having excellent adhesion to the film-formed product. As the synthetic resin, for example, a vinyl resin, an alkyd resin, an acrylic resin, a polyurethane resin, a polyester resin, a synthetic rubber, a chlorinated polyethylene or the like can be used. The vinyl resin may, for example, be a gas ethylene-vinyl acetate copolymer, a gas-ethylene-alkyl vinyl ether copolymer or a vaporized vinyl resin. Further, examples of the natural resin ' include wood rosin, gum rosin, and modified rosin. As the above-mentioned diffusion resin, it is particularly preferable to contain an acrylic resin. 14 201224083 The glass transition temperature (Tg) of the above-mentioned diffusion resin is preferably -100 to 100 ° C, more preferably -50 to 8 (rc. The weight average molecular weight (Mw) of the above-mentioned diffusion resin is preferably 5, 〇〇〇1, 〇〇〇, 〇〇〇, more preferably 10,000 to 500, 000. The content of the above-mentioned diffusion resin is not particularly limited, and is usually in the solid content of the composition of the present invention in terms of solid content. 0 to 1% by mass, preferably 1 to 45% by mass. (Other antifouling agents) The copper glass (A) containing divalent copper used in the present invention and the metal 0 are more sulphur-like vehicles (B) The antifouling agent other than the antifouling agent may contain the following antifouling agent, whereby the formed coating film can further exhibit an appropriate antifouling effect. As another antifouling agent, for example, tetrasulfide disulfide can be used. Lamb, tetraethyl thiuram disulfide compound such as tetraethyl thiuram disulfide, etc. In addition, it can also be used: gas fluorenyl-n-octyl disulfide, N,1 dimercaptodiphenyl Urea, N-(fluorodichloromethylthio) phthalimide, N, N-dimethyl-anthracene - stupid-(N-fluorodimethylmethylsulfonyl)sulfonamide, n,n,-dimethyl-indole-tolyl-(fluorene-fluorodimethylthio)sulfonamide, 4,5_ Dichloro-2-n-octyl-4-isothiazolin-3-one, 2,3-dioxa-indole-(2,6-diethylphenyl)maleimide, 2,3-di Chloro-indole-(2,-ethyl-6,-methylphenyl)maleimine, 3-phenylene[b]°cephen-2-yl-5,6-dihydro-1,4 , 2-. Ethylpyrazine-4-oxide, 2-(ozone)-3-cyano-4Obromotrifluoromethylpyrrole, tetra-p-phenylene dicyanohydrazide, etc. 15 201224083 as with the above The other antifouling agent used in combination with the copper glass (A) and the metal pyrithione (B) is particularly preferably 4, 5-diqi-2-n-octyl-4-isothiazolin-3-yl. The content of the chemical agent is not particularly limited, and is usually 8% by mass, preferably 1 to 50% by mass in the solid content of the composition of the present invention in terms of solid content (^ anti-settling agent and anti-local paint hanging) As the anti-settling agent and the anti-particulate coating sag, for example, polyethylene wax, hydrogenated castor oil wax, polyamine wax, guanamine wax, oxidized polyethylene The olefinic wax or the like is preferably a hydrogenated castor oil wax system, a polyamidamine system, a guanamine ring system, or an oxidized polyethylene snail. These anti-settling agents and anti-local paint sag agents may be used singly or in combination. (Plasticizer) Examples of the plasticizer include phthalic acid ester, adipic acid vinegar, and phosphate ester. Examples of the phthalic acid ester include phthalic acid. Dibutyl formate, dioctyl o-dicarboxylate, o-dibenzoic acid di-2-ethylhexanol as the above adipate can be exemplified by dibutyl acetonate or dioctyl adipate. And adipic acid 2-ethylhexyl ester as the above-mentioned phosphate ester, tridecyl succinate, trioctyl phosphate, etc. are mentioned. These plasticizers may be used singly or in combination of two or more. (Organic solvents)

Solvesso 作為有機溶劑，可以使用例如：二甲苯、甲笨、 16 201224083 100、Solvesso 150(均為註冊商標，Exx〇n M〇bil Corporation製）等芳香族系溶劑；異丁基甲基酮（MIBK)、二異丁基酮（DIBK)等酮系溶劑；醋酸丁酯、醋酸異丁酯、醋酸異戊酯等酯系溶劑。此外，也可以使用考慮到低毒、低味和低環境負荷的有機溶劑，可以使用例如：Pegas〇1 AN45、Pegas〇1 AS1〇〇(均為註冊商標，Exxon Mobi 1 Corporation 製）、LAWS、HAWS(均為Shell Chemicals製）等芳香族、脂環式、脂肪族烴混合溶劑；丙二醇單甲基醚醋酸酯、丙二醇單乙基醚醋酸酯等二醇系Sa /谷劑；乙基環己烧、二曱基環己烧、y力y小7，（註冊商標）900(C9芳香族氫化物）（註；曰本商標名，無對應之英文或中文商標名稱，下同）、V力'//P〆（註冊商標）l〇Q〇(Ci〇芳香族氫化物）等脂環式烴系溶劑；Shells〇l D4〇(註冊商標，Solvesso as an organic solvent, for example, an aromatic solvent such as xylene, methyl bromide, 16 201224083 100, Solvesso 150 (all registered trademarks, manufactured by Exx〇n M〇bil Corporation); isobutyl methyl ketone (MIBK), A ketone solvent such as diisobutyl ketone (DIBK); an ester solvent such as butyl acetate, isobutyl acetate or isoamyl acetate. In addition, organic solvents that take into consideration low toxicity, low odor, and low environmental load can be used, for example, Pegas〇1 AN45, Pegas〇1 AS1〇〇 (all registered trademarks, manufactured by Exxon Mobi 1 Corporation), and LAW, An aromatic, alicyclic or aliphatic hydrocarbon mixed solvent such as HAWS (all manufactured by Shell Chemicals); a glycol-based Sa/valency agent such as propylene glycol monomethyl ether acetate or propylene glycol monoethyl ether acetate; Burning, bismuth-based hexene burning, y-force y small 7, (registered trademark) 900 (C9 aromatic hydride) (Note; 曰本trade name, no corresponding English or Chinese trademark name, the same below), V force '//P〆 (registered trademark) l〇Q〇 (Ci〇 aromatic hydride) and other alicyclic hydrocarbon solvents; Shells〇l D4〇 (registered trademark,

Shell Chemicals 製）、Exxsol D30 ’ Exxsol D40(均為註冊商標，Exxon Mobil Corporation製）等脂環式、脂肪族烴混合溶劑；Isopar G、Isopar Η(均為註冊商標，Εχχ〇η M〇bu Corporat i on製）等脂肪族烴混合溶劑等。這些有機溶劑可以單獨使用，或者也可以混合兩種以上使用。本發明的組成物能夠用於形成各種漁具、水中建築結構等的防污塗膜。特別而言，本發明的組成物能夠優選用作漁網用防污塗料組成物。 17 201224083 本發明的漁網防污塗料組成物能夠藉由混合上述 [A]〜[C]成分 '以及根據需要的上述各成分來製備。對於進行混合時的各成分的添加量，適當調整為上述配合量及含量即可。對於混合各成分的順序，不受特別限制。對於混合方法，採用使用攪拌裝置進行混合等公知的方法即可。 /魚網防污塗膜形成方法、防污塗膜以及塗裝物本發明的漁網防污塗膜的形成方法的特徵在於，使用上述漁網防污塗料組成物在被塗膜形成物的表面形成防污塗膜》藉由本發明的形成方法得到的防污塗膜藉由從表面緩慢溶解而時常更新塗膜表面，從而能夠實現防止水生污損生物的附著。此外’使塗膜溶解後，藉由重新塗布上述組成物，能夠繼續發揮防污效果。作為破塗膜形成物，可以列舉例如漁具水中建築結構等作為漁具，可以列舉例如：養瘦用或固定用漁網該漁網中使用的浮標 '繩索等漁網配件等。作為水中建築結構，可以列舉例如：發電站導水管、橋樑频設備等。本心月的漁網防污塗膜可以藉由將上述漁網防污塗料 ”且成物塗布於被塗膜形成物的表面（整個或一部分）來形成0 作為塗布方法，可以列舉例如•刷塗法、噴霧法、浸潰法、流塗法、旋塗法等。寻對於些方法而言，可以使用一種或並用兩種來^隹彡- τ ° W h ’在將本發明的漁網防污塗料 18 201224083 組成物塗布到漁網上時，作為塗布方法，優選採用浸潰法。塗布後使其乾燥。乾燥溫度可以為室溫。乾燥時間根據漁網防污塗料的附著量適當設定即可。上述漁網防污塗料的附著量根據被塗膜形成物的種類等適當設定即可。例如，被塗膜形成物為漁網的情況下，乾燥塗膜的附著量相對於漁網100質量份優選為^5質量份，更加優選為4-20質量份。本發明的塗裝物在表面具有上述防污塗膜。本發明的塗裝物可以在整個表面具有上述防污塗膜，也可以在部分表面具有上述防污塗膜。【實施例】以下’示出實施例等來更進一步明確本發明的特徵。但本發明並不受這些實施例的限定。比較製造例1(含有一價銅的銅玻璃H-1的製造）將下述組成比的玻璃成分材料與銅化合物混合均勻，使用1 10 0 -13 0 0 °C的煤氣爐進行6 0分鐘溶化，然後進行急冷’從而製造含有一價銅的溶解性玻璃，然後’利用球磨機粉碎上述溶解性玻璃，得到含有一價銅的銅玻璃粉末。〈組成〉Isopar G, Isopar Η (all registered trademarks, Εχχ〇η M〇bu Corporat), such as Shell Chemicals), Exxsol D30 'Exxsol D40 (all registered trademarks, manufactured by Exxon Mobil Corporation); An aliphatic hydrocarbon mixed solvent or the like. These organic solvents may be used singly or in combination of two or more. The composition of the present invention can be used for forming an antifouling coating film of various fishing gears, underwater building structures and the like. In particular, the composition of the present invention can be preferably used as an antifouling coating composition for fishing nets. 17 201224083 The fishnet antifouling paint composition of the present invention can be prepared by mixing the above [A] to [C] components ' and the above respective components as needed. The amount of each component to be added during the mixing may be appropriately adjusted to the above-mentioned compounding amount and content. The order in which the components are mixed is not particularly limited. For the mixing method, a known method such as mixing using a stirring device may be employed. /fish net antifouling coating film forming method, antifouling coating film, and coating material The method for forming a fish net antifouling coating film according to the present invention is characterized in that the above-mentioned fishnet antifouling coating composition is formed on the surface of the coating film formed article. In the antifouling coating film obtained by the formation method of the present invention, the surface of the coating film is frequently renewed by slowly dissolving from the surface, whereby the adhesion of the aquatic fouling organism can be prevented. Further, after the coating film is dissolved, the antifouling effect can be continuously exhibited by recoating the above composition. For example, a fishing gear in a fishing gear or the like can be used as a fishing gear, and examples thereof include a fishing net fitting such as a buoy used in a fishing net for fixing or fixing a fishing net. As the underwater structure, for example, a power station water guide pipe, a bridge frequency device, and the like can be cited. The fishing net antifouling coating film of the present invention can be formed by applying the above-mentioned fishnet antifouling coating and the object to the surface (entire or part) of the coating film formation as a coating method, and for example, a brush coating method can be cited. , spray method, dipping method, flow coating method, spin coating method, etc. For some methods, one or both of them can be used to control the fishing net antifouling paint of the present invention. 18 201224083 When the composition is applied to a fishing net, it is preferable to use a dipping method as a coating method. After drying, the drying temperature may be room temperature, and the drying time may be appropriately set according to the amount of the antifouling paint of the fishnet. The amount of the anti-fouling paint to be applied may be appropriately set depending on the type of the film-formed product to be coated, etc. For example, when the film-formed product is a fishing net, the amount of the dry coating film adhered is preferably 5 masses per 100 parts by mass of the fishnet. More preferably, it is 4-20 parts by mass. The coated article of the present invention has the above-mentioned antifouling coating film on the surface. The coated article of the present invention may have the above antifouling coating film on the entire surface, or may be partially The surface has the above-mentioned antifouling coating film. [Examples] The features of the present invention will be further clarified by the following examples and the like. However, the present invention is not limited by these examples. Comparative Manufacturing Example 1 (containing monovalent copper Production of Copper Glass H-1) The glass component material having the following composition ratio is uniformly mixed with a copper compound, and is melted in a gas furnace at 1 10 0 - 1100 ° C for 60 minutes, and then quenched to produce a one. A soluble glass of copper valence, and then the above-mentioned soluble glass is pulverized by a ball mill to obtain a copper glass powder containing monovalent copper.

Si〇2:7. 7質量份Si〇2: 7. 7 parts by mass

Al2〇3:〇. 1質量份Al2〇3:〇. 1 part by mass

Na2〇: 5. 9質量份 201224083 B203: 28. 8質量份 Cu2〇:53. 3質量份 Zn0:4. 2質量份實施例1〜6和比較例1 ~ 12 以表1記載的比例（質量％)混合表1記載的配合成分，由此得到防污塗料組成物。商品名“PNU-40” ：含有二價銅的銅玻璃 (P2〇5/Na2〇/Cu0 = 30/30/40(摩爾％)，平均粒徑，東洋破璃（股）製）商品名“PNU-30” ：含有二價銅的銅玻璃 (P2〇5/Na2〇/CuO=35/35/30(摩爾％)，平均粒徑 3 //，東洋坡璃（股）製）商品名“NC-301” ：氧化亞銅（日進chemco(股）製）商品名“氧化鋅2種”：酸化鋅（正同化學工業（股）製）商品名“NoccelerPZ” ：二甲基二硫代氨基甲酸鋅（大内新興化學工業（股）製）商品名“NoccelerTET-G” ：二硫化四乙基秋蘭姆（大内新興化學工業（股）製）商品名 “Copper Omadine Powder” ：雙（2-硫代〜1__氧化0比咬）銅（Arch Chemicals Japan, Inc.製）商品名“Zinc Omadine Powder” ：雙（2-硫代〜氧化 °比咬）鋅（Arch Chemicals Japan, Inc.製） 20 201224083 商品名“FR-41” ：氧化欽（金紅石型氧化鈦，furukawa CHEMICALS CO.，LTD.製）商品名氧化鋅2種：氧化辞（正同化學工業（股）製）商品名“Tinuvin P : 2-(5-曱基-2-羥基苯基）苯並三唑（長瀨產業（股）製）商品名二O-AHN (注·日本商品名，無對應之英文或中文名稱’下同）：丙烯酸樹脂二甲苯溶液（固體成分 40%，Tg=約 20°C ’ 約 230000，日東化成（股）製）商品名“KF-6020” ：聚醚改質二甲基矽油（信越化學工業（股）製）商品名“X-22-251 6” ：聚醚長鏈烷基芳烷基改質二曱基矽油（信越化學工業（股）製）商品名“Lucant HC-40” ：乙烯-α-烯烴共聚物（三井化學（股）製）商品名“聚丁烯0Ν” ：聚丁烯（曰本油指（股）製）商品名“Disparlon 4200-20” ：氧化聚乙烯系蜡（固体成分20%，楠本化成（股）製）商品名“Disparlon A630-20X” ：聚醯胺系蠟（固體成分20%，楠本化成（股）製）二曱苯：KISHIDA CHEMICAL Co.，Ltd.製，1 級試劑 21 201224083 【1<】比較例 04 CO CVJ CO oo Cvl CM CM 一 S = CO cr> oo CSJ CM CM — ΙΛ tn g CD c〇 CM CO oo CNi CM Ol 一 s 1 σ> <N3 CD oo Csl CM ti* <>3 — ΙΛ to 〇 οο in oa ΙΛ ΙΛ Cvi CVJ 'tj· OJ —— S g c— 03 1.0 l〇 oa CM CvJ »—· s g c〇 <M »Λ ir> CNJ CVJ •cr OJ K 〇 Lf5 C4 OJ to tn CM CM OJ K C5 C3 un to c^* CM -Cf ca 〇 o CO CM CM *«r § § 04 CS3 m ca TJ* CM § g r~i ·>>>>· "5Γ ΙΛ CM CM — 2 o 實施例 CO OA CSJ ιΛ m ca CM K § in CVJ CM in L〇 <M CVJ CM ·—« S Ξ- cs CM m tn C<i CM CM 5 〇 CO 04 CVJ ΙΛ ιΛ oa S I 04 OJ m ΙΛ Cv3 04 〇i 5 g »—♦ 04 OJ in Lfa CM CSJ 〇i g !IjNU-40 PN0-30 含一俏銅的鋼玻m(H-i) 氧化亞銅(NC-301) 氡化釺2種 Nocceler PZ Nocceler TET-G Copper Omadine Powder Zinc (kadine Powder PR-41 at s •e < »- Λ 硅油（KF-6020) 硅油 Oi-22-2516) Lucant IIC-40 聚丁烯ON Disparlon 4200-20 Disparion Λ630-20Χ s- 總計鋼玻璃(A) 金屬吡啶硫飼(B) 氡化鈦(c) 鋪展樹脂溶出助劑防沉降劑溶劑 22 201224083 試驗例1 (防污效果確認試驗）將聚乙稀製的漁網（4〇〇丹尼（denier )、40根、8節），浸潰於由實施例1 ~ 6和比較例i〜丨2得到的各防污塗料級成物中進行塗布’並使其乾燥，以使乾燥塗膜的附著量相對於漁網100質量份為15質量份。將形成了塗膜的漁網固定於40x60cmSUS的框中，浸潰于作為水生污損生物的活性較強的海域的三重県尾鷲的木排的吃水部，12個月間定期觀察其防污評價。利用以下的方法來進行評價。需要說明的是’對於水生生物的附著面積（％)而言，試驗期（2、4、6、8' 10或12 個月）後從上拍攝漁網的照片，目視評價漁網中的水生生物的佔有面積。· . ◎:水生生物的附著面積為〇% 〇：水生生物的附著面積大於〇且小於1〇% △:水生生物的附著面積為10以上且小於50% X:水生生物的附著面積為5〇%以上將結果示於表2。 23 201224083Na2〇: 5. 9 parts by mass 201224083 B203: 28. 8 parts by mass of Cu2 〇: 53. 3 parts by mass of Zn0: 4.2 parts by mass of Examples 1 to 6 and Comparative Examples 1 to 12 in the ratios shown in Table 1 (mass %) The components shown in Table 1 were mixed to obtain an antifouling paint composition. Trade name "PNU-40": Copper glass containing divalent copper (P2〇5/Na2〇/Cu0 = 30/30/40 (mol%), average particle size, manufactured by Toyo Glass Co., Ltd.) PNU-30": copper glass containing divalent copper (P2〇5/Na2〇/CuO=35/35/30 (mol%), average particle size 3 //, manufactured by Toyo Satura Co., Ltd.) NC-301": cuprous oxide (made by jinjin chemco Co., Ltd.) trade name "2 kinds of zinc oxide": zinc acid hydride (manufactured by Masahiro Chemical Co., Ltd.) trade name "Nocceler PZ": dimethyldithioamino Zinc formate (made by Ouchi Emerging Chemical Industry Co., Ltd.) trade name "NoccelerTET-G": tetraethyl thiuram disulfide (made by Ouchi Emerging Chemical Industry Co., Ltd.) trade name "Copper Omadine Powder" : double ( 2-Silox~1__Oxidation 0 to bite) Copper (manufactured by Arch Chemicals Japan, Inc.) Trade name "Zinc Omadine Powder": bis (2-thio-oxidation ratio bite) zinc (Arch Chemicals Japan, Inc. 20) 201224083 Product name "FR-41": Oxidation chin (manufactured by furukawa CHEMICALS CO., LTD.) Oxidation (Identical Chemical Industry Co., Ltd.) trade name "Tinuvin P: 2-(5-mercapto-2-hydroxyphenyl)benzotriazole (manufactured by Changchun Industry Co., Ltd.) AHN (Note: Japanese product name, no corresponding English or Chinese name 'the same below): acrylic resin xylene solution (solid content 40%, Tg = about 20 ° C 'about 230,000, Nitto Chemical Co., Ltd.) "KF-6020": Polyether modified dimethyl oxime oil (Shin-Etsu Chemical Co., Ltd.) trade name "X-22-251 6": polyether long-chain alkyl aralkyl modified dimercapto eucalyptus oil ( Shin-Etsu Chemical Co., Ltd.) trade name "Lucant HC-40": ethylene-α-olefin copolymer (manufactured by Mitsui Chemicals Co., Ltd.) trade name "polybutene 0": polybutene (曰本油指( Co., Ltd.) Product name "Disparlon 4200-20": Oxidized polyethylene wax (solid content 20%, manufactured by Kudang Chemicals Co., Ltd.) Trade name "Disparlon A630-20X": Polyamide wax (solid content 20%) , Nanben Chemical Co., Ltd.) Diphenylbenzene: manufactured by KISHIDA CHEMICAL Co., Ltd., Class 1 reagent 21 201224083 [1<] Comparative Example 04 CO CVJ CO oo Cvl CM CM a S = CO cr> oo CSJ CM CM — ΙΛ tn g CD c〇CM CO oo CNi CM Ol a s 1 σ><N3 CD oo Csl CM ti* <&gt ;3 — ΙΛ to 〇οο in oa ΙΛ ΙΛ Cvi CVJ 'tj· OJ —— S gc— 03 1.0 l〇oa CM CvJ »—· sgc〇<M »Λ ir> CNJ CVJ •cr OJ K 〇Lf5 C4 CM -Cf ca 〇o CO CM CM *«r § § 04 CS3 m ca TJ* CM § gr~i ·>>>>· &quot ;5Γ CM CM CM — 2 o Example CO OA CSJ ιΛ m ca CM K § in CVJ CM in L〇<M CVJ CM ·—« S Ξ- cs CM m tn C<i CM CM 5 〇CO 04 CVJ Λ ιΛ oa SI 04 OJ m ΙΛ Cv3 04 〇i 5 g »—♦ 04 OJ in Lfa CM CSJ 〇ig !IjNU-40 PN0-30 Steel with a copper-clad m(Hi) cuprous oxide (NC-301 ) 2 kinds of Nocceler PZ Nocceler TET-G Copper Omadine Powder Zinc (kadine Powder PR-41 at s •e < »- 硅 Silicone Oil (KF-6020) Silicone Oil Oi-22-2516) Lucant IIC-40 Polybutene ON Disparlon 4200-20 Disparion Λ630-20Χ s- Total steel glass (A) Metal pyridine sulfur feed (B) Titanium telluride (c) Spreading resin dissolution aid anti-settling agent solvent 22 201224083 Test example 1 (anti-fouling effect confirmation test) Polyethylene-made fishing net (4〇 Den denier, 40, 8 knots, impregnated with each of the antifouling coating grades obtained in Examples 1 to 6 and Comparative Examples i to 2, and dried, so that The amount of adhesion of the dried coating film was 15 parts by mass based on 100 parts by mass of the fishing net. The fishnet on which the coating film was formed was fixed in a frame of 40 x 60 cm SUS, and was immersed in the draft of the raft of the triple-tailed scorpion which is a highly active sea area of aquatic fouling organisms, and the antifouling evaluation was periodically observed for 12 months. The evaluation was carried out by the following method. It should be noted that for the attachment area (%) of aquatic organisms, photographs of fishing nets were taken from above during the test period (2, 4, 6, 8' 10 or 12 months), and the aquatic organisms in the fishing nets were visually evaluated. Occupied area. · ◎: The attachment area of aquatic organisms is 〇% 〇: The attachment area of aquatic organisms is larger than 〇 and less than 1〇% △: The attachment area of aquatic organisms is 10 or more and less than 50% X: The attachment area of aquatic organisms is 5〇 The results above are shown in Table 2. 23 201224083

【表2】防污評價實施例比較例 1 2 3 4 5 6 1 2 3 4 5 6 7 8 9 10 II 12 笫2個月 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 第4個月 ◎ ◎ ◎ ◎ ◎ ◎ Δ ◎ ◎ 〇 ◎ ◎ ◎ ◎ Δ △ 〇 △ 笫6個月 ◎ ◎ ◎ ◎ ◎ ◎ X 〇〇 Δ ◎ ◎ 〇〇 X X Δ Δ _ 第8個月 ◎ ◎ ◎ ◎ ◎ ◎ X Δ △ X 〇〇〇 Δ X X X X 第10個月 ◎ ◎ ◎ ◎ ◎ ◎ X X X X Δ Δ Δ X X X X X _第12個月 ◎ ◎ 〇〇 ◎ 〇 X X X X X X X X X X X X 由表2可知，本發明的實施例1 ~ 6的防污塗料組成物與比較例1 ~ 12的防污塗料組成物的任意一個相比，長期防污性均更優良。實施例1-6含有包含二價銅的銅玻璃、金屬„比咬硫酮類以及氧化·鈇這三種成分。於此相對，比較例1僅含有包含二價銅的銅玻璃’比較例2和3僅含有包含二價銅的銅坡璃和金屬。比咬硫_類，比較例4含有包含二價鋼的銅玻螭和氧化鈦，比較例卜4的長期防污性比實施例卜6低得多。結果可知，為了使防污塗料組成物發揮出優良的長期防污性’必須全部含有上述三種成分，即使僅缺少三種成分中的一種時，長期防污性也會極端降低。此外’就比較例5〜8而言，對含有包含一價銅的銅玻螭、金屬吡啶硫酮類和氧化鈦三種成分、或含有氧化亞鋼、金屬吡啶硫酮類和氧化鈦三種成分的防污塗料組成物的長期防方性進行了調查，比較例5〜8的任意一例的長期防污 24 201224083 性均比實施例1 ~ 6低得多。由此可知，藉由添加金屬吡咬硫酮類和氧化鈦來較大提高長期防污性的效果，是含有二價銅的銅玻璃所特有的’使用含有.一價銅的銅玻璃或氧化亞銅的情況下，無法得到同樣的效果。進而，比較例9是有關含有吡咬硫酮和氧化鈦、但不含包含一價銅的銅玻璃的防污塗料組成物。根據防污評價的結果’就比較例9而言’在第4個月的觀察時附著有水生生物，長期防污性比實施例差得多。比較例10是在比較例9中加入氧化鋅的防污塗料組成物。由防污評價的結果可知，就比較例而言，在第4個月的觀察時水生生物仍有附著，即使加入了氧化鋅，也無法改善長期防污性。比較例11是在比較例9中加入二曱基二硫代氨基曱酸鋅的防污塗料組成物。由防污評價的結果可知，就比較例 11而言，儘管長期防污性稍有改善，但在第4個月的觀察時附著有水生生物，即使加入了二甲基二硫代氨基曱酸辞’仍無法大幅改善長期防污性。比較例12是在比較例9中加入二硫化四乙基秋蘭姆的防3塗料組成物。由防污評價的結果可知，&比較例12而在第4個月的觀察時附著有水生生物，即使加入二硫化四乙基秋蘭姆，幾乎無法改善長期防污性。進而可知，含有吡啶硫酮銅的實施例丨、2和5，與含 25 201224083 有°比唆硫酮鋅的實施例3、4和6相比’長期防污性更加優良。[Table 2] Antifouling Evaluation Example Comparative Example 1 2 3 4 5 6 1 2 3 4 5 6 7 8 9 10 II 12 笫 2 months ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 4th month ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Δ Δ 〇〇笫 6 months ◎ ◎ ◎ ◎ ◎ ◎ X 〇〇 Δ ◎ ◎ 〇〇 XX Δ Δ _ 8th month ◎ ◎ ◎ ◎ ◎ ◎ X Δ △ X 〇〇〇 Δ XXXX 10th month ◎ ◎ ◎ ◎ ◎ ◎ XXXX Δ Δ Δ XXXXX _ 12th month ◎ ◎ 〇〇 ◎ 〇 XXXXXXXXXXXX From Table 2, the implementation of the present invention The antifouling coating compositions of Examples 1 to 6 were superior in long-term antifouling properties to any of the antifouling coating compositions of Comparative Examples 1 to 12. Example 1-6 contains copper glass containing divalent copper, three components of metal thiophenone and oxidized ruthenium. In contrast, Comparative Example 1 only contains copper glass containing divalent copper 'Comparative Example 2 and 3 contains only copper glass and metal containing divalent copper. Compared with biting sulfur, Comparative Example 4 contains copper glass and titanium oxide containing divalent steel, and the long-term antifouling property of Comparative Example 4 is compared with Example 6 As a result, it has been found that in order for the antifouling paint composition to exhibit excellent long-term antifouling properties, it is necessary to contain all of the above three components, and even if only one of the three components is missing, the long-term antifouling property is extremely lowered. 'In the case of Comparative Examples 5 to 8, the three components containing copper boride, metal pyrithione and titanium oxide containing monovalent copper, or three components including oxidized sub-steel, metal pyrithione and titanium oxide The long-term anti-fouling property of the stain coating composition was investigated, and the long-term antifouling 24 201224083 of any of Comparative Examples 5 to 8 was much lower than those of Examples 1 to 6. It is understood that the addition of metal pyridostine Ketones and titanium oxide are greatly improved The effect of the antifouling property is that when copper glass or cuprous oxide containing monovalent copper is used in the copper glass containing divalent copper, the same effect cannot be obtained. Further, Comparative Example 9 is related. An antifouling coating composition of pyridone and titanium oxide, but not containing copper glass containing monovalent copper. According to the results of the antifouling evaluation, 'in the case of Comparative Example 9, 'the attached water was observed at the fourth month of observation. The long-term antifouling property was much worse than that of the examples. Comparative Example 10 is an antifouling coating composition in which zinc oxide was added in Comparative Example 9. As a result of the antifouling evaluation, it was found that in the comparative example, in the fourth The aquatic organisms remained attached during the observation of the month, and the long-term antifouling property could not be improved even if zinc oxide was added. Comparative Example 11 is an antifouling coating composition in which zinc dimercaptodithiocarbamic acid was added in Comparative Example 9. As a result of the evaluation of the antifouling, it was found that in Comparative Example 11, although the long-term antifouling property was slightly improved, aquatic organisms were attached at the observation of the fourth month even if dimethyldithioaminopurine was added. Sour words' still can't significantly improve long-term Comparative Example 12 is an anti-3 coating composition in which tetraethylthiuram disulfide was added in Comparative Example 9. As a result of the antifouling evaluation, it was found that & Comparative Example 12 was observed at the fourth month. Adhered to aquatic organisms, even if tetraethylthiuram disulfide was added, it was almost impossible to improve long-term antifouling properties. Further, it can be seen that Examples 丨, 2 and 5 containing copper pyrithione have a ratio of sulfur to sulfur containing 25 201224083 Examples 3, 4 and 6 of ketone zinc are more excellent in 'long-term antifouling properties.

Claims

201224083 七、申請專利範圍： 1 · 一種防污塗料組成物，包含（A)含有二價鋼的銅玻璃、（B)金屬°比啶硫酮類以及（C)氧化鈦，其中，該金屬吡啶硫酮類的金屬為銅或鋅，該防污塗料組成物還含有擴散用樹脂，該銅玻璃（A)中的一氧化銅（CuO)的含量為25〜40摩爾％，以固體成分換算，該銅玻璃（A)的含量占該防污塗料組成物的固體成分中的1〜20質量％，以固體成分換算，該金屬吡啶硫酮類（B)的含量相對於該銅玻璃（A)100質量份為25~150質量份，以固體成分換算’該氧化鈦（c)的含量相對於該銅玻璃 (A)100質量份為50-300質量份。 2. 如申請專利範圍第1項所述的防污塗料組成物，其中’該金屬°比咬硫酮為金屬雙吼咬硫酮類。 3. 如申請專利範圍第1項所述的防污塗料組成物其中，該氧化鈦為金紅石型。 4. 如中請㈣範圍射任—項料的防污塗料組成物，更包含溶出助劑。 5. —種漁網、漁網用具及水中建築結構，其表面具有使用申請專利範圍第1項至第4 中币4項T任項所述的防污塗料組成物而形成的防污塗膜。 27 201224083 英文發明摘要：無四指定代表圖· 無五、本案若有化學式時，請揭示最能顯示發明特徵的化學式：201224083 VII. Patent application scope: 1 · An antifouling coating composition comprising (A) copper glass containing divalent steel, (B) metal pyridine thioketone and (C) titanium oxide, wherein the metal pyridine The thiol-based metal is copper or zinc, and the antifouling coating composition further contains a diffusion resin, and the content of copper monoxide (CuO) in the copper glass (A) is 25 to 40 mol%, in terms of solid content, The content of the copper glass (A) is 1 to 20% by mass based on the solid content of the antifouling coating composition, and the content of the metal pyrithione (B) is relative to the copper glass (A) in terms of solid content. The content of the titanium oxide (c) is 50-300 parts by mass based on 100 parts by mass of the copper glass (A) in terms of solid content. 2. The antifouling coating composition according to claim 1, wherein the metal is a metal bismuth thione. 3. The antifouling coating composition according to claim 1, wherein the titanium oxide is rutile. 4. For example, please refer to (4) the scope of the anti-fouling coating composition of the project, and further include the dissolution aid. 5. A fishing net, a fishing net appliance and a waterborne building structure having an antifouling coating film formed on the surface thereof using the antifouling coating composition described in the first to fourth of the patents of the fourth item. 27 201224083 English Abstract: None Four Designated Representatives · None 5. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: