201122063 -τν-/jjif.doc 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種使用含水分散型金屬的樹脂之防 污塗料用樹脂分散體的製造方法。更詳細而言，本發明是 有關於一種可形成防止海中生物及海藻類附著於水中構造 物、漁網、船底上的塗膜之防污塗料用樹脂分散體的製造 方法。 【先前技術】 由防污塗料形成的塗膜是藉由其所含的防污劑成分溶 出至海中而發揮防污效果。由使用松香系化合物的崩解型 防污塗料所形成的塗膜於長時間浸潰於海中的情況下，溶 出成分逐漸變少，不溶出成分逐漸變多，因此，塗膜面成 為凹凸狀，海中生物等的生物的附著防止效果明顯下降。 另一方面，由自研磨型防污塗料形成的塗膜是藉由對 塗膜表面緩緩進行表面更新（自研磨），於塗膜表面上一直 露出防污成分，而發揮長期的防污效果。然而，該些塗料 中大置含有二甲笨或醇等各種有機溶劑，由於近年來的揮 發性有機化合物(V〇latile 〇rganic C〇mp〇un(j，vqc)問題， 而正在研究各種代替該些防污塗料的防污塗料。 作為自研磨型防污塗料，例如專利文獻1中記載有— 種含有如下樹脂組成物作為媒液(v eh丨c 1 e)的防污塗料組成 物’上述樹脂組成物包含於侧鏈的末端部具有含金屬原子 的基團的樹脂。又’作為該金屬原子，記載有鋅(Zn)、銅 (Cu)、碲(Te)。 201122063. jj^tu^pif.doc 於專利文獻2中，提出有一 其特徵在於：含有含二價金性防污塗料組成物’ 且更含有㈣化合物。作為該:曰、水以及驗性化合物， 鎮_、_)，作為驗性/匕^金屬己載^载有&、以、 該專利文獻2中記載，含二 。己載有虱、胺。而且 金屬的聚合性單體的單體物進有含二價 於專利文獻3中，接中右一絲丁歜。而獲侍。 以及來源於反紐乳化綱單 2含二價金屬的單元 二價金屬，記載有Cu、Zn、Mg、(/知水性分散液。作為 記載，上麟脂7Jc性分餘且料利文獻3中 I 劑以及有機溶劑的混合溶液進行溶液聚 合，並視f要精麟舰理，_與核合而獲得。 於專利文獻4中提出有一種水性防污塗料，其含有於 樹脂分子巾含錄基及/或金__旨基、且藉由乳液聚合 而獲得的細a酸值為1〇 mg K〇H/g〜獅mg K〇H/g的水 性樹脂減，以及視需要而含有含魏及二價以上的金屬 的水性金屬錯合物。作為該金屬，記載有Cu、Zn、Ca、 Mg、Zr、Fe。 於專利文獻5中，提出有一種含有水性樹脂乳液作為 具有防污性的黏合劑而形成的水性防污樹脂組成物，上述 水性樹脂乳液是使用乳化劑將如下樹脂加以水分散而形 成，上述樹脂是於分子内及/或分子間具有以使酸值為1〇 mg KOH/g〜300 mg KOH/g的基質樹脂中的羧基與二價金 屬之當量比達到0.1〜5的方式而形成的金屬羧酸酯結構 5 201122063. jj'tujpif.doc 的樹m該二價金屬，記載有cu、zn、ca [先則技術文獻] s [專利文獻] 利文獻1]日本專利特開昭62_57464號公報 [利文獻2]日本專利特開細3-·23號公報 [專利文獻3]日本專利特開2007_23243號公報 [專利文獻4]日本專利特開2_·1()9729號公報 [專利文獻5]日本專利特開平叫72^號公報 的古ί而’專利文獻1所記細防污塗料是麵解於-般 2有機溶射的狀態下㈣，並不滿足近年衛又 面所期望的水性化。 衣兄衛生方 專利文獻2的水性防污塗料Α量含有配位於 的^化合物，錄性化合物殘存於塗財，耐水性t屬 且塗膜的密著性有問題。 車又低 專利讀3的水性防污塗料使収紐乳化劑作為丘 構單元，故來源於乳化劑的氧化伸絲(alkyte …咖_+，料⑽驗中塗膜的 對於專利文獻4的水性防污塗料，於 聚合中導入至樹脂中的含二價金屬的單體成分== 配竣酸與金屬與鹼性化合物的水性金屬錯合物時 ^ 合物殘存於塗膜中，塗膜的耐水性、長期防污性 塗膜的密著性有問題。 & 專利文獻5的水性防污樹脂組成物是在溶解於二甲苯 201122063. 或乙酸丁酯等的有機溶劑中的樹脂中調配添加乳化劑並加 以水稀釋，進行強制乳化而形成，樹脂成分容易沈澱，保 存時會为離政固成水層與含樹脂的層，故乳液的儲存穩定 性有問題。 【發明内容】 本發明的目的在於提供一種儲存穩定性及於海水中的 耐水性優異、可長期表現出防污效果、進而密著性優異的 具有自研磨性的防污塗料用樹脂分散體。 本發明的防污塗料用樹脂分散體的製造方法包括製造 含一價金屬的聚合物(A)的步驟、以及將該聚合物分散 於包含水或水/有機溶氣合物齡散介質巾的步驟，該防 污塗料用樹脂分散體的製造方法的特徵在於：含二價金屬 的聚合物(A)是使1 wt%(重量百分比)〜4〇 wt%的含二價金 屬的乙=性我和單體(al)、〇〜8福的含誠的乙稀性 不飽和單體(a2)、G〜40 wt%的含經基的乙4性不飽和單體 (a3)以及99 wt%〜22 wt%的其他乙烯性不飽和單體㈣以 二階段以上的多階段輯溶液聚合而獲得的聚合物。 [發明的效果] 根據本發明’可提供一種儲存穩定性以及於海水中的 财水性優異、可長期表現出辦效果、進而密著性優異的 具有自研磨性的防污塗料用樹脂分散體。 為讓本發明之上述和其他目的、特徵和優點能更明顯 下文特舉較佳實關，並配合所關式，作詳 明如下。 it.doc 201122063 【實施方式】 _本發明的防污塗料用樹脂分散體的製造方法包括製造 含一價金屬的聚合物(A)的步驟、以及將該聚合物分散 於包含水或水/有機溶劑混合物的分散介質中的步驟，該防 污塗料用樹脂分散體的製造方法的特徵在於^ 是使――含二價金 ㈣' G〜8 wt%的含_㈣馳不飽和單體 (a )〜40 wt%的含經基紅烯性不飽和單體㈣以及叩 二°〜22 Wt%的其他乙婦性不飽和單體(a4)以二階段以上 的户階段進行溶液聚合而獲得的聚合物。 [含一4貝金屬的乙稀性不飽和單體(ai)] 二述聚合物(A)時作為原料中的—種而使用的含 二貝金屬的乙稀性讀和單體(al)的量為相對於作為聚合 ()了料而使用的(al)〜(a4)的合計量1〇〇而設定 = wt/0〜40 wt%的範圍。其原因在於，藉由將含二價金 屬的乙烯性不飽和單體(al)的量 :形成的塗膜賦予更優異的自===: ==和單_⑽量較好的是大於等於5^^= 和單體ra】他旦—故， 價金屬的乙烯性不飽 的：i的;等於4° ·密著性與水解性 接古I、 t 期的自研磨性’防污效果進-步 小：等d =烯性不飽和單體(ai)的量較好的是 f於25 Wt% ’更好的是小於等於20 wt%。 3 —價金屬的乙馳不飽和單體㈣是具有與二價金 8 201122063. joHujpif.doc 屬進行離子鍵結的緩基的單體’較好的是具有兩個不飽和 基的含二價金屬的乙稀性不飽和單體(ala)、及/或下述通式 (I)所表示的含一價金屬的乙歸性不飽和單體(alb)。 CR2=C(Kl)-COO-U-R2 ⑴ (式(I)中’M表示二價金屬，R1表示氫原子或曱基， R2表示有機酸殘基） 就於水中的溶解性的觀點而言，上述含二價金屬的乙 稀性不飽和單體(al)中所含的二價金屬的金屬較好的是使 用選自Mg、Ca、Zn及Cu所組成的組群中的至少一種金 屬。就所獲得的聚合物(A)的透明性的觀點而言，更好的是 Mg、Ca、Zn，進而更好的是Zn。上述金屬可使用一種， 亦可將兩種以上併用。 單體（ala)例如可列舉：丙烯酸鎂 [(CH2=CHCOO)2Mg]、甲基丙烯酸鎂 [(CH2-C(CH3)COO)2Mg]、丙稀酸!丐[(cH2=CHCOO)2Ca]、 甲基丙烯酸鈣[(CH2=C(CH3)COO)2Ca]、丙烯酸鋅 [(CH2=CHCOO)2Zn]、甲基丙烯酸鋅 [(CH2-C(CH3)COO)2Zn]、丙稀酸銅[(ch2=cHCOO)2Cu]、 曱基丙烯酸銅[(CH2=C(CH3)C00)2Cu]等的（曱基)丙烯酸二 ^[貝金屬鹽。上述單體(ala)可視需要而適當選擇使用一種或 者兩種以上。其中，於使用（曱基）丙烯酸鋅時，有藉由溶 液聚合所得的聚合物(A)的透明性變高，防污塗料的塗膜的 201122063. jj*^ujpif.doc 色調變美觀的傾向，故較好 是指:丙稀酸」或「甲二所"「(甲基)丙稀酸」 鱼疋藉由如下方法而獲4^使無機金屬化合物 飽和單體(例如⑽m⑽酸) 劑或具絲合性錢和基等的反應性 的反應物與錢_或其他單體的相容性㈣，(故可)^ 地進行聚合’因純好。上述反餘好岐於水的存在下 進行，較好的是將反應物中的水的含量設定為001 wt%〜 3〇 wt%的範圍。 上述單體(alb)的R2的有機酸殘基可列舉：由單氣乙 酸、單氟乙酸、乙酸、丙酸、辛酸、柯赫酸(Versatic acid)、 異硬脂酸、棕櫊酸(palmitic acid)、甲酴曱酸(cres〇tic acid)、 萘甲酸、/9-萘曱酸、笨曱酸、2,4,5-三氣苯氧基乙酸、 2,4_二氣苯氧基乙酸、喹啉羧酸、硝基苯甲酸、硝基萘曱 酸、普耳文酸(pulvic acid)等的一價有機酸所衍生的殘基。 該些殘基可視需要而適當選擇，就獲得可長期防止龜裂或 泰J離的耐久性高的塗膜的觀點而言，較好的是脂肪酸(脂肪 族單羧酸)系殘基、例如碳數為1〜20的脂肪酸系殘基。再 者’上述式(I)中的R2的有機酸殘基是指自有機酸的羧基中 去除了質子的殘餘部分，代替該質子而與金屬Μ進行離子 鍵結。 單體(alb)的具體例可列舉：單氯乙酸（曱基）丙烯酸 鑷、單氯乙酸（甲基)丙烯酸鈣、單氯乙酸（曱基）丙烯酸鋅、 201122063. jjHujpif.doc 單氣乙酸（甲基)丙烯酸銅；單氟乙酸（甲基）丙烯酸鎂、單氟 乙酸（甲基)丙烯酸鈣、單氟乙酸（甲基)丙烯酸鋅、單氟乙酸 (曱基)丙烯酸銅；乙酸（曱基)丙烯酸鎂、乙酸（甲基)丙烯酸 鈣、乙酸（曱基)丙烯酸鋅、乙酸（甲基）丙烯酸銅；丙酸（曱 基)丙烯酸鎂、丙酸（甲基)丙烯酸鈣、丙酸（曱基)丙烯酸鋅、 丙酸（曱基)丙烯酸銅；辛酸（曱基)丙烯酸鎂、辛酸（甲基）丙 烯酸鈣、辛酸（曱基)丙烯酸鋅、辛酸(曱基)丙烯酸銅；柯赫 酸（曱基)丙烯酸鎂、柯赫酸（曱基)丙烯酸鈣、柯赫酸（曱基） 丙烯酸鋅、柯赫酸（曱基)丙烯酸銅；異硬脂酸（曱基)丙烯酸 鎂、異硬脂酸(曱基)丙烯酸鈣、異硬脂酸（曱基)丙烯酸鋅、 異硬脂酸（曱基)丙烯酸銅；棕櫚酸（甲基)丙烯酸鎂、棕櫚酸 (曱基)丙烯酸鈣、棕櫚酸（曱基)丙烯酸鋅、棕橺酸（甲基)丙 烯酸銅；曱酚曱酸(曱基)丙烯酸鎂、曱酚曱酸(曱基)丙烯酸 鈣、曱酚曱酸（曱基)丙烯酸鋅、曱酚甲酸（曱基)丙烯酸銅； 萘曱酸(曱基)丙烯酸鎂、α_萘甲酸(曱基)丙烯酸鈣、α -萘甲酸（曱基）丙烯酸鋅、α-萘曱酸（曱基）丙烯酸銅；/3-萘曱酸（曱基)丙烯酸鎂、萘曱酸(甲基)丙烯酸鈣、沒-萘 甲酸（曱基)丙烯酸鋅、萘曱酸（曱基)丙烯酸銅；苯曱酸 (曱基)丙烯酸鎂、苯曱酸(曱基)丙烯酸鈣、苯曱酸(曱基)丙 烯酸鋅、苯曱酸(甲基)丙烯酸銅；2,4,5_三氯苯氧基乙酸（曱 基）丙烯酸酯鎂、2,4,5-三氣苯氧基乙酸（曱基）丙烯酸鈣、 2,4,5-二氣本乳基乙酸（曱基）丙稀酸鋅、2,4,5-三氣苯氧基乙 酸（曱基)丙烯酸銅；2,4-二氯笨氧基乙酸（曱基）丙烯酸鎂、 2,4-二氣苯氧基乙酸（曱基)丙烯酸鈣、2,4_二氣笨氧基乙酸 if.doc 201122063 (曱基)丙烯酸鋅、2,4-二氣苯氧基乙酸（甲基）丙烯酸銅；喹 琳叛酸（甲基)丙婦酸鎭、啥琳叛酸(曱基)丙稀酸約、嗤琳缓 酸（甲基)丙稀酸鋅、喧淋緩酸（曱基)丙烯酸銅；確基苯甲酸 (甲基)丙烯酸鎂、硝基笨甲1酸（曱基)丙烯酸鈣、硝基苯甲酸 (甲基)丙烯酸鋅、硝基苯甲酸（甲基)丙烯酸銅；硝基萘甲酸 (曱基)丙烯酸鎂、硝基萘甲酸（甲基)丙烯酸鈣、硝基萘曱酸 (甲基)丙稀酸鋅、硝基萘甲酸（曱基)丙稀酸銅；普耳文酸（曱 基）丙烯酸鎂、普耳文酸（曱基）丙烯酸鈣、普耳文酸（甲基） 丙烯酸鋅、普耳文酸（甲基)丙烯酸銅等。該些單體(alb)可 視需要而適當選擇使用一種或者兩種以上。其中，若使用 含鋅單體，則所獲得的樹脂成分的透明性變高，塗膜的色 調變美觀，故較好。進而，就塗膜的财久性的觀點而言， 更好的是使用脂肪酸（甲基)丙烯酸鋅(式⑴的M為鋅、r2 為脂肪酸殘基）。再者，所謂「（曱基)丙稀酸鹽」是指「丙 烯酸鹽」或「甲基丙烯酸鹽」。 物ΪίΓ)是藉由如下方法而獲得：使無機金屬化合 物、讀基的乙烯性不飽和單體、以及與式⑴ ===聚合性有機㈣ σ生不飽和基等的反應性稀釋劑中反應。 心======= 較好的是併用上述單體二性 體二是作為單體㈣的(甲基)丙稀酸辞盘作為單 (_θ肪酸(甲基)丙稀酸峨(I)的Μ為鋅 12 201122063^ jpii.doc 肪酸殘基)的組合。 舰^=併„用單體—與單體⑽)作為含二價金屬的乙 的莫耳比t的是將單體㈣與單體_ (ala/_m丨 為1〇/90〜9_的範圍。藉由將 更優異的^膜，〇 ’可獲得耐龜裂性或密著性 等於、10/90，、/較好。又，藉由將設定為大於 魅地’可更長時間地維持所形成的塗膜的充分的自 ^ ^好。（Μ—)更好的是麵〜麵的範圍， 進而更好的是30/70〜70/30的範圍。 ^含有單體⑽)以及單體(叫的單體混合物可藉由 而齡.使無機金屬化合物、含縣的乙烯性不 ^有^、以及與式(1)中的有機酸殘基尺2相對應的非聚合 於有機溶劑等的稀釋劑或具有聚合性不飽和基 4的反應性稀釋劑中反應。 你H ’較好的是將非聚合性有機酸的使用量設定為相 承拉1金屬化合物而為請倍莫耳〜3倍莫耳的範圍， 平人:2設定為〇.01倍莫耳〜〇.95倍莫耳的範圍。於將非 ^性有機酸的使用量設定為大於等於_倍莫耳時，可 Ρ =單體混合物製造步驟中的固體析出，並且塗膜的自研 耐龜裂性變得更良好，故較好。又，於將非聚合性 土ΐΐί的使用量設定為小於等於3倍莫耳時，可更長時間 塗膜的防污性，故較好。更好的非聚合性有機酸的 便用垔為0.1倍莫耳〜0.7倍莫耳。 再者，如後述，即便於合成聚合物⑷時於原料中不使 13 201122063. j-j*Tu^pif.doc 金屬#乙婦性不飽和單體(al)的情況下，亦 下师)〜(iii)’而使酬相對應的單元 含有含縣的乙触殘和單體(a2)的單體混 。物⑽作為第一階段的原料’來進行 (聰第-階财所獲得的聚合物與二價金屬化合物 反應，錯此於第一階段的聚合物中導入二價金屬。 性不反應物的存在下，❹含有含祕的乙烯 )的單體混合物(b3)作為第二階段的原 料，來進订第二階段的聚合。 [S緩基的乙婦性不飽和單體(a])] 製備上述聚合物⑷時作為原料中的—種而使用的含 性不鮮單郎2)的量為相對於作騎合物㈧ 的原料而使用的(al)〜(a4)的合計量⑽wt%而設〜 8邊的範圍。就儲存敎性變良好的方面^，含缓基 的乙?性不飽和單體(a2)的量較好的是大於等於工加。二 好的是大於等於2 wt%。又，若含敌基的乙烯性不飽和單 體⑹的量超=wt%，則聚合物的黏度變得極高，並且塗 膜的财水性、密著性下降。錢基的乙雜聽和單體 於等於7 wt%，更好的是小於等於6 _。 含叛基的乙稀性不飽和單體⑻可列i成^丙稀 酸、丙稀酸、丁馳、乙絲笨曱酸、反丁烯二酸t伊^ 酸(itaC画aCld)、順丁婦二酸、甲基順丁稀二酸⑽刪价 14 201122063 acid)等的一元酸或二元酸單體類，順丁烯二酸單甲醋、順 丁烯二酸單乙酯、順丁烯二酸單丁酯、順丁烯二酸單辛酯'' 伊康酸單曱酯、伊康酸單乙酯、伊康酸單丁醋 嚴 辛醋、反丁稀二酸單甲酉旨、反丁烯二酸單乙g旨、3 = 酸單丁酯、反丁烯二酸單辛酯、曱基順丁烯二酸單乙酯、 四氫鄰苯二曱酸單（曱基）丙烯酸羥基乙醋 (tetrahydrophthalic acid monohydroxyethyl(meth)acrylate) > 四風鄰本—曱酸早（曱基）丙稀酸經基丙g旨、四氮鄰苯二甲 酸單（甲基)丙烯酸羥基丁酯、鄰苯二甲酸單（曱基)丙烯酸羥 基乙酯、鄰苯二曱酸單（甲基）丙烯酸羥基丙酯、琥珀酸單 (曱基）丙烯酸羥基乙醋（suecinic add monohydroxyethyl(meth)acrylate)、琥拍酸單（甲基）丙烯酸 羥基丙酯、順丁烯二酸單（曱基）丙烯酸羥基乙酯、順丁烯 一酸單（曱基）丙烯酸經基丙酯等所代表的二元酸或酸針單 體的單酯類等。可視需要而適當選擇使用該些單體中的一 種或者兩種以上。 [含羥基的乙烯性不飽和單體(a3)] 製備上述聚合物(A)時作為原料中的一種而使用的含 羥基的乙烯性不飽和單體(a3)的量為，相對於作為聚合物 (A)的原料而使用的(ai)〜(a4)的合計量1〇〇 wt%而設定為〇 〜40 wt%的範圍。含羥基的乙烯性不飽和單體(a3)為任意 成为，但藉由設定為小於等於4〇 wt%，有塗膜的耐水性提 高、密著性變良好的傾向。含羥基的乙烯性不飽和單體(a3) 的量更好的是小於等於30 wt%，進而更好的是小於等於 15 201122063 20 wt%。 2-羥可列舉:(曱基)_ 羥基丙酯、(甲基)丙烯酸1 基丙酯、(甲基)丙烯酸3· 基丁醋等的含Μ基' _丙_ _ 2·經基乙醋與氧化乙稀曰單體;(甲基)丙稀酸 醋等的加成物，_(甲基)丙烯酸2-羥心内 =广己二 2-羥基丙酯等的二聚物或三聚物；二(甲基)丙烯酸 的具有多個經基的單體；乙 甲土）丙稀酸醋等 ^ ^^^^ ，—知烯丙醚、丙二醇烯丙醚、 “一知烯丙醚、聚丙二醇烯内醚 丙驗等的末端經基婦丙基化聚鱗單體=一_ 選擇使用該些單體中的-種或兩種以上。而要而適當 [其他乙烯性不飽和單體單元(a4)】 製備上述聚合物⑷時作為原料中的 他乙烯性不飽和單體㈣的量為， 扁 原料而使用的(a 1)〜(a4)的人計于 '作為^物(A)的 痛〜心％的範圍 ^ 1〇〇Wt%而設定為99 .^和單體㈣只要是與上述含二價金屬 」雙_相’難無特職H合物(A)含有來源 :八他乙烯性不飽和單體(a4)的單 ’、 可撓性或耐龜裂.耐剝離性與長“自研磨性： 衡阜父佳，且可使該些特性良好。 201122063. j j^tu^pif.doc 其他乙烯性不飽和單體(a4)可列舉：（甲基）丙烯酸曱 酯、(甲基)丙烯酸乙酯、(甲基)丙稀酸2_曱氧基乙酯、(曱 基)丙稀酸2-乙氧基乙醋、（甲基)丙烯酸丁氧基乙醋、丁 氧基二乙广醇(曱基)丙稀酸醋、曱氧基三乙二醇(甲基)丙稀 酸酉曰、曱氧基聚乙三醇(甲基)丙卿m (曱基)丙稀酸苯氧 基乙醋、（曱基)丙烯酸2_(2_乙基己氧基)乙醋、（曱基)丙稀 酸1-曱基-2-甲氧基乙酯、（曱基)丙烯酸3_曱氧基丁酯、（曱 基)丙稀酸3-曱基-3-甲氧基丁醋、（曱基)丙稀酸間甲氧基苯 醋、（甲基)丙烯酸對甲氧基苯醋、（曱基)丙稀酸鄰甲氧基苯 基乙酯、/甲基)丙烯酸間甲氧基苯基乙酯、（曱基)丙烯酸對 曱氧基苯基乙酯、（曱基)丙烯酸正丙酯、（曱基)丙烯酸異丙 酯、（曱基）丙稀酸正丁酯、（甲基）丙烯酸異丁酯、（甲基）丙 稀酸第二丁醋、（曱基)丙烯酸2-乙基己酯、（甲基)丙烯酸月 桂酯、（曱基）丙烯酸硬脂酯、（甲基）丙烯酸山蝓酯 (behenyKmetyaciry late)、（曱基)丙烯酸节酯、（曱基)丙烯酸 笨醋、（曱基)丙稀酸異冰片酯(is〇b〇rnyl(meth)acrylate)、（曱 基）丙烯酸環己酯、（曱基)丙烯酸縮水甘油酯、（甲基）丙烯 酸三氟乙酯、（甲基)丙烯酸全氟辛酯等的（甲基)丙烯酸酯單 體；（曱基)丙烯酸丁基胺基乙酯、（甲基)丙烯醯胺等的含一 級及一級胺基的乙烯早體，（甲基）丙稀酸二曱基胺夷乙 酯、（曱基)丙烯酸二乙基胺基乙酯、（曱基）丙烯酸二甲^胺 基丙酯、（曱基)丙烯酸二曱基胺基丁酯、（曱基)丙稀酸二丁 基胺基乙酯、二曱基胺基乙基（曱基）丙烯醯胺、二甲基胺 基丙基（甲基）丙烯醯胺等的含三級胺基的乙稀單體；乙稀 17 ii:doc 201122063 基鱗細、乙職如定、乙烯基料 的雜壤系驗性單體；苯乙埽、乙稀基甲笨、心甲基苯乙歸、 ，，腈 '曱基丙稀腈、乙酸乙烯醋、丙酸乙稀醋等的乙 糸f體：^基聚乙二醇烯丙醚、曱氧基聚丙二醇烯丙醚、 了乳基聚乙二醇稀_、丁氧基聚丙二醇稀丙醚、甲氧美 X乙一醇聚丙二醇烯丙鱗、丁氧基聚乙二醇.聚丙二醇稀 丙鱗等的末端絲麵丙基化㈣單體；乙二醇二(甲 丙烯H —乙二醇二（甲基)丙烯酸醋、三乙二醇 ^ :輪旨、聚乙二醇二(甲基)丙烤酸酷、M-丁二醇二(甲 :丙烯酸酯、1，6-己二醇二(甲基)丙烯_、新戊二醇二(曱 :丙稀H 1’9·壬二醇二（甲基)丙晞酸g旨、•癸二醇 二(甲基)丙軸旨、三經甲基丙燒三(甲基)丙烯酸I季戍 I丙HH)丙稀酸§1、二季戊四醇六(甲基)丙烯酸酿、甲 2 =巧:異三聚氛酸三烯丙醋、順丁稀二酸二: + = & 等的多官能單體。該些單體可視 兩要而適當選擇使用-種或兩種以上。 視 ^ ’亦可使収紐乳化_為其他乙職不飽和單 功：：應性乳化劑於聚合反應時作為乳化劑而發揮 '、’n體細共聚合而形成所得共聚物的結構單 聚純(A)中導人反應性乳化劑，則來源於反應性 礼化劑的單元有助於分散性的提高。 此種反應性乳化劑可使用具有自由絲合性的碳間雙 =~〇的界面活性劑，較好的是，可❹ “生的碳間雙鍵(c，的非離子系界面活性劑或陰離j 201122063^ 界面活性劑。 又，此種反應性乳化劑例如有：日本乳化劑公司製造 的「Antox MS60」’第一工業製藥公司製造的「Aqualon HS-05」、「AqualonHS-10」、「AqualonHS-20」，ADEKA 公司製造的「Adeka Reasoap SE10」、「Adeka Reasoap SR10」、「AdekaReasoapSR20」，三洋化成工業公司製 造的「Eleminol JS2」等的陰離子系反應性乳化劑；第一工 業製藥公司製造的「Aqualon RN· 1 〇」、「Aqualon RN-20」、 「Aqualon RN-30」’ ADEKA 公司製造的「Adeka Reasoap NE10」、「Adeka Reasoap NE20」、「Adeka Reasoap NE30」、 「Adeka Reasoap ER10」等的非離子系反應性乳化劑。該 些反應性乳化劑可視需要而適當選擇使用一種或兩種以 上。 π 3 F工丞的&埽性不飽和単體(a3)或其他乙烯 性不飽和單體㈣中’可將與（曱基)丙稀酸醋單體相比較缺 乏自由基聚合性的烯丙基化㈣單體用作含二價金屬的乙 =性不飽和單體⑻合成時、聚合物(A)合成時的反應性稀 ^劑。於含二價金屬的乙烯性不飽和單體⑹合成時、或 聚合物⑷合斜’必_有機溶解稀_作為反應介質 至反應容器中’藉由將上述稀丙基化聚叫體用作 可提高儲存穩^ 可減^需财機溶劑量，又， [聚合物(Α)] 藉由本發明的方法而製造的防污塗料用樹脂分散體所 201122063.. j^-rw^yif.doc 使上述(al)〜⑽)單體以二階段以上 ㈣合物㈧是藉由如下方式而獲得:首先，使作為 蘇經制φ的⑷)〜(a4)單體的""部分於溶解聚合物⑷的 、於聚合起始劑的存在下進行第—階段的聚合， 二人。上述(al)〜(a4)單體的剩餘部/分進行第二階段以後 較好=合！的儲存穩定性的觀點而言，上述聚合物(A) "：：：：：：：：：：：-；! 單體混合物(bl)‘二==烯: :=有，的乙婦性不飽和單酬、且含有含二 ίif 雜不飽和單_)的單體混合物㈣進行溶 =δ的步驟。（al)較好的是(al =用此種多階段的聚合方法，可於聚合物中局:導^ =:=:定性、塗膜的耐水性提高，製成水分散 ，體心物(M)與㈣的聚合順序不限，就聚合物的經 ::合物_合時，有二=:= 會由於絲的作料㈣賴轉離，穩定性下降。 上i«合物⑷可藉心少·下辭 液聚合而獲得：使含有至少-種含縣的乙雜不飽和; 20 201122063. j j*Tu^pif.doc 合物(M)進行溶液聚合的第-階段聚合；使 ΐ驟==得的聚合物與二價金屬化合物反應的 步驟，以及於上述步_反應物的存在下，使含有至少一 種含羧基的乙烯性不飽和單體 聚合的第n聚合。 進仃 乙烯:^ Ϊ5二便於原料申不使用上述含二價金屬的 得==金 中導^含二細的乙_錢和單體⑷合物 屬的可=;:r:6r_成金 曰本專_平_G5 顺號公報或 行。具體而言，可對第錢的公知方法來進 價金屬的氧化物、二價金屬的 ，，及-價有機酸或水，於 >皿度以下的溫度下加以加_拌而進行。 又或刀解 上述聚合反應中使用的稀釋劑 ;列二甲”醇、正丙醇、異=特正：定異r: 第二丁醇、2-丁醇、2-曱氧基乙醇、3_ : 等的-元醇類’乙二醇、1,2·丙二醇、13土氧土醇 二醇、2-甲基_2,4_戊二醇、2 ’ T —' 2’3_丁 庚二醇、二乙二醇、二丙二醇Λ=κ2,5·己二醇、2,4· 醇類，、甲基乙基酮、乙_二;= 醚、一氧陸_i_e)等的醚類’乙二醇單甲醚甲:二： 21 201122063 , 」d-r v/pi 士 · do c 單乙醚、乙二醇單正丙醚、乙二醇單異丙醚、乙二醇單正 丁醚、乙二醇單異丁醚、乙二醇單第三丁醚、乙二醇單己 醚、乙二醇單苯醚、丙二醇單曱醚、丙二醇單乙醚、丙二 醇單正丙醚、丙二醇單異丙醚、丙二醇單正丁醚、丙二醇 單異丁醚、丙二醇單第三丁醚、乙二醇二曱醚、乙二醇二 乙醚、丙二醇二曱醚、丙二醇二乙醚、二乙二醇單曱醚、 二乙二醇單乙醚、二乙二醇單正丙醚、二乙二醇單異丙醚、 二乙二醇單正丁醚、二乙二醇單異丁醚、二乙二醇單第三 丁醚、二丙二醇單曱醚、二丙二醇單乙醚、二丙二醇單正 丙醚、二丙二醇單異丙醚、二丙二醇單正丁醚、二丙二醇 單異丁醚、二丙二醇單第三丁醚、二乙二醇二曱醚、二乙 二醇二乙醚、二丙二醇二曱醚、二丙二醇二乙醚、三乙二 醇單曱醚、三乙二醇單乙醚、三丙二醇單曱醚、三丙二醇 單乙醚、三乙二醇二甲醚等的二醇醚類，乙二醇單乙酸酯、 乙二醇二乙酸酯、乙二醇單曱醚乙酸酯、乙二醇單乙醚乙 酸酯、乙二醇單正丙醚乙酸酯、乙二醇單異丙醚乙酸酯、 丙二醇單曱醚乙酸酯、丙二醇單乙醚乙酸酯、二乙二醇單 乙酸酯、二乙二醇單甲醚乙酸酯、二乙二醇單乙醚乙酸酯、 二丙二醇單甲醚乙酸酯、三乙二醇單曱醚乙酸酯等的二醇 乙酸酯類，正戊烷、正己烷等的脂肪族系烴類，甲苯、二 曱苯、溶劑油(solvent naphtha)等的芳香族系烴類，上述烯 丙基化聚醚單體。該些稀釋劑可單獨使用一種，或者併用 兩種以上。然而，較好的是含有醇系化合物，其原因在於 聚合物(A)的製造穩定性及水分散穩定性變良好。就可減少 201122063. jj^tu jpif.doc 有機溶劑量的觀點而言，進行上述第一階段聚合時的稀釋 劑較好的疋；fcffi丙基化聚縫單體。 上述聚合起始劑並無特別限定，可使用公知的聚合起 始劑。例如可列舉：過氧化_2_乙基己酸第三丁酯(t_butyl peroxy-2-ethylhexanoate)、過氧化二-第三丁基、過氧化月 桂醯、過氧化苯甲醯、過辛酸第三丁酯(t_butyl per〇ct〇ate) 等的有機過氧化物，2,2'-偶氮雙異丁腈 (Azobisisobutyronitrile，AIBN)、2,2’-偶氮雙（2-曱基丁 腈 XAzobismethylbutyronitrile，AMBN)等的偶氮系化合 物。聚合起始劑可單獨使用一種，亦可併用兩種以上。聚 &起始劑的使用置並無特別限定，可適當進行設定。 又’視需要亦可於上述聚合反應中使用公知的鏈轉移 劑。 以如上方式而獲得的聚合物(A)的分子量可根據所需 的特性而適當決定，例如可設定於重量平均分子量 (Mw)l〇〇〇〜50000的範圍内。 [防污塗料用樹脂分散體] 藉由將以如上方式而獲得的聚合物(A)分散於包含水 或水/有機溶劑混合物的分散介質中，可獲得本發明的防污 塗料用樹脂分散體。 對於上述聚合物(A)，就向水相的順暢移動的觀點而 δ ’較好的是於溶解聚合物(A)的稀釋劑的存在下或非存在 下’至少使用含羧基的乙烯性不飽和單體(a2)進行溶液聚 s 然後將所得聚合物中的竣基的一部分或全部加以中和 23 201122063 w —〆it.doc 後’分散於上述分散介質中。上述中和是藉由在聚合物(A) 中添加驗性化合物*進行。所使用的驗化合物並無特別 限定，例如可較好地列舉：氨(水溶液），三甲胺、三乙胺、 二異丙基乙基胺、丁胺等的烷基胺類，二甲基乙醇胺、二 甲基異丙醇胺、甲基二乙醇胺、二乙基乙醇胺、三乙醇胺、 丁醇胺等的醇胺類，嗎啉，異佛爾酮二胺（is〇ph〇r〇ne dmmine)等。驗性化合物可使用一種，亦可併用兩種以上。 以中和度（即中和劑相對於酸的莫耳比)達到4〇%〜15〇%、 較好的是60%〜120%的調配量來添加上述鹼性化合物。本 發明的防污塗料用樹脂分散體的pH值為6.0〜11.0，較好 的是6.5〜9.0。 又，對於上述聚合物(A)而言，至少使用含羥基的乙烯 性不飽和單體(a3)進行②液聚合，並將合物(A)分散於 亡，分散介質中，然後進一步添加羥基官能性交聯劑而進 行交聯’藉此強韌性.耐水性等的塗膜性能提高，因此較好。 羥基官能性交聯劑並無特別限定，可使用公知的羥基 官能性交聯劑。例如可列舉：三聚氰胺樹脂（melamine r=sin)、笨幷胍胺樹脂(benz〇guanamine等的胺基樹 ，，脂肪族異氰酸酯、脂環式異氰酸酯、芳香族異氰酸酯 =的I異氰酸酯等。特別就反應溫度、塗膜物性的觀點而 I，較好的是使用聚異氰酸酯，更好的是使用水溶性或水 分散型的羥基官能性交聯劑。 〇羥基官能性交聯劑的使用量並無特別限定，可於不使 操作性、造膜性、防污性下降的範圍内使用。 24 201122063 jpif.doc 就造膜性 可’的方面而言，上述防污塗料用槲浐 體較好的是一〜60wt%的範圍而;= 機溶=== 水，有機溶劑混合物。上述有 分散)反應中所使用的稀釋劑。就 中==言，該稀釋劑較好的是作為上述聚合反應 钫此作I的稀釋劑而例示的醇或二醇醚等的醇系化合物。 該：化ά合物中，醇可較好地使用沸點相對較低的碳數為i 用石的是碳數為2〜4的—元醇，二賴可較好地使 用石反數為3〜Η、較好的是碳數為3〜8的二醇醚。 上述防污塗料用樹脂分散體中的上述稀釋劑的含量較 料是〇〜2GWt%，更好的是㈣祕。#由於聚合3物里(^； 的聚合反應中所使用的稀釋㈣稀釋綱含量超過上述範 圍々’必顧少轉劑含量時’視需要亦可藉由減壓蒸顧去 除專來進行稀釋劑的去除操作(脫溶劑處理）。 本發明的防污塗料用樹脂分散體中視需要亦可調配其 他防污劑。該防污劑可根據所需求的性能而適當選擇使 用.，例如可列舉：氧化亞銅、硫氰酸亞銅（cuprous thiocyanate)、銅粉末等的銅系防污劑，以及錯、辞、鎳等 其他金屬的化合物，二苯胺等的胺衍生體，腈化合物，苯 幷噻唑系化合物，順丁烯二醯亞胺系化合物，吡啶系化合 物等。該些防污劑可單獨使用一種，或者可將兩種以上組 合使用。更具體可列舉：伸乙基雙（二硫代胺基曱酸)錳 (manganese ethylene bis(dithiocarbamate))、二甲基二硫代胺 25 rit.doc 201122063 基曱酸辞(zinc dimethyl dithiocarbamate)，2-甲硫基-4-第三 丁基胺基-6-環丙基胺基-均三嗪 (2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine) 、 2,4,5,6- 四 氯間苯 二曱腈 (2,4,5,6-tetrachloroisophthalonitrile)、Ν，Ν·二甲基二氣苯基 脲、伸乙基雙（二硫代胺基曱酸）鋅、硫氰酸銅（Copper thiocyanate)、4,5-二氣·2-正辛基-3(2H)異二氫嗟唾酮 (4,5-dichloro-2-n-octyl-3(2H)-isothiazolone)、N-(氟二氯曱 硫基)鄰苯二曱醯亞胺、N，N’-二曱基-Ν'-苯基-(N-氟二氯曱 硫 基） 確酿胺 (N,N,-dimethyl-N,-benzyl-(N-fluorodichloromethylthio)sulfa mide)、2-n比0定硫醇-1-氧化物鋅鹽（2-pyridinethioM-〇xide zinc salt)、一硫化四曱基秋蘭姆（tetramethylthiuram sulfide)、Cu-10%Ni固熔合金、2,4,6-三氣苯基順丁烯二醯 亞胺、2,3,5,6-四氯-4-(曱基磺醯基)吡啶、3-碘-2-丙炔基丁 基胺基曱酸酯(3-iodo-2-propenylbutylcarbamate)、二礙代曱 基對甲苯颯(diiodomethyl-p-tolyl sulfone)、雙(二甲基二硫 代胺甲醯基）伸乙基雙（二硫代胺基甲酸）鋅 (bis(dimethyldithiocarbamoyl) zinc ethylenebis(dithiocarbamate))、苯基（雙 °比咬基）二氯化叙 (phenyl(bispyridyl)bismuth dichloride)、2-(4-°塞0坐基)-笨幷 口米 0坐（2-(4-thiazolyl)-benzimidazole)、°比咬-三苯基删烧 (pyridine-triphenylborane)等。 於本發明的防污塗料用樹脂分散體中，亦可於對塗膜 26 201122063. jjiwjpif.doc 表面賦予潤滑性、防止生物附著之目的下調配二曱基聚石夕 氧烷(dimethyl siloxane)、矽油（silicone oil)等的矽化合物咬 氟化碳等的含氟化合物等。 進而’本發明的防污塗料用樹脂分散體亦可含有各種 顏料、消泡劑、顏料分散劑、流均劑、抗下垂劑、消光劑、 紫外線吸收劑、抗氧化劑、耐熱性提昇劑、助滑劑、防腐 劑、塑化劑、其他乳液樹脂、水溶性樹脂、黏性控制劑等。 使用本發明的防污塗料用樹脂分散體的塗膜可直接或 經由底層塗膜而形成於船舶或各種漁網、港灣設施、攔油 栅(oil fence)、橋樑、海底基地等的水中構造物等的基材表 面。上述底層塗膜可使用伐銹底漆(wash prime = 膠系或環氧㈣的底漆、巾塗漆(intennediate e⑽)等來形 成。關於塗朗形成方法，可毛刷塗佈、噴附冷佈、 報塗佈、沈浸塗佈等的方法將本發_防^ ===或基材上的底層塗膜上。塗二 燥。 、皿下進仃，視*要亦可進行加熱乾 [實例] 伯太=1’藉由實例及比較例對本發明加以更詳細說明， :重量:不以：的任何限定督實例中的份表 是利用以下所示的方污塗料用樹脂分散體的評價 [儲存穩定性評價] 27 201122063,, 防〉可塗料用樹脂分散體的儲存穩定性的評 Γ Γ:Γ分散體於溫度為4〇°C的條件下保存3天、 準來進行。’目測相沈麟的有無。評價是依照以下基 成凝料暖餘成分縣⑽.錄，並未形 有少量沈澱物，但藉由攪拌而沈澱物分散 X :樹脂成分舰.分離，發生凝固，即便麟 次分散。 [塗膜的消耗度試驗] 使用敷料器（applicator) ’以乾燥膜厚達到12〇 的 方式將柄__脂分舰分別㈣於5G mmx5〇 ·χ 2 mm(厚度)的硬質氣乙絲板上’製作雜板，將該試驗 板女裝於設置在海水中的轉桶(rotary drum)中，以7.7 m/s(15 knot)的周速進行旋轉，測定j個月後及3個月後的 消耗膜厚。 [耐水性試驗] 於包含預先塗佈有防銹塗料的喷砂鋼板的基板上，以 乾燥膜厚達到120 的方式塗佈防污塗料用樹脂分散 體，而製作試驗板。將該試驗板於滅菌過遽海水中浸潰1 個月之後，將該試驗板於溫度為20°C的室溫下乾燥1週， 觀察塗膜表面。評價是依照以下基準來進行。 ◎:完全未觀察龜裂及剝離 〇：稍許觀察到龜裂 28 201122063. j^^tujpif.doc 塗膜表面的—部分中觀察到龜裂、剝離 X.塗膜整個表面中觀察到龜裂、剝離。 [網格剝離性試驗] 海J ί 土？Γ水性試驗同樣地製作的試驗板於滅菌過濾 下參h? 貝@月之後’將該試驗板於溫度為2Qt>c的室溫 進行網格剝離試驗。網格剝離試驗中，對該 cut)，::隔?行直至基材為止的交叉切割(_ 挪i诚i作 mm的網格’於其上方貼附Sell_e(註 ^並物急劇剝離，觀察剝離的網格 依照以下基準來進行。 〇 Δ ◎:完全未觀察到網格的剝離及網格角落的剝離 網格未剝離，但僅網格的角落剝離 1個〜12個網格剝離 X : 13〜25個網格剝離。 [製造例Ml] 於具備擾拌機、溫度調整機以及滴加裝置的反應容器 :’添加MFDG(二丙二醇單甲峻)66 3份及氧化鋅(Zn〇)4i ^ ’ -邊進行擾拌-邊升溫至75t：。向其中，帛3小時句 逮滴加包含下述原料的混合物。 曱基丙浠酸(MAA)43份 丙烤酸(AA)36份 水5份 滴加結束後，反應溶液由乳白色狀態變為透明。進而 攪拌2小時後，添加1〇份的MFDG，而獲得透明的含二 29 201122063. ^v/^pif.doc 價金屬的乙烯性不飽和單體混合物Ml。將各、,； 量、所獲得的含二價金屬的乙烯性不飽和單體的添加 的金屬含量以及固體成分濃度示於表1。 &物Ml [製造例M2、製造例M3] 利用與製造例Ml相同的方法，以表丨 來製造含二價金屬的乙烯性不飽和單體混合物‘加直 價金屬的乙烯性不飽和單體混合物M3。其中 ' 含二 MFDG，於製造例M2中使用ΡΚΑ5001，於制L ’代替 使用心 於製造例吣中 [表1] 添加量(重量比) ~~~ ---~~-- 金屬含量 (wt%) 濃度 MAA AA ZnO 水 柯赫酸 乙醆 製造例Ml 43 36 41 5 16.2 (Wt%) 54 8 製造例M2 30 25 41 53 14.1 59 7 製造例M3 39 32 41 6 16.5 55.0 [製造例Ρ1] 於具備攪拌機、溫度調整機以及滴加裝置的反應容器 中，添加MFDG(二丙二醇單曱醚)25.9份，一邊授拌一邊 升溫至130。(：。 <步驟1> 其後，用1小時勻速滴加包含下述原料的混合物，進 而進行0.5小時共聚合反應（以下將該反應步驟稱為步驟 1)。 丙烯酸(AA)1份 30 201122063. nujpif.doc 丙烯醆乙酯(EA)14份 鏈轉移劑（商品名：rN〇fmerMSD」，日本油脂公 製造)0.5份 起始知彳（商品名：「PerbutylO」，曰本油脂公司製造)ι <步驟2> 其人用3小時勻速滴加包括下述原料的現合物，進 步進行0.5小時共聚合反應（以下將該反應步驟稱為步驟 含二價金屬的乙烯性不飽和單體混合物Mi 9.1份(含 一仏金屬的乙烯性不飽和單體固體成分為5份） 曱基丙烯酸曱酯(MMA)25份 丙烯酸乙酯(EA)45份 丙烯酸正丁酯(ΒΑ)1〇份 曰本油脂公司 鏈轉移劑(商品名：「NofmerMSD」 製造)1份 起始劑(商品名：「Perbutyl〇」，日本油脂公司製造)5 份0 其次’添加「Perbutyl 〇」〇.5份’進而繼續進行卜】、 時聚合反應。進而降溫至8(rc，添加二曱基乙 (DMEA)1.H分，混合至均勻為止，然後緩慢添加土 9=:分，獲得聚合物⑷水分散體ρι。將各原料的 聚合物㈧水分散體P1 @特性值、儲存穩定性示 1 [製造例P2〜製造例P12] '衣2 ° 201122063 yyrv/w_pii_cioc 利用與製造例PI相同的方法，以表2所示的添加量 來製造聚合物(A)水分散體P2〜聚合物(A)水分散體pi2 f 其中，於製造例P7中，步驟1結束後’添加氫氧化 鋅7.1份以及柯赫酸7份並攪拌2小時，其後繼續進行步 驟2。製造例P7中的含二價金屬的乙烯性不飽和單體 的使用量是以如下方式來計算。 自AA除去氫原子所得的分子量：71 自柯赫酸除去氫原子所得的分子量：174 氫氧化辞的式量(formula weight) : 99.4 鋅原子量：65.4 AA 部分：7.6 份χ71/72 = 7.49 份 虱氧化辞部分：7.1份χ65.4/99.4 = 4.67份 柯赫酸部分：7份χ174/175 = 6.96份 7.49 + 4.67 + 6.96= 19.12。 又，於製造例Ρ8中，進行與製造例ρι相同的步驟戈 後’進-步添加經基官能性交聯劑（商品名：「Bayhydu ’Bayer公司製造)7份，於該狀態下繼續翻 2小時而獲得聚合物(A)水分散體p8。 減造例P10中’不進行步驟2，而是使含有， 不飽和單綱以及含二價金屬的乙細 飽和早體齡物_的單舰合物細—階段的聚合。 32 201122063. j j^+ujpif.doc [表2] 步驟 製造例 P1 P2 P3 P4 P5 P6 P7 P8 P9 P10 ΡΠ P12 初期投入稀釋劑 MFDG 25.9 21.8 20 20 20 20 20 21.8 21.8 30 21.8 初期投入反應性稀釋劑(a4) PKA5006 20 步驟1 含二價金屬的乙烯性不飽和 單體(al) 混合物4 Ml 10 Π8.2) M2 20 (33.5) 含羧基的乙烯性不飽和單體 (a2) MAA 6 6 6 AA 1 2 5 7.6 2 2 10 含羥基的乙烯性不飽和單體 (a3) PKA5001 13.5 13.5 其他乙烯性不飽和單尬 (a4) MMA 10 10 20 EA 14 13 31.5 32.4 12 58 13 5 BA 9 9 5 10 10 9 10 SR10 3 起始劑 Perbutyl 0 1 1 1 1 1 5 5 1 1 5 1 1 鏈轉移劑 Nofmer MSD 0.5 0.5 0.5 0.5 0.5 1 1 0.5 0.5 1 0.5 0.5 進行反 應的化 合物 氫氧化鋅 7.1 柯赫酸 7 步驟2 含-價金屬的乙烯性不飽和 單體(al) 混合物^ Ml 5 (9.1) 10 (18.2) 10 (18.2) 10 (18.2) M2 20 (33.5) 30 (50.3) 20 (33.5) M3 15 (27.3) 含羧基的乙烯性不飽和單體 (a2) MAA 6 6 含羥基的乙烯性不飽和單體 (a3) HEA 3.5 PKA5001 13.5 20.3 13.5 AG 12.3 其他乙烯性不飽和單體 (a4) MMA 25 20 10 10 10 20 30 20 EA 45 45 31.5 24.7 22.7 28 45 45 45 BA 10 10 10 10 10 9 9 10 10 10 10 起始劑 Perbutyl 0 5 5 5 5 5 1 5 5 5 5 鏈轉移劑 Nofiner MSD 1 1 1 0.5 0.5 1 1 1 所添加的DMEA 1.1 2.1 5.3 5.3 5.3 5.3 5.3 5.3 2.1 2.1 10.6 所添加的去離子水 92.2 92.2 102.2 102.2 122.2 102.2 99.6 110.8 92.2 92.2 92.2 92.2 羥基官能性交聯劑 VPLS2336 7 各原料((al)〜(a4)) 使用量(wt%) al 5.0 10.0 20.0 30.0 15.0 20.0 19.1 20.0 10.0 10.0 0.0 10.0 a2 1.0 2.0 6.0 6.0 5.0 6.0 6.0 6.0 0.0 2.0 2.0 10.0 a3 0.0 0.0 13.5 20.3 12.3 13.5 13.5 17.0 0.0 0.0 0.0 0.0 a4 94.0 88.0 60.5 43.7 67.7 60.5 61.4 57.0 90.0 88.0 98.0 80.0 聚合物 (A)水分 散體 特性值 黏度 (mPa.s) 2000 1700 1200 800 1500 1700 1100 1000 1300 12400 2000 10200 固體成分 (wt%) 45.3 45.8 45.1 45.4 44.9 45.4 44.6 45.4 45.0 45.5 45.1 45.8 聚合物金 屬量 (wt%) 1.5 2.9 4.7 7.1 4.5 4.7 4.7 4.4 2.9 2.9 0.0 2.9 儲存穩定性評價 3天後 〇 〇 〇 〇 〇 〇 〇 〇 〇 Δ 〇 〇 10天後 〇 〇 〇 〇 〇 〇 〇 〇 〇 △ 〇 〇 1個月後 〇 〇 〇 △ 〇 △ △ 〇 〇 X 〇 〇 33 201122063 , 〜…叩ii.doc PKA5006 :曱氧基聚乙二醇烯丙醚（商品名：「Uniox PKA5006」，日本油脂公司製造） PKA5001 :聚乙二醇烯丙醚（商品名：「Uniox PKA5001」，日本油脂公司製造） AG:乙二醇烯丙醚（日本乳化劑公司製造） SR10 ：「Adeka Reasoap SR10」（ADEKA 公司製造） *括弧内為僅單體成分的重量份 [實例1] 對222.2份的製造例P1中獲得的聚合物(A)水分散體 P1混合30份的水，而獲得防污塗料用樹脂分散體。將各 原料的調配量以及所獲得的防污塗料用樹脂分散體的消耗 度試驗、财水性試驗及網格剝離性試驗的結果示於表3。 [實例2〜實例9] 與實例1同樣地對製造例P2〜製造例P9製備防污塗 料用樹脂分散體，並進行評價。結果示於表3。 [比較例1〜比較例3] 與實例1同樣地對製造例P10〜製造例P12製備防污 塗料用樹脂分散體，並進行評價。結果示於表3。 34 201122063^ [表3]201122063 -τν-/jjif. Doc 6. Description of the Invention: The present invention relates to a method for producing a resin dispersion for an antifouling coating using a resin containing an aqueous dispersion metal. More specifically, the present invention relates to a method for producing a resin dispersion for an antifouling coating which can form a coating film for preventing sea creatures and seaweed from adhering to underwater structures, fishing nets, and ship bottoms. [Prior Art] A coating film formed of an antifouling paint exhibits an antifouling effect by being eluted into the sea by the antifouling agent component contained therein. When the coating film formed by the disintegrating antifouling paint using the rosin-based compound is immersed in the sea for a long period of time, the elution component gradually decreases, and the insoluble component gradually increases. Therefore, the coating film surface is uneven. The effect of preventing the adhesion of organisms such as sea creatures is significantly reduced. On the other hand, the coating film formed by the self-polishing antifouling paint is characterized in that the surface of the coating film is gradually surface-renewed (self-polishing), and the antifouling component is always exposed on the surface of the coating film to exert a long-term antifouling effect. . However, these coatings contain a large amount of various organic solvents such as dimethyl benzene or alcohol, and various alternatives are being studied due to the problem of volatile organic compounds (V〇latile 〇rganic C〇mp〇un(j, vqc) in recent years. Antifouling paints of these antifouling paints. As a self-polishing antifouling paint, for example, Patent Document 1 discloses an antifouling paint composition containing a resin composition as a vehicle liquid (v eh丨c 1 e). The resin composition includes a resin having a metal atom-containing group at a terminal portion of a side chain, and 'as a metal atom, zinc (Zn), copper (Cu), and lanthanum (Te) are described. Jj^tu^pif. Doc Patent Document 2 proposes a composition comprising a divalent gold-containing antifouling coating composition and further containing a compound (IV). As the hydrazine, the water, and the test compound, the town _, _) is contained in the test, and the metal is contained in the test article. It contains bismuth and amine. Further, the monomer of the polymerizable monomer of the metal is contained in the bivalent content in Patent Document 3, and the right one is in the right. And get a waiter. And a divalent metal derived from a divalent metal containing a divalent metal, and Cu, Zn, Mg, and (/a known aqueous dispersion) are described. As a description, the upper linoleum 7Jc is residual and is available in the literature 3 A mixed solution of the I agent and the organic solvent is subjected to solution polymerization, and is obtained by nucleolining, _ and nuclear bonding. Patent Document 4 proposes an aqueous antifouling coating containing a recording base for a resin molecular towel. And/or gold __, and the fine a acid value obtained by emulsion polymerization is 1 〇 mg K 〇 H / g ~ lion mg K 〇 H / g of the aqueous resin minus, and if necessary, containing Wei And an aqueous metal complex of a metal having a divalent or higher metal content, and Cu, Zn, Ca, Mg, Zr, and Fe are described as the metal. Patent Document 5 proposes an aqueous resin emulsion as an antifouling property. An aqueous antifouling resin composition formed by a binder, wherein the aqueous resin emulsion is formed by dispersing a resin having an acid value of 1 〇 mg KOH in the molecule and/or between molecules using an emulsifier. Carboxyl groups and divalent metals in matrix resin of /g~300 mg KOH/g When the ratio reaches zero. Metal carboxylate structure formed by the method of 1 to 5 5 201122063. Jj'tujpif. In the tree m of the doc, the divalent metal is described as cu, zn, and ca. [PRIOR ART DOCUMENT] s [Patent Document] Patent Document 1] Japanese Patent Laid-Open No. 62-57464 [Library Document 2] Japanese Patent Special Publication 3 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2007-23243 [Patent Document 4] Japanese Patent Laid-Open Publication No. Hei. No. Hei. In the state in which the antifouling paint described in Patent Document 1 is surface-dissolved in the state of the organic solvent (fourth), it does not satisfy the wateriness desired in recent years. The fabric of the water-based antifouling coating of Patent Document 2 contains a compound which is coordinated, and the recording compound remains in the coating, and the water resistance t is a problem, and the adhesion of the coating film is problematic. The water-based antifouling paint with low patent reading 3 makes the emulsifier as the mound unit, so the oxidized stretched wire derived from the emulsifier (alkyte ... coffee _ +, material (10) in the test film for the water of patent document 4 Antifouling coating, divalent metal-containing monomer component introduced into the resin during polymerization == When the aqueous metal complex of the ruthenium acid and the metal and the basic compound is mixed, the compound remains in the coating film, and the film is coated. There is a problem in the adhesion between the water resistance and the long-term antifouling coating film. The aqueous antifouling resin composition of Patent Document 5 is dissolved in xylene 201122063. In an organic solvent such as butyl acetate or the like, an emulsifier is added and diluted with water to form a forced emulsification. The resin component is easily precipitated, and the aqueous layer and the resin-containing layer are separated from each other during storage. There is a problem with the storage stability. SUMMARY OF THE INVENTION An object of the present invention is to provide a resin dispersion for an antifouling coating having self-lubricating properties which is excellent in storage stability and water resistance in seawater, and which exhibits an antifouling effect for a long period of time and is excellent in adhesion. The method for producing a resin dispersion for an antifouling coating of the present invention comprises the steps of producing a monovalent metal-containing polymer (A), and dispersing the polymer in a water-containing or water-soluble/organic dissolved gas-containing medium-sized tissue towel. The method for producing a resin dispersion for an antifouling coating is characterized in that the divalent metal-containing polymer (A) is a B-valent metal containing divalent metal in an amount of 1% by weight to 4% by weight. I am a monomeric (al), 〇~8 fu-containing ethylenically unsaturated monomer (a2), G~40 wt% of a trans-group-containing ethylenically unsaturated monomer (a3) and 99 wt %~22 wt% of other ethylenically unsaturated monomers (IV) A polymer obtained by multistage polymerization of two stages or more. [Effects of the Invention] According to the present invention, it is possible to provide a resin dispersion for an antifouling coating having self-lubricating properties which is excellent in storage stability and water-saving property in seawater, and which can exhibit long-term effects and excellent adhesion. The above and other objects, features, and advantages of the present invention will become more apparent from the description of the appended claims. It. Doc 201122063 [Embodiment] The method for producing a resin dispersion for an antifouling coating of the present invention comprises the steps of producing a monovalent metal-containing polymer (A), and dispersing the polymer in a water or water/organic solvent mixture The step of dispersing the medium, the method for producing the resin dispersion for an antifouling coating is characterized in that it comprises - containing divalent gold (four) 'G~8 wt% of a _(tetra)-containing unsaturated monomer (a)~ 40 wt% of a polymer containing a erythridene-based unsaturated monomer (IV) and another ethyl ethoxylate unsaturated monomer (a4) having a enthalpy of 2 to 22 Wt% as a solution obtained by solution polymerization of a two-stage or more household phase . [Ethylene-unsaturated monomer (ai) containing one or four shell metals] Ethylene read and monomer (al) containing dibeite metal used as a kind of raw material in the case of the polymer (A) The amount is set to a range of = wt/0 to 40 wt% with respect to the total amount of (al) to (a4) used as the polymerization material. The reason for this is that, by the amount of the divalent metal-containing ethylenically unsaturated monomer (al): the formed coating film is imparted more excellently from ===:== and the amount of _(10) is preferably greater than or equal to 5^^= and monomer ra] hedan--so, the ethylene of the valence metal is not full: i; equal to 4 ° · adhesion and hydrolysis of the ancient I, t period of self-grinding 'anti-fouling effect Step-by-step small: The amount of d = ethylenically unsaturated monomer (ai) is preferably f at 25 Wt% 'more preferably less than or equal to 20 wt%. 3 - the valence metal of the ethylenically unsaturated monomer (four) is with the divalent gold 8 201122063. joHujpif. Doc is a monomer for ionic bonding tempering', preferably a divalent metal-containing ethylenically unsaturated monomer (ala) having two unsaturated groups, and/or the following general formula (I) A monovalent ethylenically unsaturated monomer (alb) containing a monovalent metal. CR2=C(Kl)-COO-U-R2 (1) (In the formula (I), 'M represents a divalent metal, R1 represents a hydrogen atom or a fluorenyl group, and R2 represents an organic acid residue) from the viewpoint of solubility in water. The metal of the divalent metal contained in the divalent metal-containing ethylenically unsaturated monomer (al) is preferably at least one selected from the group consisting of Mg, Ca, Zn, and Cu. metal. From the viewpoint of the transparency of the obtained polymer (A), Mg, Ca, Zn, and more preferably Zn are more preferable. One type of the above metals may be used, or two or more types may be used in combination. Examples of the monomer (ala) include magnesium acrylate [(CH2=CHCOO) 2Mg], magnesium methacrylate [(CH2-C(CH3)COO) 2Mg], and acrylic acid! 丐 [(cH2=CHCOO) 2Ca] , calcium methacrylate [(CH2=C(CH3)COO)2Ca], zinc acrylate [(CH2=CHCOO)2Zn], zinc methacrylate [(CH2-C(CH3)COO)2Zn], copper acrylate [(ch2=cHCOO)2Cu], (mercapto)acrylic acid bis[beta metal salt] such as copper methacrylate [(CH2=C(CH3)C00)2Cu]. The above monomers (ala) may be appropriately selected from one type or two or more types as needed. Among them, when zinc (meth) acrylate is used, the transparency of the polymer (A) obtained by solution polymerization becomes high, and the coating film of the antifouling paint is 201122063. Jj*^ujpif. Doc The tendency of the color tone to become beautiful, so it is better to refer to: "acrylic acid" or "A second" & "(meth)acrylic acid" fish carp to obtain an inorganic metal compound saturated monomer by the following method (For example, a (10) m(10) acid) agent or a reactive reactant such as a silky money and a base may be compatible with money or other monomers (IV), and the polymerization may be carried out as it is pure. The above reaction is carried out in the presence of water, and it is preferred to set the content of water in the reactant to a range of 001 wt% to 3 〇 wt%. The organic acid residue of R2 of the above monomer (alb) may, for example, be monoacetic acid, monofluoroacetic acid, acetic acid, propionic acid, octanoic acid, versatic acid, isostearic acid or palmitic acid (palmitic). Acid), cres〇tic acid, naphthoic acid, /9-naphthoic acid, alum acid, 2,4,5-trisphenoxyacetic acid, 2,4-diphenoxy A residue derived from a monovalent organic acid such as acetic acid, quinolinecarboxylic acid, nitrobenzoic acid, nitronaphthoic acid or pulvic acid. These residues are appropriately selected as needed, and from the viewpoint of obtaining a coating film having high durability against cracking or detachment for a long period of time, a fatty acid (aliphatic monocarboxylic acid)-based residue, for example, is preferable. A fatty acid residue having a carbon number of 1 to 20. Further, the organic acid residue of R2 in the above formula (I) means a residual portion from which a proton is removed from a carboxyl group of an organic acid, and is ion-bonded to a metal ruthen instead of the proton. Specific examples of the monomer (alb) include monochloroacetic acid (mercapto)acrylic acid, calcium mono(methyl)acrylate, and monochloroacetic acid (mercapto) zinc acrylate, 201122063. jjHujpif. Doc Single gas acetic acid (meth) acrylate; magnesium monofluoroacetate (meth) acrylate, calcium mono(meth) acrylate, zinc monofluoroacetate (meth) acrylate, copper monofluoroacetate Acetic acid (mercapto) magnesium acrylate, calcium (meth) acrylate, zinc (meth) acrylate, copper (meth) acrylate; magnesium propionate (Mercapto) acrylate, calcium (meth) acrylate , propionic acid (mercapto) zinc acrylate, propionic acid (mercapto) copper acrylate; octanoic acid (mercapto) magnesium acrylate, octanoic acid (meth) acrylate, octanoic acid (mercapto) zinc acrylate, octanoic acid (fluorenyl) copper acrylate ; ochreic acid (mercapto) magnesium acrylate, keh acid (mercapto) calcium acrylate, kocholic acid (fluorenyl) zinc acrylate, keh acid (fluorenyl) copper acrylate; isostearic acid (mercapto) acrylic acid Magnesium, isostearic acid (mercapto) calcium acrylate, isostearic acid (mercapto) zinc acrylate, isostearic acid (mercapto) copper acrylate; palmitic acid (meth) acrylate, palmitic acid (mercapto) Calcium acrylate, zinc palmitate (mercapto) zinc acrylate, copper citrate (meth) acrylate; Acid (mercapto) magnesium acrylate, phenolic phenolic acid (mercapto) calcium acrylate, phenolic phenolic acid (mercapto) zinc acrylate, nonylphenolic acid (fluorenyl) copper acrylate; naphthoic acid (mercapto) magnesium acrylate, __naphthoic acid (mercapto) calcium acrylate, α-naphthoic acid (mercapto) zinc acrylate, α-naphthoic acid (fluorenyl) copper acrylate; /3-naphthoic acid (mercapto) magnesium acrylate, naphthoic acid Calcium (meth) acrylate, zinc non-naphthoic acid (mercapto), copper phthalic acid (mercapto), magnesium benzoate, calcium benzoate, benzoquinone Acid (mercapto) zinc acrylate, copper benzoate (meth) acrylate; magnesium 2,4,5-trichlorophenoxyacetic acid (mercapto) acrylate, 2,4,5-trisole phenoxyacetic acid (mercapto) calcium acrylate, 2,4,5-di-gas, lactyl acetic acid (mercapto) zinc acrylate, 2,4,5-triseophenoxyacetic acid (fluorenyl) copper acrylate; 2,4 - dichloro-p-oxyacetic acid (mercapto) magnesium acrylate, 2,4-diphenoxyacetic acid (mercapto) calcium acrylate, 2,4_digas stupidoxyacetic acid if. Doc 201122063 (Mercapto) zinc acrylate, 2,4-diphenoxyphenoxyacetic acid (meth) acrylate; quinoline retinoic acid (methyl) acetophenone oxime, 啥 叛 叛 叛 (曱 )) acrylic acid About, 嗤 缓 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸Zirconium methacrylate (meth) acrylate, copper methacrylate (meth) acrylate, nitro naphthoic acid (mercapto) magnesium acrylate, nitro naphthoic acid (meth) acrylate, nitro naphthoic acid ( Methyl)zinc acrylate, nitronaphthoic acid (mercapto) copper acrylate; prasic acid (mercapto) magnesium acrylate, perrylic acid (mercapto) calcium acrylate, prion acid (methyl Zinc acrylate, copper (meth) acrylate, etc. These monomers (alb) may be appropriately selected from one type or two or more types as needed. Among them, when a zinc-containing monomer is used, the transparency of the obtained resin component becomes high, and the color tone of the coating film becomes beautiful, which is preferable. Further, from the viewpoint of the long-term durability of the coating film, it is more preferable to use a fatty acid (meth)acrylic acid (M of the formula (1) is zinc and r2 is a fatty acid residue). Further, "(mercapto)acrylic acid salt" means "acrylic acid salt" or "methacrylic acid salt". The substance is obtained by reacting an inorganic metal compound, a read group of an ethylenically unsaturated monomer, and a reactive diluent such as a compound (1) === a polymerizable organic (tetra) σ-unsaturated group. . Heart ======= It is preferred to use the above-mentioned monomeric dimer 2 as the monomer (4) (meth)acrylic acid dial as a single (_? fatty acid (methyl) acrylate bismuth ( I) The Μ is zinc 12 201122063^ jpii. A combination of doc fatty acid residues. The ship ^= and _ monomer - and monomer (10) as the divalent metal of the molar ratio of B is the monomer (four) and monomer _ (ala / _ m 丨 1 〇 / 90 ~ 9 _ Scope. By using a more excellent film, 耐' can obtain crack resistance or adhesion equal to, 10/90, / / better. Also, by setting it to be larger than the charm ' can be longer It is preferable to maintain a sufficient self-formation of the formed coating film. (Μ-) is more preferably in the range of face to face, and more preferably in the range of 30/70 to 70/30. ^ contains monomer (10)) Monomer (called monomer mixture can be used by age. The inorganic metal compound, the ethylene-containing compound of the county, and the diluent which is not polymerized in an organic solvent or the like corresponding to the organic acid residue 2 in the formula (1) or has a polymerizable unsaturated group 4 The reaction is carried out in a reactive diluent. It is preferable that the amount of the non-polymerizable organic acid is set to be a range of the amount of the non-polymerizable organic acid to be 1 to 3 times the molar ratio of the metal compound, and the number of the non-polymerizable organic acid is set to 〇. 01 times Mo Er ~ 〇. 95 times the range of moles. When the amount of the non-organic acid used is set to be equal to or greater than _ megamolar, the solid in the monomer mixture production step can be precipitated, and the self-developing crack resistance of the coating film becomes better, so it is good. In addition, when the amount of use of the non-polymerizable soil is set to 3 times or less, the antifouling property of the film can be applied for a longer period of time, which is preferable. The better non-polymeric organic acid is used for 便. 1 times Moer ~ 0. 7 times Moule. Further, as will be described later, even when the polymer (4) is synthesized, it is not made in the raw material. 13 201122063. J-j*Tu^pif. Doc metal #乙婆不 unsaturated monomer (al), also the lower division) ~ (iii) 'and the corresponding unit contains the county's B-contact and monomer (a2) monomer mixture . The material (10) is used as the raw material of the first stage (the polymer obtained by the Cong-Dian Cai Cai reacts with the divalent metal compound, and the divalent metal is introduced into the polymer of the first stage. The presence of the non-reactant Next, the monomer mixture (b3) containing the secreted ethylene) was used as the raw material of the second stage to prepare the polymerization of the second stage. [S-stable ethylenically unsaturated monomer (a])] The amount of the saponin 2) used as a raw material in the preparation of the above polymer (4) is relative to the compound (eight) For the raw materials, the total amount of (al) to (a4) is used (10) wt% and the range of ~8 sides is set. In the aspect where the storage property becomes good, the amount of the ethylenically unsaturated monomer (a2) containing a slow group is preferably equal to or greater than the working amount. Second, the better is greater than or equal to 2 wt%. Further, when the amount of the ethylenically unsaturated monomer (6) containing an ester group exceeds wt%, the viscosity of the polymer becomes extremely high, and the water solubility and adhesion of the coating film are lowered. Qianji's B-heavy and monomer are equal to 7 wt%, and more preferably less than or equal to 6 _. The tert-containing ethylenically unsaturated monomer (8) can be classified into acrylic acid, acrylic acid, butyl ketone, ethene succinic acid, fumaric acid t ic acid (itaC aCld), cis Dimethic acid, methyl cis-butane diacid (10) devaluation 14 201122063 acid), such as monobasic or dibasic acid monomers, maleic acid monomethyl acetate, maleic acid monoethyl ester, cis Butylene succinate, monooctyl maleate ''Ikonic acid monodecyl ester, itaconic acid monoethyl ester, itaconic acid monobutyl vinegar Yan vinegar, antibutmental acid monomethyl hydrazine Purpose, fumaric acid monoethyl ketone, 3 = acid monobutyl ester, fumaric acid monooctyl ester, decyl maleic acid monoethyl ester, tetrahydrophthalic acid mono (indenyl) ) tetrahydrophthalic acid monohydroxyethyl (meth)acrylate > tetragen phthalic acid-decanoic acid (mercapto) acrylic acid via propyl chloroformate mono(meth) acrylate Butyl ester, hydroxyethyl mono(decyl) acrylate, hydroxypropyl mono(meth)acrylate, suecinic add monohydroxyethyl(meth) Ac Rylate), hydroxypropyl methacrylate, hydroxyethyl methacrylate, maleic acid mono(indenyl) acrylate, propyl acrylate, etc. Monoesters of dibasic acids or acid needle monomers, and the like. One or two or more of these monomers may be appropriately selected as needed. [Hydroxy group-containing ethylenically unsaturated monomer (a3)] The amount of the hydroxyl group-containing ethylenically unsaturated monomer (a3) used as one of the raw materials in the preparation of the above polymer (A) is relative to the polymerization. The total amount of (ai) to (a4) used as the raw material of the material (A) is 1% by weight, and is set to a range of 〇40% by weight. Although the hydroxyl group-containing ethylenically unsaturated monomer (a3) is arbitrarily formed, the water resistance of the coating film tends to be improved and the adhesion is improved by setting it to 4% by weight or less. The amount of the hydroxyl group-containing ethylenically unsaturated monomer (a3) is more preferably 30% by weight or less, and even more preferably 15 201122063 20% by weight. Examples of the 2-hydroxy group include: (fluorenyl)-hydroxypropyl ester, (meth)acrylic acid 1-propyl ester, and (meth)acrylic acid 3·butyl vinegar-containing sulfhydryl group _-propyl _ _ 2· An adduct of vinegar and ethylene oxide oxime monomer; (meth)acrylic acid vinegar, etc., a dimer or a trisole of _(meth)acrylic acid 2-hydroxynecholine = hexamethylene di-2-hydroxypropyl ester a polymer; a monomer having a plurality of radicals of di(meth)acrylic acid; a substrate of ethyl acetoacetate; a ^^^^^, an allyl ether, a propylene glycol allyl ether, The end of the ether, polypropylene glycol ene ether, etc., the propylated polyfluoride monomer = a _ selected one or more of the monomers, and appropriate and appropriate [other ethylenic unsaturation Monomer unit (a4) The amount of the ethylenically unsaturated monomer (IV) used as the raw material in the preparation of the above polymer (4) is the amount of (a 1) to (a4) used for the flat raw material. (A) The range of pain ~ heart% ^ 1〇〇Wt% is set to 99. ^ and monomer (4) as long as it is with the above-mentioned divalent metal containing "double phase" difficult to no special H compound (A) contains the source: octaethyl ethylenically unsaturated monomer (a4) single ', flexibility or Resistance to cracking. Peeling resistance and long "self-grinding: good balance, and can make these characteristics good. 201122063. j j^tu^pif. Doc Other ethylenically unsaturated monomers (a4) may be exemplified by decyl (meth) acrylate, ethyl (meth) acrylate, 2-methyloxyethyl (meth) acrylate, (decyl) propyl Diluted acid 2-ethoxyethyl acetonate, butoxyethyl (meth)acrylate, butoxydiethanol (mercapto) acrylate vinegar, decyloxytriethylene glycol (meth) propylene Acid bismuth, decyloxypolyethylene triol (methyl) propyl m m (mercapto) acrylic acid phenoxyacetic acid, (mercapto)acrylic acid 2_(2-ethylhexyloxy) acetoacetate, Mercapto) 1-mercapto-2-methoxyethyl acrylate, 3-hydroxybutyl (meth) acrylate, 3-mercapto-3-methoxy butyl (mercapto) acrylate Vinegar, (mercapto) methic acid m-methoxy benzene vinegar, (meth)acrylic acid p-methoxy phenyl vinegar, (mercapto) acrylic acid o-methoxy phenyl ethyl ester, / methyl acrylate Methoxyphenylethyl ester, p-nonylphenylethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (mercapto) acrylate , (butyl) (meth) acrylate, (2) butyl acetonate, 2-ethylhexyl (meth) acrylate, (A) ) lauryl acrylate, stearyl (meth) acrylate, beheny Kmetyaciry late, (mercapto) acrylate, (mercapto) acrylic acid, (mercapto) acrylic acid Isoprene (meth)acrylate, (cyclo)cyclohexyl acrylate, glycidyl (meth) acrylate, trifluoroethyl (meth) acrylate, perfluoro(meth) acrylate a (meth) acrylate monomer such as octyl ester; a vinyl precursor containing primary and primary amine groups such as butylaminoethyl (meth) acrylate, (meth) acrylamide, etc., (meth) propyl Dilute dimercaptoacetate, diethylaminoethyl (meth) acrylate, dimethyl propyl propyl (decyl) acrylate, didecyl butyl acrylate Tertiary amino acid-containing dibutylaminoethyl acrylate, didecylaminoethyl (fluorenyl) acrylamide, dimethylaminopropyl (meth) acrylamide, etc. Ethylene monomer; Ethylene 17 ii: doc 201122063 base scale fine, B-rated, vinyl material, heterogeneous monomer; phenelzine, ethylene, stupid, Ethyl phenyl hydride, , nitrile thioglycolonitrile, vinyl acetate vinegar, ethyl vinegar propionate, etc.: ethoxylated propylene glycol, decyl propylene glycol allyl ether 1. Lacto-based polyethylene glycol dilute _, butoxy polypropylene glycol dilute propyl ether, methoxyox X-ethyl alcohol, polypropylene glycol propylene butyl scale, butoxy polyethylene glycol. Polypropylene glycol propylene scales, etc., end-filament-propylated (tetra) monomer; ethylene glycol bis(methacrylic acid H-ethylene glycol di(meth)acrylic acid vinegar, triethylene glycol ^: rim, polyethylene glycol Di(methyl)propene-roasted acid, M-butanediol di(A: acrylate, 1,6-hexanediol di(meth) propylene _, neopentyl glycol di(曱: propylene H 1 ' 9·decanediol di(methyl)propionic acid g, • decanediol di(methyl)propene axis, tris-methyl propyl tris(meth)acrylic acid I 戍 I propyl HH) propylene Acidic §1, dipentaerythritol hexa(meth)acrylic acid, 甲2 = Qiao: isotrimer acid triene propylene vinegar, cis-succinic acid di: + = & The body can be appropriately selected and used in a variety of types or two or more. Depending on the ^ ' can also make the emulsified _ _ other non-saturated single work:: emulsifier acts as an emulsifier in the polymerization reaction, The structure in which the n-body is finely copolymerized to form the obtained copolymer, and the structure-integrated pure (A)-inducing reactive emulsifier, the unit derived from the reactive ritual agent contributes to the improvement of dispersibility. Can use carbon with free silkiness Double = ~ 〇 surfactant, preferably, can be ❹ "raw carbon double bond (c, non-ionic surfactant or anion j 201122063 ^ surfactant). Again, this reactive emulsification For example, "Aqualon HS-05" manufactured by Japan Emulsifier Co., Ltd., "Aqualon HS-05" manufactured by First Industrial Pharmaceutical Co., Ltd., "Aqualon HS-10", "Aqualon HS-20", and "Adeka Reasoap SE10" manufactured by ADEKA Corporation. "Adeka Reasoap SR10", "AdekaReasoap SR20", an anionic reactive emulsifier such as "Eleminol JS2" manufactured by Sanyo Chemical Industries Co., Ltd.; "Aqualon RN·1 〇" and "Aqualon RN-20" manufactured by Daiichi Kogyo Co., Ltd. "Aqualon RN-30" is a non-ionic reactive emulsifier such as "Adeka Reasoap NE10", "Adeka Reasoap NE20", "Adeka Reasoap NE30", and "Adeka Reasoap ER10" manufactured by ADEKA. The emulsifier may be appropriately selected to use one or two or more kinds as needed. π 3 F process & unsaturated unsaturated steroid (a3) or other ethylenically unsaturated monomer (IV) may be combined with (fluorenyl) propyl The acid vinegar monomer is compared with the allylate (4) monomer lacking free radical polymerizability as a bivalent metal-containing ethylenically unsaturated monomer (8), and the polymer (A) is synthesized as a reactive thinner. When the divalent metal-containing ethylenically unsaturated monomer (6) is synthesized, or the polymer (4) is slanted, the organic solvent is dissolved as a reaction medium into the reaction vessel, by using the above-mentioned propylated polycondensate It can improve the storage stability and reduce the amount of solvent required for the storage. Further, [Polymer] Resin dispersion for antifouling coating manufactured by the method of the present invention 201122063. . j^-rw^yif. Doc The above (al) to (10)) monomers are obtained in two or more stages. The four compounds (eight) are obtained by first: making the "" portion of the (4)) to (a4) monomer which is sir. The first stage polymerization was carried out in the presence of a polymerization initiator in the dissolved polymer (4), two persons. The remaining part/minute of the above (al) to (a4) monomers is preferably after the second stage. From the viewpoint of storage stability, the above polymer (A) ":::::::::::;! monomer mixture (bl) 'two == alkene: := have, the woman The step of dissolving = δ is carried out by a monomer mixture containing a bis-unsaturated mono-(). (al) It is preferred that (al = using this multi-stage polymerization method, in the polymer: guide ^ =: =: qualitative, the water resistance of the coating film is improved, made into water dispersion, body and mind ( The order of polymerization of M) and (4) is not limited. In the case of the polymer::, when the compound is combined, there are two =: = the stability of the silk is reduced due to the rotation of the silk material (4). The heart is less than the liquid syrup obtained by polymerization: to make at least one species containing the county's ethyl unsaturation; 20 201122063. j j*Tu^pif. The doc compound (M) is subjected to a first-stage polymerization of solution polymerization; a step of reacting the obtained polymer with a divalent metal compound, and containing at least one carboxyl group in the presence of the above-mentioned step_reactant The n-th polymerization of the polymerization of the ethylenically unsaturated monomer. Into the ethylene: ^ Ϊ 5 2 to facilitate the raw materials do not use the above-mentioned divalent metal obtained == gold in the guidance ^ contains two fine B_ money and monomer (4) compound can =;: r: 6r_ into gold This special _ flat _G5 compliant bulletin or line. Specifically, a known method of the first money can be carried out by adding a metal oxide, a divalent metal, and a valence organic acid or water at a temperature equal to or lower than the degree of the dish. Alternatively, the diluent used in the above polymerization reaction is disintegrated; dimethyl alcohol, n-propanol, iso = specific: different r: second butanol, 2-butanol, 2-decyloxyethanol, 3_ : iso-alcohols 'ethylene glycol, 1,2·propylene glycol, 13 earth oxyethylene glycol, 2-methyl-2,4-pentylene glycol, 2 'T —' 2'3_butyl Ethers such as diol, diethylene glycol, dipropylene glycol Λ=κ2,5·hexanediol, 2,4·alcohol, methyl ethyl ketone, B-di; = ether, monooxygen _i_e) Class 'ethylene glycol monomethyl ether A: two: 21 201122063 , "dr v / pi · do c monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether Ethylene glycol monoisobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, propylene glycol monoterpene ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-iso Propyl ether, propylene glycol mono-n-butyl ether, propylene glycol monoisobutyl ether, propylene glycol mono-tert-butyl ether, ethylene glycol diterpene ether, ethylene glycol diethyl ether, propylene glycol dioxime ether, propylene glycol diethyl ether, diethylene glycol monoterpene Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethyl Glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-isobutyl ether, diethylene glycol mono-tert-butyl ether, dipropylene glycol monoterpene ether, dipropylene glycol monoethyl ether, dipropylene glycol single positive Propyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol monoisobutyl ether, dipropylene glycol mono-tert-butyl ether, diethylene glycol dioxime ether, diethylene glycol diethyl ether, dipropylene glycol Glycol ethers such as oxime ether, dipropylene glycol diethyl ether, triethylene glycol monoterpene ether, triethylene glycol monoethyl ether, tripropylene glycol monoterpene ether, tripropylene glycol monoethyl ether, triethylene glycol dimethyl ether, etc. Alcohol monoacetate, ethylene glycol diacetate, ethylene glycol monoterpene ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol monoisopropyl Ether acetate, propylene glycol monoterpene ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, A glycol diol such as dipropylene glycol monomethyl ether acetate or triethylene glycol monoterpene ether acetate, or an aliphatic hydrocarbon such as n-pentane or n-hexane. An aromatic hydrocarbon such as toluene, diphenylbenzene or solvent naphtha, or an allylated polyether monomer. These diluents may be used alone or in combination of two or more. However, it is preferred to contain an alcohol compound because the production stability and water dispersion stability of the polymer (A) are good. Can reduce 201122063. Jj^tu jpif. From the viewpoint of the amount of the organic solvent, it is preferred to carry out the above-mentioned first-stage polymerization as a diluent; the fcffi-propylated poly-slit monomer. The polymerization initiator is not particularly limited, and a known polymerization initiator can be used. For example, t-butyl peroxy-2-ethylhexanoate, di-tert-butyl peroxide, laurel peroxide, benzammonium peroxide, and peroctanoic acid can be cited. Organic peroxide such as butyl ester (t_butyl per〇ct〇ate), 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2-mercaptobutyronitrile XAzobismethylbutyronitrile An Azo compound such as AMBN). The polymerization initiator may be used alone or in combination of two or more. The use of the poly & starter is not particularly limited and can be appropriately set. Further, a known chain transfer agent may be used in the above polymerization reaction as needed. The molecular weight of the polymer (A) obtained in the above manner can be appropriately determined depending on the desired properties, and can be, for example, set in the range of the weight average molecular weight (Mw) of from 10 50,000 to 50,000. [Resin dispersion for antifouling coating] The resin dispersion for an antifouling coating of the present invention can be obtained by dispersing the polymer (A) obtained in the above manner in a dispersion medium containing water or a water/organic solvent mixture. . With respect to the above polymer (A), δ ' is preferably in the presence or absence of a diluent for dissolving the polymer (A) from the viewpoint of smooth movement of the aqueous phase. The saturated monomer (a2) is subjected to solution polymerization and then a part or all of the thiol group in the obtained polymer is neutralized 23 201122063 w —〆it. After doc, it is dispersed in the above dispersion medium. The above neutralization is carried out by adding an inspective compound* to the polymer (A). The test compound to be used is not particularly limited, and examples thereof include ammonia (aqueous solution), alkylamines such as trimethylamine, triethylamine, diisopropylethylamine and butylamine, and dimethylethanolamine. Alkanolamines such as dimethylisopropanolamine, methyldiethanolamine, diethylethanolamine, triethanolamine, butanolamine, morpholine, isophoronediamine (is〇ph〇r〇ne dmmine) Wait. The test compound may be used alone or in combination of two or more. The above basic compound is added in such a manner that the degree of neutralization (i.e., the molar ratio of the neutralizing agent to the acid) is from 4% to 15% by weight, preferably from 60% to 120%. The pH of the resin dispersion for an antifouling coating of the present invention is 6. 0~11. 0, preferably 6. 5~9. 0. Further, in the above polymer (A), at least a hydroxyl group-containing ethylenically unsaturated monomer (a3) is used for two-liquid polymerization, and the compound (A) is dispersed in a dispersion medium, and then a hydroxyl group is further added. Functional cross-linking for cross-linking 'toughness. It is preferred because the coating film properties such as water resistance are improved. The hydroxy functional crosslinking agent is not particularly limited, and a known hydroxy functional crosslinking agent can be used. For example, melamine resin (melamine r=sin), alum amide resin (amine tree such as benz〇guanamine, aliphatic isocyanate, alicyclic isocyanate, aromatic isocyanate = I isocyanate, etc.), in particular, reaction temperature From the viewpoint of coating physical properties, I preferably use a polyisocyanate, and more preferably a water-soluble or water-dispersible hydroxy-functional crosslinking agent. The amount of the hydroxy-functional crosslinking agent used is not particularly limited. It is used in a range where the workability, film forming property, and antifouling property are not lowered. 24 201122063 jpif. In terms of film-forming property, the above-mentioned antifouling paint is preferably in the range of from 1 to 60% by weight; = machine soluble === water, organic solvent mixture. The above-mentioned diluent used in the dispersion reaction. In the meantime, the diluent is preferably an alcohol compound such as an alcohol or a glycol ether exemplified as the diluent of the polymerization reaction described above. In the chelate compound, the alcohol can preferably use a carbon having a relatively low boiling point, a carbon having a carbon number of 2 to 4, and a carbon number of 3 Preferably, it is a glycol ether having a carbon number of 3 to 8. The content of the above diluent in the resin dispersion for an antifouling paint is preferably 〇 2 2 GW t %, more preferably (4) secret. #Because the dilution (4) used in the polymerization of the polymerization product (4) exceeds the above range 々 'When the amount of the agent is reduced, the diluent may be removed by vacuum distillation as needed. Removal operation (desolvation treatment). The anti-fouling coating resin dispersion of the present invention may be formulated with other antifouling agents as needed. The antifouling agent may be appropriately selected according to the required properties. Examples thereof include a copper-based antifouling agent such as cuprous oxide, cuprous thiocyanate, and copper powder, and a compound of another metal such as a wrong metal or nickel, an amine derivative such as diphenylamine, or a nitrile. A compound, a benzothiazole compound, a maleimide compound, a pyridine compound or the like. These antifouling agents may be used singly or in combination of two or more. More specifically, it can be exemplified by manganese ethylene bis (dithiocarbamate) and dimethyl dithioamine 25 rit. Doc 201122063 zinc dimethyl dithiocarbamate, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine (2-methylthio-4-t-butylamino-6) -cyclopropylamino-s-triazine), 2,4,5,6-tetrachloroisophthalonitrile, 2,4,5,6-tetrachloroisophthalonitrile, hydrazine, dimethyl dimethyl phenyl urea, s Zinc (dithiocarbamic acid) zinc, copper thiocyanate, 4,5-digas·2-n-octyl-3(2H)isoindoline (4,5- Dichloro-2-n-octyl-3(2H)-isothiazolone), N-(fluorodichlorosulfanyl) phthalimide, N,N'-didecyl-Ν'-phenyl-( N-N,-dimethyl-N,-benzyl-(N-fluorodichloromethylthio)sulfa mide, 2-n-specific thiol-1-oxide zinc salt 2-pyridinethioM-〇xide zinc salt), tetramethylthiuram sulfide, Cu-10%Ni solid solution alloy, 2,4,6-trisylphenylbutyleneimine, 2,3,5,6-tetrachloro-4-(indolylsulfonyl)pyridine, 3-iodo-2-propenylbutylcarbamate, Deuterated toluene (diiodomethyl-p-tolyl sulfone), bis(dimethyldithiocarbamoyl) zinc ethylenebis (dithiocarbamate), phenyl (di(dithiocarbamoyl)) Phenyl(bispyridyl)bismuth dichloride, 2-(4-°塞零坐基)- 2-(4-thiazolyl)-benzimidazole, ° More than pyridine-triphenylborane and the like. In the resin dispersion for an antifouling coating of the present invention, it can also be applied to the coating film 26 201122063. Jjiwjpif. The doc compound such as dimethyl siloxane or silicone oil is blended with a fluorinated compound such as fluorinated carbon such as dimethyl siloxane or silicone oil for the purpose of imparting lubricity and preventing bio-adhesion. Further, the resin dispersion for an antifouling coating of the present invention may contain various pigments, antifoaming agents, pigment dispersing agents, flow leveling agents, anti-sagging agents, matting agents, ultraviolet absorbers, antioxidants, heat resistance enhancers, and assistance. A lubricant, a preservative, a plasticizer, other emulsion resins, a water-soluble resin, a viscosity control agent, and the like. The coating film using the resin dispersion for an antifouling coating of the present invention can be formed directly or through a primer film on water structures such as ships or various fishing nets, harbor facilities, oil fences, bridges, and seabed bases. The surface of the substrate. The above primer film can be formed by using a priming primer (wash prime = glue or epoxy (4) primer, towel coating (intennediate e (10)), etc. Regarding the coating method, the brush coating, spray cooling The method of cloth coating, coating application, immersion coating, etc. will be carried out on the underlying coating film on the substrate, coated with two drying materials, and placed under the dish, and may be heated and dried. EXAMPLES: 伯太=1' The present invention will be described in more detail by way of examples and comparative examples. Weight: No part of the list of the examples is the evaluation of the resin dispersion for the smudge coating shown below [ Evaluation of storage stability] 27 201122063, Evaluation of storage stability of resin dispersions for coatings Γ: The Γ dispersion was stored at a temperature of 4 ° C for 3 days, and was allowed to proceed. The presence or absence of Shen Lin. The evaluation is based on the following base ingredients: (10). Recorded, there is no small amount of sediment, but the sediment is dispersed by stirring. X: Resin component ship. Separation, solidification occurs, even if it is dispersed. [Evaluation of the consumption of the coating film] Using an applicator 'The stalk __ is divided into 4 以 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The 'making slabs, the test board was worn in a rotary drum set in seawater to 7. The peripheral speed of 7 m/s (15 knot) was rotated, and the film thickness after 1 month and 3 months was measured. [Water resistance test] A test plate was prepared by applying a resin dispersion for an antifouling coating to a substrate including a sandblasted steel sheet coated with a rust preventive paint in a dry film thickness of 120. After the test plate was immersed in sterilized seawater for 1 month, the test plate was dried at room temperature of 20 ° C for 1 week, and the surface of the coating film was observed. The evaluation was carried out in accordance with the following criteria. ◎: Cracks and peeling were not observed at all. 〇: Cracks were observed slightly 28 201122063. j^^tujpif. Doc Cracks and peeling were observed in the surface of the coating film. Cracks and peeling were observed on the entire surface of the coating film. [Grid stripping test] Sea J ί soil? The test piece prepared in the same manner as in the water repellency test was subjected to a mesh peeling test at room temperature of 2Qt>c under the sterilization filtration under the condition of "?". In the mesh peeling test, the cut):: cross-cutting until the substrate is separated (_ 挪 i 诚 i y mm grid) attached to the top of the Sell_e (Note ^ sharply peeled off, observe The peeled mesh was performed according to the following criteria: 〇Δ ◎: The peeling of the mesh and the peeling mesh of the mesh corner were not observed at all, but only the corners of the mesh were peeled off by 1 to 12 mesh peeling X: 13 to 25 mesh peeling. [Production Example M1] In a reaction vessel equipped with a scrambler, a temperature adjuster, and a dropping device: 'Add MFDG (dipropylene glycol monomethyl) 66 3 parts and zinc oxide (Zn〇) 4i ^ ' - while stirring - while raising the temperature to 75t:. To this, 帛 3 hours sentenced to add a mixture containing the following materials. Mercaptopropionic acid (MAA) 43 parts of acrylic acid (AA) 36 parts After the completion of the dropwise addition of 5 parts of water, the reaction solution changed from a milky white state to a transparent state. After stirring for 2 hours, 1 part of MFDG was added to obtain a transparent y 2 29 201122063. ^v/^pif. Doc valence metal ethylenically unsaturated monomer mixture Ml. The amount of each, and the amount of the obtained metal content of the divalent metal-containing ethylenically unsaturated monomer and the solid content concentration are shown in Table 1. & M1 [Production Example M2, Production Example M3] An ethylenically unsaturated monomer mixture containing a divalent metal was produced by the same method as in Production Example M1. Body mixture M3. Where 'containing two MFDG, ΡΚΑ5001 is used in the production example M2, and L' is used instead of the core in the manufacturing example [Table 1] Adding amount (weight ratio) ~~~ ---~~-- Metal content (wt %) Concentration MAA AA ZnO Water acetyl acetophenone production example Ml 43 36 41 5 16. 2 (Wt%) 54 8 Manufacturing example M2 30 25 41 53 14. 1 59 7 Manufacturing example M3 39 32 41 6 16. 5 55. 0 [Production Example 1] MFDG (dipropylene glycol monoterpene ether) was added to a reaction vessel equipped with a stirrer, a temperature adjuster, and a dropping device. 9 parts, warmed to 130 while mixing. (:. <Step 1> Thereafter, a mixture containing the following raw materials was dropwise added at a constant rate for 1 hour, and then a copolymerization reaction was carried out for 0.5 hours (hereinafter, this reaction step is referred to as Step 1). Acrylic acid (AA) 1 part 30 201122063. nujpif.doc Acryl oxime ethyl ester (EA) 14 parts chain transfer agent (trade name: rN〇fmerMSD), manufactured by Nippon Oil & Fat Co., Ltd. 0.5 part of the original knowledge (trade name: "PerbutylO" , manufactured by Sakamoto Oil Company) <Step 2> The person invented the present compound including the following raw materials at a constant rate for 3 hours, and progressed for 0.5 hours of copolymerization (hereinafter, this reaction step is referred to as a step of a divalent metal-containing ethylenically unsaturated monomer mixture). Mi 9.1 parts (5 parts of solid content of ethylenically unsaturated monomer containing one bismuth metal) decyl methacrylate (MMA) 25 parts of ethyl acrylate (EA) 45 parts of n-butyl acrylate (ΒΑ) 1 〇 This grease company chain transfer agent (trade name: "NofmerMSD") 1 part of the starter (trade name: "Perbutyl", manufactured by Nippon Oil Co., Ltd.) 5 parts 0 Next 'Add "Perbutyl 〇" 〇. 5 copies' Continue to carry out the polymerization reaction, and then cool down to 8 (rc, add dimethyl ethane (DMEA) 1.H, mix until uniform, then slowly add soil 9 =: points to obtain polymer (4) aqueous dispersion ρ 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ Addition amount shown in 2 to produce polymer (A) aqueous dispersion P2 ~ poly (A) aqueous dispersion pi2 f In the production example P7, after the completion of the step 1, 7.1 parts of zinc hydroxide and 7 parts of koco acid were added and stirred for 2 hours, and then the step 2 was continued. Production Example P7 The amount of the divalent metal-containing ethylenically unsaturated monomer used is calculated as follows: Molecular weight obtained by removing a hydrogen atom from AA: 71 Molecular weight obtained by removing a hydrogen atom from kocholic acid: 174 Formula weight: 99.4 Zinc atomic weight: 65.4 AA Part: 7.6 parts χ71/72 = 7.49 parts 虱 虱 虱 part: 7.1 parts χ 65.4/99.4 = 4.67 parts koco acid part: 7 parts χ 174/175 = 6.96 parts 7.49 + 4.67 + 6.96 = 19.12. In the production example 8, the same procedure as in the production example is carried out, and then a radical functional crosslinking agent (trade name: "Bayhydu 'Bayer Co., Ltd.") is added. In this state, the polymer (A) aqueous dispersion p8 was obtained by continuing to turn for 2 hours. In the reduction example P10, 'the step 2 is not carried out, but the unsaturated, mono- and divalent metal-containing ethyl esters are saturated. The single-ship compound of the early age _ is a fine-stage polymerization. 32 201122063. Jj^+ujpif.doc [Table 2] Step Manufacturing Example P1 P2 P3 P4 P5 P6 P7 P8 P9 P10 ΡΠ P12 Initially charged diluent MFDG 25.9 21.8 20 20 20 20 20 21.8 21.8 30 21.8 Initially charged reactive diluent (a4) PKA5006 20 Step 1 Ethylene unsaturated monomer containing divalent metal (al) Mixture 4 Ml 10 Π 8.2) M2 20 (33.5) Carboxylated ethylenically unsaturated monomer (a2) MAA 6 6 6 AA 1 2 5 7.6 2 2 10 Hydroxyl-containing ethylenically unsaturated monomer (a3) PKA5001 13.5 13.5 Other ethylenically unsaturated monoterpenes (a4) MMA 10 10 20 EA 14 13 31.5 32.4 12 58 13 5 BA 9 9 5 10 10 9 10 SR10 3 Starting agent Perbutyl 0 1 1 1 1 1 5 5 1 1 5 1 1 Chain transfer agent Nofmer MSD 0.5 0.5 0.5 0.5 0.5 1 1 0.5 0.5 1 0.5 0.5 Reaction compound Zinc hydroxide 7.1 Koch acid 7 Steps 2 Ethylene-unsaturated monomer (al) mixture containing valence metal ^ Ml 5 (9.1) 10 (18.2) 10 (18.2) 10 (18.2) M2 20 (33.5) 30 (50.3) 20 (33.5) M3 15 ( 27.3) Carboxyl group-containing ethylenically unsaturated monomer (a2) MAA 6 6 Hydroxy group-containing ethylenically unsaturated monomer (a3) HEA 3.5 PKA5001 13.5 20.3 13.5 AG 12.3 Other ethylenically unsaturated monomers (a4) MMA 25 20 10 10 10 20 30 20 EA 45 45 31.5 24.7 22.7 28 45 45 45 BA 10 10 10 10 10 9 9 10 10 10 10 Starting agent Perbutyl 0 5 5 5 5 5 1 5 5 5 5 Chain transfer agent Nofiner MSD 1 1 1 0.5 0.5 1 1 1 Addition of DMEA 1.1 2.1 5.3 5.3 5.3 5.3 5.3 5.3 2.1 2.1 10.6 Deionized water added 92.2 92.2 102.2 102.2 122.2 102.2 99.6 110.8 92.2 92.2 92.2 92.2 Hydroxyl functional crosslinker VPLS2336 7 Raw materials ((al) ~(a4)) Usage (wt%) al 5.0 10.0 20.0 30.0 15.0 20.0 19.1 20.0 10.0 10.0 0.0 10.0 a2 1.0 2.0 6.0 6.0 5.0 6.0 6.0 6.0 0.0 2.0 2.0 10.0 a3 0.0 0.0 13.5 20.3 12.3 13.5 13.5 17.0 0.0 0.0 0.0 0.0 A4 94.0 88.0 60.5 43.7 67.7 60.5 61.4 57.0 90.0 88.0 98.0 80.0 Polymer (A) Aqueous dispersion characteristic value Viscosity (mPa.s) 2000 1700 1200 800 1500 1700 1100 1000 1300 12400 2000 10200 Solid content (wt%) 45.3 45.8 45.1 45.4 44.9 45.4 44.6 45.4 45.0 45.5 45.1 45.8 Amount of polymer metal (wt%) 1.5 2.9 4.7 7.1 4.5 4.7 4.7 4.4 2.9 2.9 0.0 2.9 Storage stability evaluation after 3 days〇〇〇 〇〇〇〇〇〇Δ 〇〇10 days later 〇〇〇〇〇〇〇〇〇△ 〇〇1 month later 〇〇〇△〇△ △ 〇〇X 〇〇33 201122063 , ~...叩ii.doc PKA5006 : Hydroxypolyethylene glycol allyl ether (trade name: "Uniox PKA5006", manufactured by Nippon Oil & Fats Co., Ltd.) PKA5001: Polyethylene glycol allyl ether (trade name: "Uniox PKA5001", manufactured by Nippon Oil & Fats Co., Ltd.) AG: Ethylene glycol allyl ether (manufactured by Nippon Emulsifier Co., Ltd.) SR10: "Adeka Reasoap SR10" (manufactured by Adeka Co., Ltd.) * Parts by weight of monomer components in parentheses [Example 1] Obtained in 222.2 parts of Production Example P1 The polymer (A) aqueous dispersion P1 was mixed with 30 parts of water to obtain a resin dispersion for an antifouling coating. The blending amount of each raw material and the results of the consumption test, the water-storage test, and the mesh peeling test of the obtained resin dispersion for an antifouling coating are shown in Table 3. [Example 2 to Example 9] A resin dispersion for an antifouling coating was prepared and produced in the same manner as in Example 1 except for Production Example P2 to Production Example P9. The results are shown in Table 3. [Comparative Example 1 to Comparative Example 3] A resin dispersion for an antifouling coating was prepared and produced in the same manner as in Example 1 except for Production Example P10 to Production Example P12. The results are shown in Table 3. 34 201122063^ [Table 3]
製造例PI〜製造例P9中所製備的聚合物(A)水分散體 P1〜聚合物(A)水分散體P9的儲存穩定性、即分散穩定性 良好(表2)。又，於儲存了丨個月以上時，雖然產生了一部 分沈澱，但是藉由再次進行攪拌，沈澱樹脂分散。又，使 用聚合物(A)水分散體P1〜聚合物(A)水分散體P9的防_ 塗料用樹脂分散體(實例丨〜實例9)的於海水中的耐水性= 異’且自研磨性、密著性亦良好(表3)。 另一方面，不進行步驟2、而是藉由使單體混合物進 行一階段的聚合而製備的聚合物(A)水分散體p1〇的黏度 極高(表2)，使用聚合物(A)水分散體Pl〇的防污塗料用樹 脂分散體(比較例υ的耐水性、密著性較低'本又，利 35 201122063“ ^^-ru^pii.doc 用不使用含二價金屬的乙烯性不飽和單體(al)而製備的聚 合物(A)水分散體P11的防污塗料用樹脂分散體(比較例2) 並未表現出自研磨性(表3)。又，利用使用1〇 wt%的含綾 基的乙雜不飽和單體(a2)㈣合物(A)水分散體ρι >可塗料關脂分散體(比㈣3)_度極高 性、密著性均較低(表3)。 、衣）且耐水 =本發明已贿錄施_露如上，然其 發明，任何熟習此技藝者，在不脫離本發明乂 和乾圍内，當可作些許之更動與潤飾 精砷 範圍當視後附之中請專利範圍所界 b本㈣之保護 【圖式簡單朗】 ° fel 〇 【主要元件符號說明】The polymer (A) aqueous dispersion P1 to the polymer (A) aqueous dispersion P9 prepared in Production Example PI to Production Example P9 had good storage stability, i.e., dispersion stability (Table 2). Further, when it was stored for more than one month, although a part of the precipitate was generated, the precipitated resin was dispersed by stirring again. Further, the resin dispersion of the anti-coating coating resin (Example 丨 to Example 9) of the polymer (A) aqueous dispersion P1 to the polymer (A) aqueous dispersion P9 was used for water resistance in seawater = different 'self-grinding Sex and adhesion are also good (Table 3). On the other hand, the viscosity of the polymer (A) aqueous dispersion p1〇 prepared by carrying out the polymerization of the monomer mixture in one stage without using step 2 is extremely high (Table 2), and the polymer (A) is used. Resin dispersion for antifouling coating of aqueous dispersion Pl〇 (Comparative example, water resistance and adhesion are low) </ br> <br><br><br><br><br><br> ^^-ru^pii.doc No use of divalent metals The resin dispersion for antifouling coating of the polymer (A) aqueous dispersion P11 prepared by the ethylenically unsaturated monomer (al) (Comparative Example 2) did not exhibit self-polishing property (Table 3). 〇wt% thiol-containing ethylenically unsaturated monomer (a2) (tetra) compound (A) aqueous dispersion ρι > coatable lipid dispersion (ratio (4) 3) _ degree high, low adhesion (Table 3), clothing, and water resistance = the present invention has been smuggled as described above, but the invention, any person skilled in the art, without departing from the invention and the dry circumference, when making some changes and retouching The scope of the refined arsenic is regarded as the scope of the patent. The protection of the scope of the patent (4) is protected [Figure is simple] ° fel 〇 [main symbol description]
Ml t 36Ml t 36