546413 玫、發明說明 (發明說明應敘明：發明所屬之技術領域、先前技術、㈣、實施方式及圖式簡單說明） 【發明所屬之技術領域】 發明領域 本發明有關於7jC性可自動沉積組成物的浸潰應用。 【先前技術】 發明背景 自動沉積係-種用於塗覆金屬的水性方法，當小量的 多原子價金屬離子從該金屬表面釋放時，其可藉由介於該 W塗覆與金屬基板之間的反應驅動。該水性組成物必須含有 -經穩定化的聚合物分散劑。可自動沉積之塗覆的必要特 徵在於該經分散的材料係由位於聚合物上及/或介面活性 劑所提供的官能基所穩定化，該等介面活性劑對於進入水 相的多價離子是敏感的。沉積作用發生於當足夠濃度的多 U價離子發生於金屬表面時，藉由該等多價離子與這些引起 分散的安定官能基互相影響產生沉澱。 自動沉積組成物的例子已描述於如歐洲專利_請案第 0Π2828號、Bashir M· Ahmed所擁有之美國專月利第 4,647,48G號以及Wilbur s. _之美國專利第4，咖，⑽號 、美國專利第4,657,788號、第5,691，⑽號及第4,⑹，⑽ 號，以及在此併入參考的每一引證專利。當其樹脂材料係 以如石黃酸鹽官能化_清漆、或由至少兩種可聚合之乙稀 化不飽和單體所聚合之乳化產^的乳㈣形柄提供時， 該等經設計的組成物特別地有效。 6 20 546413 玖、發明說明 在應用浸潰之自動沉積塗覆的實施中，通常該塗覆可 在從水浴撤出之後沖洗。在-些情況下，沖洗並不被進行 。對於在金屬部件無沖洗步驟的自動沉積塗覆方法仍存有 -些限制。無沖洗步驟產生—個問題，係有關於排水沿著 5邊緣的邊緣，當乾燥時導致有關於水潰的邊緣。這些水潰 邊緣導致較差的保護塗覆。在嘗試減輕水潰邊緣可產生的 其他問題，如該部件表面不同區域中乾燥薄膜厚度(DPT)的 變化。用於無沖洗塗覆法的需求在於沉積符合可接受之 ㈣-致性的足量塗覆以減少錢邊緣的料，在應用浸 10潰的自動沉積塗覆中是高度令人期待的。 【發明内容】 發明概要 依據本發明的-較佳觀點，係提供有—無沖洗自動沉 積方法以在-含有料固體濃度、在—特定水浴溫度、浸 入時間的水性塗覆洗祕中對—金屬部件應用浸潰，其中 經浸潰部件的移除速率保持在相同或低於流動液體部分的 排出速率’因此依據該部件的移除，水潰邊緣的形成得以 最小化且DFT保持在可接受的容限程度。 【實施方式】 較佳具體實施例之詳述 上除非以其他方式指出，化合物在化學命名的敘述係參 考該等化合物在添加至敘述中所指定的任何組" 寺，但 7 546413 玖、發明說明 不需成為混合物一但經混合之該等化合物間化學互相影響 的前導。 在此所用之”經自動沉積的樹脂”的術語意指所有在自 動沉積方法中可被自動沉積的樹脂。 5 附為乾薄膜厚度，且利用X光測厚儀（Fisherscope MMS Permascope)測量並在每一部件或面板上取十次讀值 的平均作為統計樣本。 底漆意指一施用至表面的液體組成物，該表面作為 隨後施用面漆之下的底漆。該面漆可為一黏著劑且該底漆 1〇 /黏著劑的面漆形成用於接著兩基板的黏著系統。 塗覆意指一液體組成物施用至一表面以形成在該表 面上的一保護及/或合乎美觀的塗覆。 “電化學活潑金屬，，意指離子與所有金屬及合金在電動 勢序較氫為活潑者。電化學活潑之金屬表面的例子包括辞 15、鐵、銘與經冷軋、經磨光、經酸性溶液清洗、經熱滾乾 以及經錢辞的鋼。 ‘‘含鐵的”意指鐵以及鐵合金。 經自動沉積的塗覆係含樹脂的酸性水性組成物，包含 一種酸、-氧化劑以及該經水性分散的樹脂、經自動沉積 2〇之組成物的例示為已知。這些適用於本發明者係如在歐洲 專利公告第〇132828號以及美國專利第4,647,48〇及 4，186,219號所提出者來製造。 可被自動沉積之額外之經聚合的樹脂通常包含至少一 乙烯化不飽和單體化合物(如乙烯為主的樹脂）。較佳的乙 8 546413 玖、發明說明 烯化不飽和單體包括苯乙烯-丁二烯、丙烯酸酯、如甲基丙 烯酸曱酯與乙基丙烯酸甲酯之經烷基取代的丙烯酸酯、如 氣化乙烯之函化乙烯、如氯化亞乙烯以及二氯亞乙烯之鹵 化亞乙烯、如伸乙基之亞烷基、如四氟乙烯之經齒素取代 5的亞烷基以及如丙烯腈之丙烯腈物質，及上述之組合物與 相似物。 考量適用於此之類型的樹脂為經修飾之酚的酚醛清漆 樹脂的水性分散劑。這些為酚樹脂前驅物、修飾劑與多羥 酚化合物的反應產物。該修飾劑包括至少一能使修飾劑與 1〇該酚樹脂前驅物反應的有效部分以及一離子部分。據此， 。亥飾？=!彳之較佳貫施例為一方香族化合物。據此，該修飾 劑之離子部分的另一較佳實施例為硫酸鹽、磺酸鹽、亞硫 酸鹽、次硫酸鹽或氧磺酸鹽，且該經分散之酚樹脂反應產 物具有20:1至200:1之碳/硫原子數比。 15 該酸為可與一金屬反應以生成多原子價離子之有效濃 度的任何酸。可用於該自動沉積組成物的酸包括無機以及 強有機酸，例如氫氟酸、氫氣酸、硫酸、硝酸、磷酸、醋 酉文、如氯乙酸及二氯醋酸之經鹵素取代的以及擰檬酸。有 關於用在經聚合之經自動沉積的樹脂乳化之較佳的酸為氫 2〇氟酸。用在有關於經修飾之酚分散之具體實施例的較佳酸 為鱗酸。至於鋼，由該金屬表面游離之多原子價離子為鐵 及/或亞鐵的離子。當該酸經混合至該組成物中，推測該 個別的離子經形成且在游離酸外存在為獨立的種類。換句 話說，對於磷酸，磷酸鹽離子與游離的磷酸同存在於該塗 9 546413 玖、發明說明 覆水浴中。對於經修飾之酚分散劑的實施例，以樹脂分散 劑為100份的重量計，該酸較佳地以5至300份之重量的 里存在’更佳為至160份的重量存在。 可用於本發明之自動沉積組成物中的氧化劑包括如過 5 氧化氫之過氧化物、如鉻酸以及二鉻酸化鉀的鉻酸鹽及二 鉻酸鹽、如硝酸及硝酸鈉的硝酸鹽、如過硫化鈉及過硫化 銨的過硫酸鹽、如過硼酸鈉的過硼酸鹽、如氟酸鐵（II)的三 價鐵等。過氧化氫以及氟酸鐵（11)為較佳的氧化劑。 用於本發明之示範的自動沉積組成物其樹脂係為乳膠 1〇的型悲（即至少一種可聚合之乙烯化不飽和單體的乳化聚合 產物）。此等組成物的例子包括由Henkel製造之以聚亞乙 烯樹脂為主之Autophoretic® 800系列的自動沉積組成物與 以丙烯酸樹脂為主之Autophoretic® 700系列的自動沉積組 成物。此等組成物較佳含有作為氧化劑之氫氟酸以及過氧 15化氫或氟酸鐵（ΙΠ)化物。其他商業上可得之可自動沉積之 塗覆物為羅德公司之Autoseal，如已描述於共同申請案第 〇9/235,201號的M;211G，在此—併作為參考。在施用一浸 潰應用之自動沉積塗覆之前，最佳的金屬處理係由描述於 共同申請案第G9/235,778號的水性金屬處理初級組成物所 20 提供，在此一併作為參考。 在自動沉積狀態下由自動沉積化合物所產生的塗覆一 般具有名義上0.5至3密爾、較佳為約1〇至2〇密爾的平 均厚度’施用於具有（U至〇·5密爾+/_〇〇5密爾的金屬處 理上。較佳為去離子水的水係利用於建立—預定的固體量 10 546413 玖、發明說明 。即使該等量可依所需變化，該塗覆水浴的固體量係在3 至10%的範圍。 β玄水冷組成物係漂浮於水面上且大體上無易揮發的有 機化合物。在本發明的實踐中，在該部件表面上藉由5至 5 10重里〇/〇、較佳為6重量％之固體範圍的固體水浴，水浴 溫度為15〇C至40。(：，浸入時間為2〇至8〇秒、較佳為％ 至75秒’以及-部件撤出速率為i至1()英尺/分鐘、較 佳為3至6英尺/分鐘的處理之經自動沉積塗覆的丁平 均保持在+/-〇·3密爾，較佳為+/-0.2密爾的範圍。 10 纟塗覆—金屬部件n輯法的較佳具體實施例中 ，水性自動沉積水浴包含一酚的樹脂分散劑，特別為—預 先混合之水性㈣清漆分散劑與一沉積控制劑以及—任擇 的撓性物組合物。 自動沉積的速率係獨立於該部件的撤出速率之外。典 15型地該沉積的瞬間速率與消逝的浸入時間一樣慢。沉積速 率與自限的特徵有關，然而浸入時間被限制以維持最 大的DFT。甚至在該經浸入部件上之膠化沉積的形成，有 進-步從部件的排水之自動沉積系統的元件係被撤出。在 本發明的實踐中，該撤出速率維持在或低於排水速率，根 據完全的撤出，水滴邊緣減少且最佳地被消除。無關於緩 慢的撤出速率’在該部件上1〇個點所計算之請的標準 誤差保持在0.05密爾至0.16密爾之内。 在最佳實施例中’在該金屬基板介面當該塗覆乾燦為 一齡/金屬《鹽的薄、經緊密結合之渗透有機/無機基 11 546413 玖、發明說明 質。此基質可進一步以聚合物撓性化。該撓性物係對由該 等組成物所形成的膜提供任一可撓性及/或韌性的材料。 由該撓性物所提供的韌性使得該膜具破裂抗性。該撓性物 在室溫應為非玻璃的，且為一可相容於酚的酚醛清漆樹脂 5分散劑的水性乳化乳膠或水性分散劑。該撓性物較佳為以 水性乳化乳膠或水性分散劑之形式所組成的組成物。 合適的樹脂分散劑包括（聚）丁二烯、新平橡膠、苯乙 烯-丁二烯橡膠、丙烯腈-丁二烯橡膠（如已知的腈橡膠）、氫 化聚烯烴、丙烯酸聚合物、胺甲酸酯聚合物、乙烯_丙烯共 10聚物橡膠、乙烯-丙烯··二烯三聚物橡膠、苯乙烯-丙烯酸共 聚物、聚醯胺、聚（醋酸乙烯酯）以及其相似物之水性乳膠 、乳化劑或分散劑。較佳為經氫化之聚烯烴、腈橡膠以及 苯乙烯-丙烯酸共聚物。 適合的苯乙烯-丙烯酸聚合物乳膠可購自〇00(1%訂輪 15胎及橡膠公司之名為PLIOTEC者以及如描述於美國專利第 4’968’741、5，122,566及5,616,635號者。依據美國專利第 5,616,635號，此一共聚物乳膠係由45_85重量百分比之乙 烯芳香族單體、15-50重量百分比之至少一烷基丙烯酯單 體X及1 6重里百分比之不飽和幾基化合物所製得。苯乙 2〇烯係較佳的乙烯芳香族單體，丁基丙烯酯係較佳的丙烯酯 單體，且丙烯酸與曱基丙烯酸為較佳的不飽和羰基化合物 製k乳膠的混合物亦包括至少一鱗酸酯介面活性劑、至 不溶於水之非離子介面活性劑以及至少一自由基起始 劑0 12 546413 玖、發明說明 腈橡膠乳化劑乳勝一般由至少一丙稀腈或其烧基衍生 物之單體以及至少一共軛二烯，較佳為丁二烯之單體所製 得。依據美國專利第4,920，176號，該丙烯腈或烷基衍生物 單體應以該等單體為總重之〇或1至50重量百分比的量存 5 在。該共軛二烯單體應以該等單體為總重之50至99重量 百分比的量存在。該腈橡膠亦可任擇地包括如丙烯酸之各 種共聚單體或其各種酯類、二羧酸或其組成物。該等單體 的聚合反應典型地經由自由基催化劑開始。典型地亦添加 陰離子介面活性劑。合適的腈橡膠乳膠可得自b f. 10 Goodrich之HYCAR®。代表性之經氫化的聚烯烴包括氯化 天然橡膠；包括聚氣丁二烯、氣化聚氣丁二烯、氣化聚丁 一烯、六氯五二烯、丁二烯/鹵化環共軛二烯添加劑、氯化 丁二嫦苯乙烯共聚物、氯化乙嫦丙稀共聚物以及乙婦/丙稀 /非共軛二烯三聚物的含氣及含溴之合成橡膠；氣化聚乙烯 15 ;氯石黃化聚乙烯；聚（2,3-二氯-1，3-丁二烯）；漠化聚（2,3_二 氯-1，3-丁二烯）；心齒化丙烯腈及2,3_二氣丁二烯的共 聚物，氣化聚（氯乙烯）以及包括此含鹵素之彈性體的混合 物。 鹵化聚烯烴之乳膠可依照在溶劑中溶解㈣化聚稀煙 20並添加介面活性劑所得溶液的習知方法來製備。水接者在 高切變下添加至該溶液中以乳化該聚合物。該溶液接者經 擠乾以獲付礼膠。該乳膠亦可由齒化乙稀化不飽和單體的 乳化聚合反應製得之。 丁一稀乳膠特別地適用為該繞性物。製造丁二稀乳膠 13 玖、發明說明 的方法廣泛地用於商業上’以及如美國專利第4，Q54,547及 ’920,600號亦在此併入參考。此外，美國專利第 5,2〇〇,459、5,300,555及5,496,884號描述了在聚乙婦醇以 及如有機醇或乙二醇存在下之丁二烯單體的乳化聚合反應 5 〇 ^ 有利於製備丁 一晞聚合物乳膠作為挽性物的丁二烯單 體貫質上可為任何含有共軛不飽和之單體。典型的單體包 括 2,3-氯-1，3-丁一婦、ι，3-丁二烯、2,3-二溴-i，3-丁二烯異 戊二烯、異戊二烯、2,3-二甲基丁二烯、氯戊二烯、溴戊 10二稀、2,3_二溴-1，3·丁二烯、三氣丁二烯、腈戊二烯 、六氣丁二烯以及該等組成物。特別較佳為使用2,3_二氯-1，3-丁二烯，因為含有其2,3-二氯_1，3-丁二烯單體單元之主 要部分的聚合物已被發現其在黏著應用特別有用，肇因於 2,3-二氣-1，3-丁二烯為主之聚合物的出色接著性以及阻絕 15特性。如上述，本發明之一絕佳實施例為其中該丁二烯聚 合物包括至少60重量百分比、較佳為至少7〇重量百分比 的2,3-二氣-1，3-丁二烯單體的單元。 該丁二烯單體可與其他單體共聚化。此可共聚化之單 體包括如α-溴丙烯腈以及α-氯丙烯腈的化丙烯腈；如 2〇丙婦S欠、曱基丙婦酸、2 -乙基丙稀酸、2 -丙基丙稀酸、2 -丁 基丙烯酸以及分解鳥頭酸的α，β-不飽和羧酸；如乙基-2_氯 丙稀酯以及乙基-2-溴丙稀酯之烧基-2-鹵化丙稀酯；α_溴乙 烯酮；氯化亞乙烯；乙烯甲苯；乙烯萘；諸如甲基乙烯酯 、醋酸乙烯以及甲基乙烯酮的乙烯酯、酯類以及酮；酯醯 14 546413 玖、發明說明 胺以及如甲基丙稀酯、甲基甲丙朗、甘油基丙㈣、甲 基丙稀酸酉旨以及丙烯腈之丙稀酸以及甲基丙稀酸的睛類， 以及此等單體的組成物。若使用可共聚合之單體，較佳為 α-鹵化丙烯腈及/或α，β_不飽和鲮酸。以總單體重量之〇 1 5至30重量百分比的該可共聚合之單體可用於形成該丁二婦 聚合物。 在實施生產乳膠的乳化聚合反應，可用常見之陰離子 及/或非離子介面活性劑以協助乳膠的形成。典型地陰離 子介面活性劑包括如來自於月桂酸、硬脂酸以及油酸之脂 ^肪酸的魏酸鹽；如甲基甘胺酸之肌胺酸賴化衍生物；如 十二硫酸鈉的硫酸鹽類；如Turkey Red 〇i}之硫酸化天然 油以及酯類；硫酸烷醯聚乙烯；鹼金屬烷基硫酸鹽；環氧 化磺酸鹽類；烷醯聚乙烯聚醚磺酸鹽；異丙基萘磺酸鹽； ’、琥珀敲鹽，如複合填酸鹽之短鏈脂醇部分酯化的罐酸鹽 酉曰類以及♦環氧化脂醇的鱗酸鹽酯類。典型的非離子介面 活性劑包括如環氧化烷醯衍生物之環氧化（氧化乙烯）衍生 物；單氫化醇及聚氫化醇；氧化乙烯/氧化丙烯間體共聚 物，如單硬脂酸甘油酯的酯類；諸如單硬酯酸去水山梨醇 及氧化聚乙烯去水山梨醇單月桂酸酯之山梨醇的去水產物 0 ，月女類，月桂酸以及鹵化異丙烯。若使用常見的介面活性 劑以總單體之重量為1〇〇份計，其〇〇1至5份、較佳為 0·1至2份的量可用於形成該丁二烯聚合物。 車乂佳的二氣丁二烯同種聚合物具有以陰離子介面活性 训為特徵的膠狀安定系統。此陰離子介面活性劑包括烷基 15 546413 玖、發明說明 續酸鹽及烷醯磺酸鹽（商業上可購自Stepan之商標名為 POLYSTEP者）以及烷基化之氧化聯苯的磺酸或鹽類（如商 業上可購自Dow化學公司之商標名為doWFAX的二磺酸 雙十一基二申苯基氧醋或二續酸二己基雙苯基氧g旨）。 5 特別地，較佳之作為撓性物的丁二烯乳膠係在苯乙烯 磺酸、磺酸化苯乙烯、聚（苯乙烯磺酸）或聚（磺酸化苯乙烯） 安定劑存在的狀態下經聚合化形成乳膠。聚（磺酸化苯乙烯 )為較佳的安定劑。此安定系統對丁二烯聚合物特別有效， 戎丁二烯聚合物係衍生自用於形成丁二烯聚合物之單體總 10重之至少60重量百分比的二氣丁二烯單體。該丁二烯聚合 物乳膠可在水以及苯乙烯磺酸、磺酸化苯乙烯、聚（苯乙烯 石尹、酸）或聚（磺酸化苯乙稀）安定劑存在下，由已知有關於聚 合该丁二烯單體（及若存在可共聚合之單體）的乳化聚合反 應技術製得。该％酸鹽可為任何如鈉、鉀或四級胺之陽離 15子基的鹽類。磺酸化苯乙烯鈉為較佳的磺酸化苯乙烯化合 物。聚（磺酸化苯乙烯）聚合物包括聚（磺酸苯乙烯）同種共聚 物以及如順丁烯二酸酐的聚（磺酸化苯乙烯）共聚物。聚（磺 酸化苯乙婦）的納鹽為特別較佳，且商業上可購自Nati〇nal Starch公司之以VERSA TL為商標者。該聚（磺酸化苯乙烯 2〇 )的平均分子量為5xl〇4至15xl〇6，較佳為15χ1〇5至 2·5χ105。至於聚（磺酸化笨乙烯）或聚（苯乙烯磺酸），重要 需確認的是該乳化聚合反應在預形成之聚合物存在時發生 。換句活說，該丁二烯單體係與預形成之聚（磺酸化苯乙烯 )或聚(苯乙烯磺酸)接觸。以用於形成該丁二烯聚合物的單 16 546413 玖、發明說明 體總重為100份計，該安定劑以〇·1至10份、較佳以1至 5份的量存在。 若存在該撓性物，其較佳地以所欲之酚的酚醛清漆樹 月曰刀放劑之總重為100份計的5份重量至3〇〇份重量包括 於組成物中。更佳地，該撓性物以所欲之酚的酚醛清漆樹 月曰分散劑之總重為1〇〇份計的25份重量至1〇〇份重量的量 存在。 及經修飾之紛樹脂分散劑可由已知的紛樹脂硬化方法 經硬化形成高度交聯的熱固物。硬化機制取決於該酚樹脂 1〇分散劑的用途及型態而變化。例如，經分散的可溶酚醛樹 脂硬化的實施例典型地可由加熱該酚樹脂分散劑來達成。 該經分散之酚醛清漆硬化的實施例典型地可藉由添加供醛 化合物來達成。 由於该經分散之酚樹脂為一酚醛清漆，可硬化物應被 15採用以硬化由金屬處理組成物所形成的膜。須注意的是該 金屬處理組成物本身不包括酚樹脂可硬化物，因為這些可 硬化物在酸性環境下無法安定地儲存。膜的硬化可由在該 金屬處理膜上之含可硬化之上塗層的施用來達成。典型地 該金屬處理組成物係施用於一金屬表面（不是以常見方式就 2〇是經自動沉積）然後乾燥。含可硬化物之經自動沉積的上塗 層係經施用而處理該金屬表面。包含於該上塗層中的可硬 化物可為一供醛化合物或一芳香族亞硝基化合物。包含上 述可硬化物之其一或兩者的上塗層組成物為已知且商業上 可購得者。 17 546413 玖、發明說明 該供醛物實質上可為與羥基芳香族化合物反應以形成 硬化或交聯之酚醛清漆之酚樹脂之任何型態的酸。在本發 明中，作為醛（如甲醛）的典型化合物包括甲醛以及如福馬 林的甲醛溶液；乙醛；丙醛；異丁醛；2_乙基己酸；2_甲 5基戊醛；苯甲醛；以及如三聚f醛、三噪烷、呋喃f醇、 六亞甲四胺、無水甲醛苯胺、乙烯二胺甲醛之分解為甲醛 的化合物；加熱時釋放甲醛的縮醛類；尿素與甲醛之甲脲 衍生物；羥甲酚化合物；以及其相似物。 經發現已描述於美國專利第09/235,778，號的底漆塗覆 10之金屬部件的預塗底漆，自存在於該底漆之可溶酚醛樹脂 所生成的甲醛種類似乎經由擴散共硬化該金屬處理塗覆中 的酚醛清漆。另外，該酚醛清漆的硬化或交聯可由離子交 聯以及與藉由酸金屬基板反應所生成的金屬離子螯合來發 生。 [5 此外在本發明中，高分子量醛同種共聚物及共聚物可 作為'曰在的甲酸來源。在此提及甲酸來源之潛在甲酸來 源在如黏著系統應用加熱時將僅釋放曱醛。典型地高分子 酸同種共^物以及共聚物包括⑴縮酸同種共聚物，⑺縮酿 共聚物，（3)具有下列特徵結構的加馬聚氧·亞甲_ : 20 Ri0〇-(CH2〇)n.Rn 以及⑷具有下列特徵結構的聚氧亞甲基乙二醇： H〇-(Ri2〇)x.(CH2〇)n.(R13〇)x-H 其中Rio以及Ru可為相同或相異且個別為一具有約i 車又佳為1至4個碳原子的烷基基團，R12以及R13可 18 546413 玖、發明說明 為相同或相異且個別為一具有2至12、較佳為2至8個碳 原子的伸烷基基團，n係大於100且較佳為約2〇〇至約 2000的範圍；以及χ為約〇至8、較佳為}至4的範圍且 至少一 X係相當於至少為丨。該高分子醛同種共聚物以及 5共聚物係進一步以至少、75〇c的炫點即實質上嵌入該酚系統 至加熱活化；以及實質上在低於熔點的溫度完全不溶於水 為特徵。該縮醛同種共聚物以及縮醛共聚物為商業上已知 的商品。該聚氧亞甲基材料亦為已知且可藉由具有丨至8 個石反原子的單醇或二經乙二醇及縫乙二醇在酸性催化劑存 在下與聚氧亞甲基乙二醇的反應迅速地合成。一製備這些 交聯劑的代表方法係描述於美國專利第2,512,95〇號，在 此並用作為參考。加馬·聚氧亞甲鱗—般為潛在甲㈣較佳 來源，且在實際上用於本發明之特別較佳的潛在甲酸來源 為2-聚氧亞甲基二甲基醚。 15 ㈣香族亞石肖基化合物可為任何芳香族烴，諸如苯、 萘、葱、聯苯以及其相似物之含有至少二亞石肖基基團直接 附加至非相鄰環的碳原子者。此等芳香族亞硝基化合物如 描述於美國專利第3,258,388、4，119,587及Μ%，·號者 上述之控制劑在前述發明中之金屬處理組成物是特別 有用的 <旦其在任何包含於可自動沉積化合物中之多組份 組成物亦為有料。該可自動沉積化合物為任何可使該多 成物（不嗍由本身或由與該組成物其他組份的組合） 自動沉積於一金屬表面上的材料。較佳地，該可自動沉積 19 玖、發明說明 的組份為任何可對㈣成物提 4、 切/儿積旎力之經水分散 或可溶於水的樹脂。相信本發明 .^ 用於絕大部分有關於以 機聚合物所形成的塗覆，特別是這些聚合物係衍生自乙 稀化不飽和化合物。其他用於本發明之有機聚合物為取自 可適於化合至一水性塗覆水浴 $式者。有機樹脂包括這 些衍生自如聚偏二氣乙烯、聚氣 乳G碲聚乙烯、丙烯酸、 ㈣t乙酸“以及苯乙稀丁二烯之乙烯化不飽和單體（ 參見美國專利第4,4M，350、4,994,521 “427,863號，以 10 及PCT公開專利申請t wo 93/15154號）。胺甲酸醋及聚 醋樹脂亦被提及為有用的。某些環氧樹脂及環氧丙稀醋樹 脂據稱亦為有用之自動沉積樹脂（參見美國專利第 5,500,46()號以及PCT公開專利巾請f w〇 97聰63號）。 亦可使用這些樹脂的摻合物。 較佳的可自動沉積的樹脂係描述於定為美國第 15 09/235,201號申請案之共同申請案的水性盼樹月旨分散劑， 在此併用作為參考，此分散劑樹脂的盼酸清漆變體係有關 於上述之金屬處理組成物。亦有一可溶酚醛樹脂變體包含 在本發明之可形成為一多組份組成物的控制劑内。 用於製造該經分散之可溶酚醛樹脂的酚樹脂前驅物以 20及修飾劑係與敘述用於該經分散之酚醛清漆者相同。然而 。該經分散之可溶酚醛樹脂係由1莫耳的修飾劑與1至2〇 莫耳的酚樹脂前驅物反應所製得。經分散之可溶酚醛樹脂 典型的可藉由一可溶酚醛樹脂前驅物或一可溶酚醛樹脂前 驅物的混合物與該修飾劑或無其他反應劑、添加劑或催化 20 546413 玖、發明說明 州的此合物反應來獲得。然而，亦可使用其他所欲的反應 劏、添加劑或催化劑。多羥酚化合物可任擇地相對小量的 包含在用於可溶酚醛樹脂之反應劑混合物中。該可溶酚醛 樹脂的合成並不需要酸催化劑。 親水I*生可浴盼終樹脂典型地具有至少1 · 〇的F/p比例 。依據本發明，具有遠大於1〇之F/p比例的親水性可溶 酚醛樹脂可被成功地分散。例如，製造具有F/P比例至少 為2之親水性可〉谷紛盤樹脂的水性分散劑是可能的，其 F/P比例可達到3，為F/P比例理論上的限制。 依據揭示於09/235,201號案之特別較佳實施例，其中 忒經分散之酚樹脂為一可溶酚醛樹脂，且該修飾劑為一具 有離子懸滴積團X及二個可反應取代基γ的萘，該經分散 之_脂反應產物含有_具有可藉由下列化學式m表現其 結構之养聚合物的混合物：546413 Description of the invention (The description of the invention should state: the technical field to which the invention belongs, the prior art, the description, the embodiment, and the drawings are brief descriptions. Application of materials. [Prior Art] Background of the Invention An automatic deposition system is an aqueous method for coating a metal. When a small amount of polyatomic metal ions is released from the metal surface, it can be interposed between the W coating and the metal substrate. Response-driven. The aqueous composition must contain a stabilized polymer dispersant. A necessary feature of a coating that can be deposited automatically is that the dispersed material is stabilized by functional groups on the polymer and / or provided by a surfactant, which is a polyvalent ion that enters the aqueous phase. Sensitive. Deposition occurs when sufficient U-valent ions occur on the metal surface, and the multivalent ions interact with these stable functional groups that cause dispersion to cause precipitation. Examples of the auto-deposition composition have been described in European Patent No. 0Π2828, U.S. Patent No. 4,647,48G owned by Bashir M. Ahmed, and U.S. Pat. US Patent Nos. 4,657,788, 5,691, ⑽, and 4, ⑹, ，, and each of the cited patents incorporated herein by reference. When the resin material is provided with, for example, a lutein-functionalized varnish, or an emulsified scum-shaped handle polymerized from at least two polymerizable ethylenically unsaturated monomers, these designed The composition is particularly effective. 6 20 546413 (ii) Description of the invention In the implementation of an automatic deposition coating using dipping, the coating can usually be rinsed after being withdrawn from the water bath. In some cases, flushing is not performed. There are still some limitations to the automatic deposition coating method without a washing step on metal parts. The non-rinsing step creates a problem related to the edges of the drainage along the 5 edges, which, when dried, cause the edges of the water to break. These water ruptured edges result in poorer protective coating. Other problems that can arise from trying to mitigate water-collapsed edges, such as variations in dry film thickness (DPT) in different areas of the part's surface. The need for flush-free coating methods is to deposit a sufficient amount of coating that meets the acceptable specifications to reduce the edge of the money, which is highly desirable in the application of immersion auto-deposition coating. [Summary of the Invention] Summary of the Invention According to a preferred aspect of the present invention, there is provided a non-rinsing automatic deposition method for a metal coating in a water-based coating solution containing a solid concentration of a material, a specific water bath temperature and an immersion time. The component is impregnated, where the rate of removal of the impregnated component remains the same or lower than the discharge rate of the flowing liquid portion '. Therefore, the formation of water break edges is minimized and the DFT is kept acceptable based on the removal of the component. Tolerance. [Embodiments] The detailed description of the preferred embodiments, unless otherwise indicated, refers to the chemical nomenclature of the compounds by referring to the addition of these compounds to any group specified in the narrative, but 7 546413 发明, invention Explain that it is not necessary to be a leader of the chemical interaction between the compounds once they have been mixed. The term "automatically deposited resin" as used herein means all resins that can be automatically deposited in an automatic deposition method. 5 Attach the thickness of the dry film, and use an X-ray thickness gauge (Fisherscope MMS Permascope) to measure and take the average of ten readings on each part or panel as a statistical sample. Primer means a liquid composition applied to a surface that serves as a primer underneath a subsequent application of the topcoat. The topcoat may be an adhesive and the topcoat of the primer 10 / adhesive forms an adhesive system for adhering two substrates. Coating means the application of a liquid composition to a surface to form a protective and / or aesthetically pleasing coating on the surface. "Electrochemically active metals, which means that ions and all metals and alloys are more active in the electromotive force sequence than hydrogen. Examples of electrochemically active metal surfaces include Ci 15, Iron, Ming and cold rolled, polished, acid Solution-washed, hot-roll-dried, and depreciated steel. "Iron-containing" means iron and iron alloys. An example of a coating-containing, acid-containing, aqueous composition that is automatically deposited, including an acid, an oxidizing agent, and the water-dispersed resin, and that is automatically deposited 20 is known. These are suitable for the present inventors to manufacture as proposed in European Patent Publication No. 0132828 and U.S. Patent Nos. 4,647,480 and 4,186,219. The additional polymerized resin that can be automatically deposited usually contains at least one ethylenically unsaturated monomer compound (such as an ethylene-based resin). Preferred ethylene 8 546413 玖, description of the invention The ethylenically unsaturated monomers include styrene-butadiene, acrylates, such as alkyl acrylates such as methyl methacrylate and methyl ethacrylate, such as gas Ethylene-functionalized ethylene, such as vinylidene chloride and vinylidene chloride, halogenated vinylidene, such as ethylene, alkylene such as tetrafluoroethylene, substituted with dentin, and alkylene such as acrylonitrile. Acrylonitrile materials, and the above-mentioned compositions and analogs. Considering that this type of resin is a water-based dispersant for novolac resins with modified phenols. These are the reaction products of phenol resin precursors, modifiers and polyphenol compounds. The modifier includes at least one effective portion capable of reacting the modifier with the phenol resin precursor and an ionic portion. Accordingly,. Hai decoration? =! 彳 The preferred embodiment is an aromatic compound. Accordingly, another preferred embodiment of the ionic portion of the modifier is sulfate, sulfonate, sulfite, hyposulfite or oxysulfonate, and the dispersed phenol resin reaction product has a ratio of 20: 1 To 200: 1 carbon / sulfur atom ratio. 15 The acid is any acid that can react with a metal to produce an effective concentration of polyatomic ions. Acids that can be used in the auto-deposition composition include inorganic and strong organic acids such as hydrofluoric acid, hydrogen acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, halogen-substituted such as chloroacetic acid and dichloroacetic acid, and citric acid . A preferred acid for emulsification of polymerized, auto-deposited resins is hydrofluoric acid. A preferred acid for use in a specific example of modified phenol dispersion is linoleic acid. As for steel, the polyatomic valence ions released from the metal surface are iron and / or ferrous ions. When the acid is mixed into the composition, it is speculated that the individual ions are formed and exist as separate species outside the free acid. In other words, with respect to phosphoric acid, phosphate ions and free phosphoric acid coexist in the coated water bath. For the modified phenol dispersant example, the acid is preferably present at 5 to 300 parts by weight, more preferably at 160 parts by weight, based on 100 parts by weight of the resin dispersant. Oxidizing agents that can be used in the auto-deposition composition of the present invention include peroxides such as hydrogen peroxide, chromates and dichromates such as chromic acid and potassium dichromate, nitrates such as nitric acid and sodium nitrate, Such as sodium persulfide and ammonium persulfide persulfate, such as sodium perborate perborate, such as ferric (II) trivalent iron, and the like. Hydrogen peroxide and iron fluoride (11) are preferred oxidants. The resin of the exemplary auto-deposition composition used in the present invention is a latex 10 type (ie, an emulsion polymerization product of at least one polymerizable ethylenically unsaturated monomer). Examples of such compositions include autophoretic® 800 series autodeposition compositions based on polyethylene resin manufactured by Henkel and autophoretic® 700 series autodeposition compositions based on acrylic resin. These compositions preferably contain hydrofluoric acid as an oxidizing agent and hydroperoxyhydrogen or iron (III) fluoride. Other commercially available coatings that can be deposited automatically are Rohde & Co. Autoseal, as described in joint application No. 09 / 235,201; M; 211G, here-and incorporated herein by reference. Prior to the application of an automatic deposition coating for an immersion application, the optimal metal treatment was provided by the Waterborne Metal Treatment Primary Composition 20 described in co-application G9 / 235,778, which is incorporated herein by reference. The coating produced by the auto-deposition compound in the auto-deposition state generally has an average thickness of nominally 0.5 to 3 mils, preferably about 10 to 20 mils. + / _ 〇〇5 mil for metal processing. The water system, preferably deionized water, is used to establish—predetermined solid amount 10 546413 发明, invention description. Even if the amount can be changed as required, the coating The amount of solids in the water bath is in the range of 3 to 10%. The β mystic water-cooled composition floats on the water surface and is substantially free of volatile organic compounds. In the practice of the present invention, the surface of the part is replaced by 5 to 5 A solid water bath with a solid range of 10% 0/0, preferably 6% by weight, with a water bath temperature of 15 ° C to 40. (:, immersion time is 20 to 80 seconds, preferably% to 75 seconds' and -Parts withdrawn at a rate of i to 1 () ft / min, preferably 3 to 6 ft / min, treated with auto-deposited coated Ding averaged to remain at +/- 0.3 mils, preferably + /-0.2 mil range. 10 纟 Coating-In a preferred embodiment of the n-series method for metal parts, an aqueous automatic deposition water bath Monophenol-containing resin dispersants, in particular-pre-mixed waterborne varnish dispersant with a deposition control agent and-optionally a flexible composition. The rate of automatic deposition is independent of the withdrawal rate of the part The typical rate of this type of deposition is as slow as the elapsed immersion time. The deposition rate is related to the self-limiting characteristics, but the immersion time is limited to maintain the maximum DFT. Even the gelled deposit on the immersed part Formed, the elements of the automatic deposition system with progressive-drainage from the component are withdrawn. In the practice of the present invention, the withdrawal rate is maintained at or below the drainage rate. According to the complete withdrawal, the water droplet edge is reduced and Optimally eliminated. Regardless of the slow withdrawal rate 'the standard error calculated at 10 points on the part is kept within 0.05 mils to 0.16 mils. In the preferred embodiment' in this The interface of the metal substrate when the coating is dry can be a one-year-old / metal thin, tightly bonded organic / inorganic base 11 546413 玖, the description of the invention. This matrix can be further flexible with polymer The flexible material is any material that provides any flexibility and / or toughness to a film formed from the compositions. The toughness provided by the flexible material makes the film resistant to cracking. The flexible material is The room temperature should be non-glass, and it is an aqueous emulsion latex or aqueous dispersant compatible with phenolic novolak resin 5 dispersant. The flexible material is preferably in the form of an aqueous emulsion latex or an aqueous dispersant. A suitable resin dispersant includes (poly) butadiene, neoflat rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber (such as known nitrile rubber), hydrogenated polyolefin, acrylic acid Polymers, urethane polymers, ethylene-propylene co-polymer rubbers, ethylene-propylene · diene terpolymer rubbers, styrene-acrylic copolymers, polyamides, poly (vinyl acetate), and others Similar latexes, emulsifiers or dispersants. Preferred are hydrogenated polyolefins, nitrile rubbers, and styrene-acrylic copolymers. Suitable styrenic-acrylic polymer latexes are commercially available from OO (1% Order 15 Tires and Rubber Company under the name PLIOTEC and as described in US Patent Nos. 4'968'741, 5,122,566, and 5,616,635. According to U.S. Patent No. 5,616,635, this copolymer latex is composed of 45-85 weight percent of ethylene aromatic monomer, 15-50 weight percent of at least one alkyl propylene ester monomer X, and 16 weight percent of unsaturated aryl compounds. Resulting. Styrene 20 olefin is a preferred vinyl aromatic monomer, butyl propylene ester is a preferred propylene ester monomer, and acrylic acid and fluorenyl acrylic acid are the preferred unsaturated carbonyl compounds. The mixture also includes at least one phosphonate surfactant, a non-ionic surfactant that is insoluble in water, and at least one free radical initiator 0 12 546413. Description of the invention The nitrile rubber emulsifier emulsion is generally composed of at least one acrylonitrile. Or monomers thereof, and at least one conjugated diene, preferably butadiene monomer. According to US Patent No. 4,920,176, the acrylonitrile or alkyl derivative monomer should be Of these monomers There is 5 in the total weight of 0 or 1 to 50 weight percent. The conjugated diene monomer should be present in an amount of 50 to 99 weight percent of the total weight of the monomers. The nitrile rubber can also be optionally Including various comonomers such as acrylic acid or its various esters, dicarboxylic acids or their compositions. The polymerization of these monomers typically starts via a free radical catalyst. Anionic surfactants are also typically added. Suitable nitrile rubbers Latex is available from bf. 10 Goodrich's HYCAR®. Representative hydrogenated polyolefins include chlorinated natural rubber; includes polybutadiene, gasified polybutadiene, gasified polybutadiene, six Chloropentadiene, butadiene / halogenated ring conjugated diene additives, chlorinated butadiene styrene copolymer, ethylene chloride propylene copolymer, and ethene / propylene / non-conjugated diene terpolymer Gas-containing and bromine-containing synthetic rubber; gasified polyethylene 15; chlorite yellowing polyethylene; poly (2,3-dichloro-1,3-butadiene); desertified poly (2,3_dichloro- 1,3-butadiene); copolymers of carburizing acrylonitrile and 2,3_digas butadiene, gasifying poly (vinyl chloride) and including It is a mixture of natural elastomer and halogenated polyolefin. The latex of halogenated polyolefin can be prepared according to the conventional method of dissolving trifluoride 20 in a solvent and adding a surfactant. The water connector is added to the solution under high shear. The polymer is emulsified in medium. The solution is squeezed to obtain a gift latex. The latex can also be prepared by the emulsification polymerization of toothed ethylenically unsaturated monomers. Butadiene latex is particularly suitable for this. Winding materials. The method of manufacturing succinic latex 13 玖, the invention description method is widely used in commerce ', and for example, US Patent Nos. 4, Q54,547 and' 920,600 are also incorporated herein by reference. In addition, US Patent No. Nos. 2,00,459, 5,300,555, and 5,496,884 describe the emulsification polymerization of butadiene monomers in the presence of polyethylene glycol and organic alcohols or ethylene glycol, etc.5. It is advantageous for the preparation of butadiene polymer latex as a polymer. The butadiene monomer of the nature may be any monomer containing a conjugated unsaturated monomer. Typical monomers include 2,3-chloro-1,3-butadiene, ι, 3-butadiene, 2,3-dibromo-i, 3-butadiene isoprene, isoprene , 2,3-dimethylbutadiene, chloroprene, bromopentadiene, 2,3-dibromo-1,3 · butadiene, trigas butadiene, nitrile pentadiene, hexamethylene Gas butadiene and these compositions. Particularly preferred is the use of 2,3-dichloro-1,3-butadiene, because polymers containing a major part of its 2,3-dichloro-1,3-butadiene monomer units have been found It is particularly useful in adhesive applications due to the excellent adhesion of 2,3-digas-1,3-butadiene-based polymers and its 15-barrier properties. As mentioned above, an excellent embodiment of the present invention is one in which the butadiene polymer includes at least 60% by weight, preferably at least 70% by weight of 2,3-digas-1,3-butadiene monomer. The unit. The butadiene monomer can be copolymerized with other monomers. The copolymerizable monomers include acrylonitrile such as α-bromoacrylonitrile and α-chloroacrylonitrile; such as 20 propyl acrylonitrile, ethyl acrylonitrile, 2-ethyl acryl acid, 2-propane Acrylic acid, 2-butylacrylic acid, and α, β-unsaturated carboxylic acids that decompose ornithic acid; such as ethyl-2-chloropropionate and ethyl-2-bromopropionyl-2 -Halogenated propylene esters; α-bromoketene; vinylidene chloride; vinyl toluene; vinyl naphthalene; vinyl esters, esters, and ketones such as methyl vinyl ester, vinyl acetate, and methyl ketene; esters 醯 14 546413 玖, Invention description, amines, such as methacrylic acid esters, methacrylamide, glyceryl propionate, methacrylic acid, acrylic acid and acrylonitrile acrylic acid and methyl acrylic acid, and the like Monomer composition. If a copolymerizable monomer is used, α-halogenated acrylonitrile and / or α, β-unsaturated acetic acid are preferred. The copolymerizable monomer may be used to form the dimer polymer in an amount of 15 to 30% by weight based on the total monomer weight. In the implementation of emulsion polymerization for the production of latex, common anionic and / or non-ionic surfactants can be used to assist the formation of the latex. Typically anionic surfactants include, e.g., weirates from fatty acids such as lauric acid, stearic acid, and oleic acid; sarcosine lysine derivatives such as methyl glycine; and sodium lauryl sulfate Sulfates; Sulfated natural oils and esters such as Turkey Red 〇}} alkyl sulfate polyethylene; alkali metal alkyl sulfates; epoxidized sulfonates; alkyl polyethylene polyether sulfonates; Propylnaphthalene sulfonate; ', amber salt, such as short-chain fatty alcohol partially esterified tank salts of complex filling salts and epoxidized fatty alcohol scale esters. Typical non-ionic surfactants include epoxidized (ethylene oxide) derivatives such as epoxidized alkylamidine derivatives; monohydric alcohols and polyhydric alcohols; ethylene oxide / propylene oxide interpolymers such as glyceryl monostearate Esters such as sorbitan monostearate and sorbitan monolaurate, oxidized polyethylene sorbitan monolaurate, sorbitan, laurics, lauric acid, and halogenated isopropene. If a common surfactant is used based on 100 parts by weight of the total monomer, an amount of 0.01 to 5 parts, preferably 0.1 to 2 parts may be used to form the butadiene polymer. Che Dijia's digas butadiene homopolymer has a colloidal stabilization system characterized by anionic interface activity training. This anionic surfactant includes alkyl 15 546413 sulfonium, description of the invention acid salt and alkane sulfonate (commercially available from Stepan under the trade name POLYSTEP) and alkylated sulfonic acid or salt of biphenyl oxide (E.g., commercially available from Dow Chemical Company under the trade name doWFAX, diundecyldishenyloxyphenyl disulfonate or dihexylbisphenyloxydiacetate). 5 In particular, a preferred butadiene latex as a flexible material is polymerized in the presence of a styrene sulfonic acid, sulfonated styrene, poly (styrene sulfonic acid) or poly (sulfonated styrene) stabilizer. Into latex. Poly (sulfonated styrene) is a preferred stabilizer. This stabilization system is particularly effective for butadiene polymers, which are derived from digas butadiene monomers that are at least 60 weight percent of the total 10 weight of monomers used to form the butadiene polymer. The butadiene polymer latex can be polymerized in the presence of water and styrene sulfonic acid, sulfonated styrene, poly (styrene stone, acid) or poly (sulfonated styrene) stabilizers. The butadiene monomer (and, if a copolymerizable monomer is present) is prepared by an emulsion polymerization technique. The% acid salt may be any salt such as sodium, potassium or quaternary ammonium. Sulfonated sodium styrene is a preferred sulfonated styrene compound. Poly (sulfonated styrene) polymers include poly (sulfonated styrene) homopolymers and poly (sulfonated styrene) copolymers such as maleic anhydride. Poly (sulfonated acetophenone) sodium salts are particularly preferred and are commercially available under the trademark VERSA TL from Natoon Starch. The poly (sulfonated styrene 20) has an average molecular weight of 5 × 104 to 15 × 106, preferably 15 × 105 to 2.5 × 105. As for poly (sulfonated stupid ethylene) or poly (styrene sulfonic acid), it is important to confirm that the emulsion polymerization reaction occurs in the presence of the preformed polymer. In other words, the butadiene monosystem is contacted with pre-formed poly (sulfonated styrene) or poly (styrenesulfonic acid). The stabilizer is present in an amount of 0.1 to 10 parts, preferably 1 to 5 parts, based on 100 parts by weight of the monomers used to form the butadiene polymer. If such a flexible substance is present, it is preferably included in the composition in an amount of 5 to 300 parts by weight based on 100 parts by weight of the novolak shovel of the desired phenol. More preferably, the flexible substance is present in an amount of 25 parts by weight to 100 parts by weight based on 100 parts by weight of the novolak dispersant of the desired phenol. And modified resin dispersants can be hardened by known resin hardening methods to form highly crosslinked thermosets. The hardening mechanism varies depending on the use and type of the phenol resin 10 dispersant. For example, the hardened examples of dispersed soluble phenolic resins are typically achieved by heating the phenol resin dispersant. This dispersed hardening of the novolak can typically be achieved by adding an aldehyde-donating compound. Since the dispersed phenol resin is a novolac, a hardenable material should be used to harden a film formed from a metal-treated composition. It should be noted that the metal-treated composition itself does not include phenol resin hardenables because these hardenables cannot be stored stably in an acidic environment. The hardening of the film can be achieved by the application of a hardenable top coating on the metal-treated film. Typically the metal treatment composition is applied to a metal surface (not automatically in the usual manner, 20 is automatically deposited) and then dried. An auto-deposited top coat containing a hardenable is applied to the metal surface. The hardenable compound contained in the overcoat layer may be an aldehyde-donating compound or an aromatic nitroso compound. An overcoat composition comprising one or both of the above-mentioned hardenables is known and commercially available. 17 546413 (ii) Description of the invention The aldehyde-donating substance may be substantially any type of acid of a phenol resin that reacts with a hydroxy aromatic compound to form a hardened or cross-linked novolak. In the present invention, typical compounds as aldehydes (such as formaldehyde) include formaldehyde and formaldehyde solutions such as formalin; acetaldehyde; propionaldehyde; isobutyraldehyde; 2-ethylhexanoic acid; 2-methyl 5-pentylvaleraldehyde; benzene Formaldehyde; and compounds such as trimeric faldehyde, trinoxane, furan f alcohol, hexamethylenetetramine, anhydrous formaldehyde aniline, ethylene diamine formaldehyde decomposed into formaldehyde; acetals that release formaldehyde when heated; urea and formaldehyde Methylurea derivatives; hydroxycresol compounds; and analogs thereof. It has been found that the primer 10 has been described in U.S. Patent No. 09 / 235,778, as a precoat primer for metal parts. The formaldehyde species generated from the soluble phenolic resin present in the primer appear to be co-hardened by diffusion. Novolac in metal treatment coatings. In addition, the hardening or cross-linking of the novolac can occur by ionic cross-linking and chelation with metal ions generated by the reaction of an acid metal substrate. [5] In the present invention, high molecular weight aldehyde homopolymers and copolymers can be used as a source of formic acid. Potential formic acid sources mentioned herein as formic acid sources will only release formaldehyde when heating is applied as in an adhesive system. Typical high molecular acid homopolymers and copolymers include acetic acid homopolymers, condensation copolymers, (3) Gama polyoxymethylene with the following characteristic structure: 20 Ri0- (CH2〇 ) n. Rn and ⑷ polyoxymethylene glycol with the following characteristic structure: H0- (Ri2〇) x. (CH2〇) n. (R13〇) xH wherein Rio and Ru can be the same or different And each is an alkyl group having about 1 car and preferably 1 to 4 carbon atoms, R12 and R13 may be 18 546413 玖, the description of the invention is the same or different and each is 2 to 12, preferably An alkylene group of 2 to 8 carbon atoms, n is greater than 100 and preferably in the range of about 2000 to about 2000; and χ is in the range of about 0 to 8, preferably} to 4 and at least one X is equivalent to at least 丨. The high molecular aldehyde homopolymer and 5 copolymer system are further characterized by at least 75 ° C dazzling point, that is, substantially embedded in the phenol system to heat activation; and substantially insoluble in water at a temperature lower than the melting point. The acetal homopolymer and the acetal copolymer are commercially known products. The polyoxymethylene material is also known and can be used with polyoxymethylene ethylene in the presence of an acidic catalyst by a mono- or diethylene glycol and diethylene glycol with 丨 to 8 stone counteratoms. The reaction of alcohol is quickly synthesized. A representative method for preparing these crosslinking agents is described in U.S. Patent No. 2,512,95, which is incorporated herein by reference. Gama · polyoxymethylene scale is generally a better source of potential formazan, and a particularly preferred source of potential formic acid used in the present invention is 2-polyoxymethylene dimethyl ether. 15 Huoxiangshilischokyl compounds can be any aromatic hydrocarbons, such as benzene, naphthalene, onion, biphenyl, and the like, which contain at least two dischinoschokyl groups directly attached to non-adjacent ring carbon atoms. These aromatic nitroso compounds are described in U.S. Pat. Nos. 3,258,388, 4,119,587, and M%. The above-mentioned control agents are particularly useful in the metal-treating compositions of the foregoing invention. ≪ Multi-component compositions in auto-depositable compounds are also expected. The auto-depositable compound is any material that can automatically deposit the compound (either by itself or in combination with other components of the composition) on a metal surface. Preferably, the component capable of automatically depositing 19 发明, which is described in the invention, is any water-dispersible or water-soluble resin which can improve the cutting power of the ㈣ product, and has a shearing force. It is believed that the present invention is used for most of the coatings related to organic polymers, especially these polymers are derived from ethylenically unsaturated compounds. Other organic polymers used in the present invention are those which are suitable for compounding into an aqueous coating water bath. Organic resins include these ethylenically unsaturated monomers derived from, for example, polyvinylidene fluoride, polystyrene, tellurium polyethylene, acrylic acid, acetic acid, and styrene butadiene (see US Patent No. 4,4M, 350, 4,994,521 "427,863, published under 10 and PCT Patent Application No. wo 93/15154). Urethane and polyester resins have also been mentioned as useful. Certain epoxy resins and propylene glycol resins are also said to be useful auto-deposition resins (see U.S. Patent No. 5,500,46 () and PCT Publication Patent No. f 97 97 Cong 63). Blends of these resins can also be used. A preferred auto-depositable resin is described in the water-based pandemic dispersant as a co-application of US Application No. 15 09 / 235,201, and is hereby incorporated by reference. The system relates to the above-mentioned metal treatment composition. A soluble phenolic resin variant is also included in the control agent of the present invention that can be formed into a multi-component composition. The phenol resin precursors and modifiers used to make the dispersed soluble phenol resin are the same as those described for the dispersed novolac. However. The dispersed soluble phenolic resin is prepared by reacting 1 mole of a modifier with 1 to 20 mole of a phenol resin precursor. Dispersed soluble phenolic resin can typically be obtained by mixing a soluble phenolic resin precursor or a soluble phenolic resin precursor with the modifier or without other reagents, additives or catalysis. 20 546413 This compound was obtained by reaction. However, other desired reaction rhenium, additives or catalysts may be used. The polyhydric phenol compound is optionally contained in a relatively small amount in a reactant mixture for a soluble phenol resin. The synthesis of this soluble phenolic resin does not require an acid catalyst. Hydrophilic I * bathable final resins typically have an F / p ratio of at least 1.0. According to the present invention, a hydrophilic soluble phenol resin having an F / p ratio much larger than 10 can be successfully dispersed. For example, it is possible to manufacture an aqueous dispersant having a hydrophilicity ratio of F / P ratio of at least 2> cereal resin, and its F / P ratio can reach 3, which is the theoretical limit of the F / P ratio. According to a particularly preferred embodiment disclosed in the case No. 09 / 235,201, wherein the dispersed phenol resin is a soluble phenolic resin, and the modifier is an ionic suspension drop group X and two reactive substituents γ Naphthalene, the dispersed lipid reaction product containing a mixture of nutrient polymers having a structure that can be expressed by the following chemical formula m:
XX
其中X以及Y係與化學式1&及lb中相同，a係〇或i ; n 係0至5 ; R2係獨立為谓5)2备c(r5)2_〇_c(r5^，其中 21 546413 玖、發明說明 R5係獨立為氫、院基醇、經基、院基、芳基或芳基喊：以 及R3係獨立為烧基醇、⑥基、芳基或芳基鍵。較佳地’ r2 係伸乙基或氧二亞甲基且經甲基。若6,7-二經_2_萘績 酸之鈉鹽為該修飾劑，X將為s〇3-Na+且各個γ將為0H。 需了解的是在Υ _基基團時亦可作為金屬離子㈣合基 該可自動沉積組份能以提供有效之自動沉積的任何量 存在於該組成物中。-般而言，基於該組成物中之非揮發 性成分的總#，其可為丨至5()、較佳為5至2()且更佳為7 10至14重量百分比的量。 該控制劑為可促進金屬表面上形成自動沉積塗覆的任 何材料，且任擇地可改善在含控制劑之自動沉積塗覆之後 所施用之其他自動沉積塗覆的形成。該促進劑的添加亦促 進自動冰積塗覆之厚度的一致性。含控制劑的組成物並不 而要砰置期來形成完全的塗覆。換句話說，該金屬塗覆 的轉換係取決於該經塗覆基板的乾燥以及隨後在塗覆及該 含控制劑組成物乾燥後能被立即施用之塗覆、底漆及黏著 且成物來完成。該控制劑亦必須在該組成物無過早凝固 或不穩定的酸性狀態下與該組成物的其他組份相容。 °亥控制劑可為一硝基化合物、亞确基化合物、將化合 物、確酸鹽化合物、經胺或類似材料。亦可使用控制劑的 混合物。有機硝化合物為較佳的控制劑。 該有機石肖化合物係包括硝基（_Ν〇2)連接至一有機部分 的任何材料。較佳地’該有機硝化合物係可溶於水的，若 22 546413 玖、發明說明 不溶於水則需可分散於水中。例示之有機硝化合物包括硝 基脈，諸如硝基或二硝基苯績酸鹽以及如其鈉、鉀、胺或 任何單價金屬離子（特別為3,5-二硝基苯磺酸鹽的鈉鹽）之 鹽類的芳香族硝磺酸鹽；萘盼黃S ;以及苦味酸（已知如三 5 硝基苯酚）。基於商業上可取得以及一般理由特別較佳係确 基胍以及硝基苯礦酸鹽鈉的混合物。 在一多組份組成物中之控制劑的量可特別依據該組成 物中任何酸的量來變化。較佳地，該量以該組成物中非揮 發成伤的總量計最高可達2〇重量％、較佳為高可達丨〇重 10量％，以及最佳為2至5重量％。依據一較佳實施例，該硝 基胍對硝基苯磺酸鹽的重量比率應為1:1〇至5:1的範圍。 該有機硝化合物典型地為混合至水性溶液或分散劑之 形式的組成物中。例如，硝基胍在室溫為一固體，且在配 置為該組成物之前溶於水中。 15 轉明之組成物可藉由習知技射已知的任何方法製 備’但較佳為在球磨粉機、砂磨粉機、陶珠磨粉機、鋼珠 磨粉機、高速介質磨粉機或其相似物中藉由將該等組份與 & =及磨杨或搖動。杈佳為在—如水性分散劑的液體狀 態將各個組份添加至該混合物中。 20 纟晶鹽受11試驗中，該等部件對該金屬表面以-十字 搶口方式用-«彳刀且置於_標準鹽受器彻小時來評分 。獲得逐漸腐蝕的評估。 實驗： 可自動沉積的塗覆： 23 25 546413 玖、發明說明 組份 固體 濕重 (%) 乾重(碌） Raven® 14 粉 100 0.43 1.448 Marasperse® BBOSO- 4 100 0.14 0.472 盼樹脂 Ga. Pacific 4000 51 1.42 19.616 ABS乳膠 50.250 10.4 17.696 确基脈 75 0.090 0.227 去離子水 0 77.52 00Where X and Y are the same as in Chemical Formulas 1 & and lb, a is 0 or i; n is 0 to 5; R2 is independently referred to as 5) 2 c (r5) 2_〇_c (r5 ^, where 21 546413 发明, description of the invention, R5 is independently hydrogen, nosyl alcohol, meridian, nosyl, aryl or aryl group: and R3 is independently alkenyl alcohol, ⑥ group, aryl group or aryl bond. Preferably 'r2 is ethylene or oxydimethylene and is methyl. If sodium salt of 6,7-diazonal-2-naphthamic acid is the modifier, X will be s03-Na + and each γ will be It is 0H. It should be understood that the Υ Υ group can also be used as a metal ion chelating group. The auto-depositionable component can be present in the composition in any amount that provides effective auto-deposition.-In general, Based on the total # of the non-volatile components in the composition, it may be an amount ranging from 5 to 5 (), preferably 5 to 2 (), and more preferably 7 to 10 to 14 weight percent. The control agent may promote Any material that forms an automatic deposition coating on a metal surface, and optionally can improve the formation of other automatic deposition coatings applied after the automatic deposition coating with a control agent. The addition of the accelerator also promotes automatic ice deposition coating Consistency of the thickness. The composition containing the control agent does not require a stagnation period to form a complete coating. In other words, the conversion of the metal coating depends on the drying of the coated substrate and subsequent application of the coating. Covering the composition containing the control agent can be applied immediately after drying, coating, primer and adhesion and finished. The control agent must also be in contact with the composition without premature solidification or unstable acidic state of the composition. The other components of the composition are compatible. The control agent may be a mononitro compound, an arylene compound, a compound, an acid salt compound, an amine, or a similar material. A mixture of control agents may also be used. Organic nitrate compounds Is a better control agent. The organic stone compound system includes any material in which a nitro group (_NO2) is connected to an organic part. Preferably, the organic nitrate compound is water-soluble, if 22 546413 玖, DESCRIPTION OF THE INVENTION Insoluble in water needs to be dispersible in water. Exemplary organic nitrate compounds include nitro veins, such as nitro or dinitrobenzoate salts, and such as its sodium, potassium, amine or any monovalent metal ion (especially 3, 5- Sodium salts of nitrobenzene sulfonate) are salts of aromatic nitrates; naphthol yellow S; and picric acid (known as tri-5 nitrophenol). It is particularly available based on commercial availability and general reasons. It is preferably a mixture of guanidine and sodium nitrobenzene mineral salt. The amount of the controlling agent in a multi-component composition may be specifically changed depending on the amount of any acid in the composition. Preferably, the amount is The total amount of non-volatile wounds in the composition can be up to 20% by weight, preferably up to 10% by weight, and most preferably 2 to 5% by weight. According to a preferred embodiment, The weight ratio of the nitroguanidine to the nitrobenzene sulfonate should be in the range of 1:10 to 5: 1. The organic nitrate compound is typically mixed into a composition in the form of an aqueous solution or dispersant. For example, nitroguanidine is a solid at room temperature and is soluble in water before being formulated into the composition. 15 The turned-on composition can be prepared by any method known in the art, but it is preferably in a ball mill, a sand mill, a ceramic ball mill, a steel ball mill, a high-speed media mill, or In its analogy, the components are mixed with & It is preferable to add each component to the mixture in a liquid state such as an aqueous dispersant. 20 In the 11 test of osmium salt, these components scored on the metal surface with a-«trowel and placed in a standard salt receiver for one hour. Obtain an assessment of gradual corrosion. Experiments: Coatings that can be deposited automatically: 23 25 546413 发明, Description of the composition Solid wet weight (%) Dry weight (Lu) ® Raven® 14 powder 100 0.43 1.448 Marasperse® BBOSO- 4 100 0.14 0.472 Hope resin Ga. Pacific 4000 51 1.42 19.616 ABS latex 50.250 10.4 17.696 Coronary vein 75 0.090 0.227 DI water 0 77.52 00
塗覆的撤出速率：微小的黏著劑浸潰線係用於該變該 撤出速率。係利用下列撤出速率。 5 第1回合-7.5英尺/分鐘 第2回合2 - 5.7英尺/分鐘 第3回合-3.4英尺/分鐘 第4回合-1.0英尺/分鐘 第5回合-控制組-以手動模擬40英尺/分鐘的工 10 業上的撤出速率。 以下為HRS面板的方法： 24 15 546413 玖、發明說明 方法步驟 化學處理浸入時間 溫度 註 去驗性 Challenge 1245 4分鐘 175°F 8盎司/加命， 有超音波 沖洗 自來水 3分鐘 RT 空氣喷口打開 酸浸 Challenge 2527 5分鐘 130°F 7%體積，有 超音波 沖洗 自來水 15秒 80°F 沖洗 自來水 30秒 120°F MJ金屬處 理 MJ 1100 30秒 RT 批號 03221006 ，DFT等級為 0.19-0.25 密爾 乾燥 7分鐘 220°F 冷卻部件 4分鐘 120- 130°F MJ塗覆 MJ 2110 15秒 RT 批號 03271006 乾燥 8分鐘 200°F B-階段 20分鐘 350°F Blue-M 爐Withdrawal rate of coating: a tiny adhesive dip line is used to change the withdrawal rate. The following withdrawal rates are used. 5 Round 1-7.5 ft / min. Round 2-5.7 ft / min. Round 3-3.4 ft / min. Round 4-1.0 ft / min. Round 5-Control group-to manually simulate 40 ft./min. 10 Industry withdrawal rate. The following is the method of HRS panel: 24 15 546413 发明, invention description method steps chemical treatment immersion time temperature note test 1245 4 minutes 175 ° F 8 ounces / plus life, ultrasonic washing tap water 3 minutes RT air nozzle open acid Soak in Challenge 2527 5 minutes 130 ° F 7% volume, with ultrasonic flush tap water 15 seconds 80 ° F rinse tap water 30 seconds 120 ° F MJ metal treatment MJ 1100 30 seconds RT batch number 03221006, DFT grade 0.19-0.25 mil dry 7 220 ° F Cooling parts 4 minutes 120-130 ° F MJ coated MJ 2110 15 seconds RT Lot 03271006 Drying 8 minutes 200 ° F B-stage 20 minutes 350 ° F Blue-M furnace
結果： 回合數 最後水滴的平均DFT(標準偏 消逝時間 差) (秒） 1 (7.5英尺/分） 17秒（一滴） 1·03 (0.156)密爾 2 (5·7英尺/分） 無水滴 1.14 (0.045)密爾 3 (3.4英尺/分） 無水滴 1.15 (0.054)密爾 4 (1.0英尺/分） 無水滴 1.20 (0.053)密爾 5 (控制組） 3 0秒水滴 1.03 (0.152)密爾 25 546413 玖、發明說明 【圖式簡單說明】 無0 5 【圖式之主要元件代表符號表】 無0 26Results: The average DFT (standard deviation elapsed time difference) of the last water drop for the number of rounds (seconds) 1 (7.5 feet / minute) 17 seconds (one drop) 1.03 (0.156) mil 2 (5 · 7 feet / minute) without water drops 1.14 (0.045) Mill 3 (3.4 ft / min) No water drop 1.15 (0.054) Mill 4 (1.0 ft / min) No water drop 1.20 (0.053) Mill 5 (Control group) 3 0 second water drop 1.03 (0.152) Mill 25 546413 发明. Description of the invention [Simplified description of the drawing] No 0 5 [Representative symbol table of main components of the drawing] No 0 26