TWI395835B - 免沖洗之預處理方法及組合物 - Google Patents
免沖洗之預處理方法及組合物 Download PDFInfo
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Description
本發明係關於用於金屬之不含鉻塗層。特定言之,本發明係關於一種用於鋼、鍍鋅鋼及鋁表面之免沖洗之無鉻酸鹽、無金屬磷酸鹽之塗層,其包含一穩定劑以改良乾燥塗層與表面之黏著性及提供增強之腐蝕防護。
已知各種組合物用於商業應用以製備金屬表面。舉例而言,鉻及重金屬磷酸鹽轉化塗層用於商業應用以在塗漆操作之前製備金屬表面。然而,對於鉻之毒性概況及鉻酸鹽、磷酸鹽及其他重金屬自該等工業製程之廢物流排入河流及水道之污染效應的關注漸增。
因此,此項技術中需要提供一種有效處理物以於適當位置提供乾燥之轉化或鈍化塗層以防止金屬表面腐蝕且增強油漆或其他可塗覆之塗層與表面之黏著性。
本發明係關於一種用以處理諸如鋼、鍍鋅鋼及鋁之金屬表面的方法及組合物,以提供形成轉化或鈍化塗層,該塗層增加了裸金屬或塗漆金屬之抗腐蝕性及/或該金屬之黏著特性。本發明之方法包含使必需金屬表面與穩定之水性溶膠相接觸,該溶膠包含膠狀氧化物粒子(諸如金屬氧化物或二氧化矽粒子)及脲基矽烷化合物。金屬表面與上述處理物接觸之後,該處理物可於適當位置乾燥以形成所要塗層。該處理物較佳大體上無鉻及磷酸鹽。
根據本發明,已發現無鉻且較佳無磷酸鹽之轉化或鈍化塗層可藉由使所要表面與含有膠狀氧化物(含有諸如金屬氧化物溶膠或二氧化矽溶膠之溶膠)之穩定水性溶膠相接觸而提供於金屬表面上,諸如電鍍鋅鋼、冷軋鋼、熱浸鍍鋅鋼、鋁及其他金屬。該等溶膠較佳包括二氧化矽及/或氧化鈰粒子。該等溶膠組合物進一步包含一或多種經水解或部分水解之脲基矽烷。在本發明之一較佳態樣中,將穩定劑(一或多種)添加至溶膠-矽烷混合物中以增強產品之穩定性及存放期。本發明之水性預處理組合物提供裸金屬及塗漆金屬之改良抗腐蝕性及塗覆塗層與塗漆金屬之黏著性。在本發明之上下文中,術語"金屬"係指經本發明之轉化或鈍化塗層處理但未經塗漆之金屬表面。
二氧化矽溶膠材料包含較佳具有酸性pH之水性矽膠。例示性二氧化矽溶膠材料可購自Cabot Corporation及其他供應商,諸如Wacker Chemie、Degussa、Nissan Chemical及Nalco Chemical Company。有效二氧化矽溶膠之一實例(Cab-O-Sperse A205)為溶於去離子水中之高純度煅製二氧化矽之水性分散液。該溶膠具有約5-7之pH及約12%之固體含量。黏度<100 cPs且比重為約1.07。
例示性氧化鈰溶膠亦可購得。一般言之,該等包含水性膠狀懸浮液中之氧化鈰粒子。可舉例說明之市售氧化鈰溶膠包括購自Rhodia及Nyacol Nano Technologies Inc之膠狀氧化鈰硝酸鹽及氧化鈰乙酸鹽。較佳之氧化鈰乙酸鹽溶膠包括約20%之氧化鈰粒子。例示性氧化鈰溶膠包括具有小於約100 nm之粒徑之氧化鈰溶膠。例示性pH為約1-9之級別。亦可提及其他金屬氧化物溶膠,諸如ZnO、ZrO2
、TiO2
及Al2
O3
。
關於現存之脲基矽烷材料,該等包括如式I所述之脲基矽烷,
或該矽烷之水解產物或縮合物,其中D係獨立選自(R3
)或(OR),其限制條件為至少一個D為(OR)。該式中,每一R均係獨立選自由以下各基組成之群:氫、烷基、經烷氧基取代之烷基、醯基、烷基矽烷基或烷氧基矽烷基,且每一R基均可為直鏈或支鏈且可相同或不同。R較佳係個別選自由以下各基組成之群:氫、乙基、甲基、丙基、異丙基、丁基、異丁基、第二丁基及乙醯基。
式I中之X為選自由以下各基組成之群之一員:一鍵或一經取代或未經取代之脂族或芳族基團。X較佳係選自由以下各基組成之群之成員:一鍵、C1
-C1 0
伸烷基、C1
-C6
伸烯基、經至少一個胺基取代之C1
-C6
伸烷基、經至少一個胺基取代之C1
-C6
伸烯基、伸芳基及烷基伸芳基。
R1
及R2
部分係個別選自由以下各基組成之群:氫、C1
-C6
烷基、環烷基、C1
-C6
烯基、經至少一個胺基取代之C1
-C6
烷基、經至少一個胺基取代之C1
-C6
烯基、伸芳基及烷基伸芳基。R1
較佳係個別選自由以下各基組成之群:氫、乙基、甲基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基、環己基及乙醯基。
如本文所用之術語"經取代之"脂族或芳族意謂其中碳主鏈可具有位於該主鏈內之雜原子或連接至該碳主鏈上之雜原子或含有雜原子之基團的脂族或芳族基團。
式I中之R3
為具有1至10個碳原子之單價烴基。R3
基包括烷基、芳基及芳烷基,諸如甲基、乙基、丁基、己基、苯基、苄基。其中,低碳數C1
-C4
烷基為較佳。R3
通常為甲基。
本發明中使用之尤其較佳脲基矽烷為具有以下結構之γ-脲基丙基三甲氧基矽烷:
該化合物可自GE Silicones以名稱"Silquest A-1524"而購得。3-脲基丙基三乙氧基矽烷亦可用於製備水解產物。純3-脲基丙基三乙氧基矽烷為蠟狀固體材料。需要有用之溶解該固體之溶劑或方法。市售之3-脲基丙基三乙氧基矽烷溶解於甲醇中,且因此其非純化合物,而含有連接至相同矽原子上之甲氧基及乙氧基。當完全水解時,矽烷之特性將相同。
除上述溶膠與脲基矽烷之組合以外,已發現該組合之存放期可藉由向其中添加穩定劑而顯著改良。初步資料表明,添加某些穩定劑可延長溶膠/脲基矽烷組合物之存放期。可舉例說明穩定劑之主體。舉例而言,例示者為醇、二元醇、三元醇、多元醇、二醇醚、酯、酮、吡咯啶酮及聚醚矽烷。
特定穩定劑包括:乙醇、1-丙醇、2-丙醇(異丙醇)、2-甲基-1-丙醇(異丁醇)、2-甲基-2-丙醇(第三丁醇)、1-丁醇、2-丁醇、2-甲基-1-丁醇、2-甲基-2-丁醇、2,2-二甲基-1-丙醇、1-戊醇、2-戊醇、4-甲基-2-戊醇;二元醇,包括丙二醇、1,3-丁二醇、1,4-丁二醇、2-甲基-1,3-丙二醇、2-甲基-2,4-戊二醇(己二醇)、二乙二醇、三乙二醇、四乙二醇、聚(乙二醇)、二丙二醇、三丙二醇、聚(丙二醇)、1,5-戊二醇、酯二醇204、2,2,4-三甲基戊二醇、2-乙基-1,3-己二醇;甘油、乙氧基化甘油、乙氧基化-共-丙氧基化甘油三元醇、丙氧基化甘油;異戊四醇;二醇醚,諸如1-甲氧基-2-丙醇(丙二醇甲基醚)、1-乙氧基-2-丙醇、1-丙氧基-2-丙醇、1-丁氧基-2-丙醇、2-甲氧基乙醇、2-乙氧基乙醇、2-丙氧基乙醇、2-丁氧基乙醇、2-(2-甲氧基乙氧基)乙醇、2-(2-乙氧基乙氧基)乙醇、2-(2-丙氧基乙氧基)乙醇、2-(2-丁氧基乙氧基)乙醇(丁基卡必醇(carbitol))、二(丙二醇)丁基醚、甲氧基三乙二醇(三(乙二醇)單甲基醚)、乙氧基三乙二醇(三(乙二醇)單乙基醚)、丁氧基三乙二醇(三(乙二醇)單丁基醚)、甲氧基聚乙二醇(聚(乙二醇)甲基醚)、聚(乙二醇)丁基醚、聚(乙二醇)二甲基醚、聚(乙二醇-共-丙二醇)、聚(乙二醇-共-丙二醇)單丁基醚、聚(丙二醇)單丁基醚、二(丙二醇)二甲基醚;酯,包括乙酸甲酯、乙酸乙酯、乳酸乙酯、2-甲氧基乙酸乙酯、2-乙氧基乙酸乙酯、2-丁氧基乙酸乙酯、2-(2-甲氧基乙氧基)乙酸乙酯、2-(2-乙氧基乙氧基)乙酸乙酯、2-(2-丁氧基乙氧基)乙酸乙酯、二乙酸乙二醇酯、二乙酸三乙二醇酯、丙二醇甲基醚乙酸酯(1-甲氧基-2-丙醇乙酸酯)、丙二醇乙基醚乙酸酯;及酮,包括丙酮、甲基乙基酮、2,4-戊二酮、二丙酮醇及聚醚矽烷(包括Silquest A-1230)。
此外,作為上述組份之可選佐劑,本發明之組合物可包括C1
-C4
烷氧基化矽烷化合物以在工作溶液中提供Si-O鍵。該等佐劑化合物可由下式表示:
其中R4
為具有1至10個碳原子之單價烴基或OR5
且每一R5
係獨立選自C1
-C4
烷基。目前可提及四乙基正矽酸酯(TEOS)或甲基三乙氧基矽烷。該化合物及上式所涵蓋之其他化合物將於溶液中水解以提供Si-O鍵之來源。
目前,本發明之例示性方法包含使所要之金屬表面與水性溶膠相接觸,該水性溶膠包含:(a)Si及/或Ce氧化物粒子及(b)脲基矽烷化合物。如上文所述,該溶膠可包括穩定劑(c)及可選佐劑(d)。
例示性溶膠組合物大體上無鉻酸鹽且較佳大體上無磷酸鹽,且包括:(a)0.001至36重量%之膠狀金屬氧化物或二氧化矽溶膠粒子;(b)0.01至80重量%之脲基矽烷及其水解產物形式;(c)百分比量為約0.00至25重量%之可選穩定添加劑;及(d)約0.00-25重量%之量之可選烷氧基化矽烷化合物或其水解產物;剩餘物主要為水及最小量之pH調節劑。該組合物之重量總計為100重量%。該等溶膠組合物之pH較佳可在約1-7之範圍內。
最佳為具有以下範圍(以重量%計)之組份之組合物:(a)0.001至10重量%之Si及/或Ce氧化物粒子;(b)3至60重量%之脲基矽烷或其水解產物形式;(c)1至15重量%之穩定劑及(d)1-15重量%之佐劑,剩餘物主要為水及微量pH調節劑。
必需金屬表面可藉由噴霧、浸漬或輥軋應用中之處理物來接觸。該處理物經乾燥,且該金屬表面準備用於塗漆或其他塗覆應用。
本發明之轉化或鈍化處理物係塗覆於經處理表面以產生每平方呎經處理表面大於約0.5毫克重量之轉化塗層,每平方呎約2-500毫克之重量為更佳。對於用於商業應用而言,將包含約1-100重量%,較佳5-70重量%濃度之上述調配物的工作溶液用於與所要之金屬表面相接觸。
在本發明之另一實施例中,將諸如MeOH之危險空氣污染物自混合製程中移除,其中首先將脲基矽烷及鈰溶膠混合。在移除相當大量之經由該混合所形成之MeOH或其他揮發物之後,將穩定劑及視情況之水添加至反應混合物中以增強產品之穩定性。在移除MeOH之前,亦可添加穩定劑,尤其為沸點高於水之沸點的穩定劑。
現將結合以下實例來描述本發明,該等實例應認為係對於本發明之某些實施例的說明,而不應將其視為限制本發明。
對以下調配物進行評估以檢查膠狀金屬氧化物矽烷混合物之效能。預處理溶液係藉由混合矽烷、膠狀氧化鈰及水而製備(表1A)。
使用先進塗層實驗室(ACT)面板:冷軋鋼(CRS)及EZ60/60電鍍鋅鋼(EG)。將面板進行如下處理:清潔-Kleen 182,經由在120℉下浸漬,3分鐘接觸時間(CRS)或1分鐘(EG)沖洗-使DI水溢過該面板直至獲得無中斷之水表面於室溫下以空氣乾燥該面板預處理-於室溫下將面板浸入溶液中歷時5秒鐘(CRS)及30秒鐘(EG)使處理溶液自該面板排乾歷時30秒鐘乾燥-使用熱空氣槍來乾燥面板表面上之溶液。
將面板經購自PPG Industries之白Polycron III(AG452W3223)塗漆。根據製造商之說明書塗覆且固化該油漆。塗漆之後,使面板經受根據ASTM B-117之中性鹽噴霧測試(NSS)歷時96小時且根據ASTM D 1654評定自劃線蔓延之毫米數(表1B)。將效能與工業標準鐵及磷酸鋅預處理物相比較。
製備以下調配物以比較各種矽烷之效能。預處理溶液係藉由混合矽烷、膠狀氧化鈰(20%活性物及穩定化乙酸鹽)、矽膠及水來製備(表2A)。使用先進塗層實驗室(ACT)面板-冷軋鋼(CRS)及G70/70熱浸鍍鋅鋼(HDG)。將面板進行如下處理:清潔-3% Kleen 132(可購自GEWPT),130℉,經噴霧塗覆(HDG歷時10秒鐘,CRS歷時30秒鐘)沖洗-5秒鐘,自來水沖洗-5秒鐘,DI水吹風乾燥以自表面移除水
預處理物之旋轉塗覆-將約30至40 ml之預處理溶液溢至面板表面上。旋轉面板以使得過量物質經由離心力而移除。隨後使用暖空氣槍乾燥金屬表面上之剩餘預處理溶液。
將預處理面板如下進行塗漆:HDG-以PPG Truform ZT2黑3MB72689I塗漆CRS-以Akzo Nobel照明設備白PW8R30708塗漆根據製造商之說明書塗覆且固化油漆。
隨後使經塗漆之面板經受根據ASTM B117之中性鹽噴霧測試(NSS)。隨後如經由ASTM D1654所指示,在面板暴露於鹽噴霧中數小時後,經由量測自劃線蔓延之毫米數來評定其抗腐蝕性(表2B)。
注意-對於樣品B至G而言,添加乙酸以將處理溶液之pH調節為4.0至4.3。
Cabosperse A205-12%活性矽膠Silquest A-1524-γ-脲基丙基三甲氧基矽烷Silquest A-1100-γ-胺基丙基三乙氧基矽烷Silquest A-186-β-(3,4-環氧基環己基)乙基三甲氧基矽烷Silquest A-1637-6-胺基己基三甲氧基矽烷Silquest A-1110-γ-胺基丙基三甲氧基矽烷
為證明穩定劑改良基於γ-脲基丙基三甲氧基矽烷+膠狀氧化鈰之預處理物穩定性的能力,在添加及不添加穩定劑之情況下製備濃溶液且對其進行監控以測定直至溶液產生沉澱或凝膠所歷經之天數。(表3及4)。
為詳述可產生穩定水溶液之試劑,製備額外樣品。(表4)。如實例3中,監控溶液以測定直至產生沉澱或凝膠之天數。
根據本發明為使所存在之危險空氣污染物最少化且增強CeO2
/脲基矽烷溶膠之穩定性,移除自γ-脲基丙基三甲氧基矽烷之水解所形成之甲醇。因此,將150公克Silquest A-1524(γ-脲基丙基三甲氧基矽烷)、50公克膠狀CeO2
乙酸鹽溶液(購自Rhodia)及10公克Silquest A-1230(聚醚矽烷)於一32盎司(oz.)瓶中混合20分鐘。混合之後,伴隨攪拌添加365公克D.I.水,繼而添加25.4公克2-甲基-2,4-戊二醇(己二醇,HG)。在約40℃及150-60 mmHg下,將甲醇自反應混合物移除,繼而在周圍溫度下以氮氣噴射以產生362公克黃色澄清溶液。此指示移除了238公克物質,推測為甲醇及水。隨後添加138公克D.I.水以產生含有該活性脲基丙基矽烷化合物(矽烷含量與30%之γ-脲基丙基三甲氧基矽烷水溶液相等)、10% CeO2
(20%固體)及5%己二醇之水溶液。
隨後添加15公克1-甲氧基-2-丙醇(Dowanol PM),且分析該混合物並發現其僅含有0.3%之MeOH。根據ASTM D-2369測定非揮發物之百分比含量為26.8%。
製備以下調配物以評估穩定劑對膠狀氧化鈰+矽烷溶液之效能的影響。
根據實例5中所述之程序,藉由混合矽烷、膠狀氧化鈰、水及添加劑(Dowanol PM、2-甲基-1,3-丙二醇、2-甲基-2,4-丙二醇、Silquest A-1230)來製備預處理濃縮物。(表6A)。
表6A
將ACT實驗室冷軋鋼(CRS)及G70熱浸鍍鋅鋼(HDG)及Q面板3105合金鋁進行如下處理:清潔-Kleen132,於130℉下,HDG噴霧5秒鐘,CRS噴霧30秒鐘及鋁噴霧5秒鐘沖洗-DI水,5秒鐘於室溫下以空氣乾燥面板預處理-將預處理濃縮物以DI水稀釋至10%重量比且經由反輥塗佈而塗覆乾燥-使用熱空氣槍面板表面上之溶液
將冷軋鋼面板以購自Akzo Nobel Coatings之照明設備白(PW8R30708)塗漆,將鋁面板以購自Valspar Corporation之熱固性白聚酯(91101-76441)塗漆,且將熱浸鍍鋅面板以購自PPG Industries之黑Truform ZT2(3MB72689I)塗漆。根據製造商之說明書塗覆及固化該油漆。塗漆之後,使CRS及HDG面板經受根據ASTM B-117之中性鹽噴霧測試(NSS)分別歷時336小時及500小時。使鋁面板經受根據ASTM B 117-97,附錄I之乙酸鹽噴霧(AASS)歷時500小時。隨後根據ASTM D 1654評定所有面板上自劃線蔓延之毫米數(mm)(表6B、C、D)。
表6D
AASS暴露鋁蔓延mm
儘管本發明已結合其特定實施例而詳述,但應易於瞭解,本發明並非限於該等所揭示之實施例。相反,本發明可經修正以併入任意數目之至今尚未描述但與本發明之精神與範疇相符之變化、變更、替代物或等效物。因此,本發明並非受限於前文之描述。
Claims (13)
- 一種組合物,其實質上由下列所組成:(a)具有以下式(II)結構之脲基矽烷之部分或完全縮合物
- 如請求項1之組合物,其中該脲基矽烷(a)為γ-脲基丙基三甲氧基矽烷或3-脲基丙基三乙氧基矽烷。
- 如請求項1之組合物,其中該包含氧化鈰粒子之膠狀氧化物溶膠係選自由具有小於約100 nm之粒徑之氧化鈰硝酸鹽及氧化鈰乙酸鹽所組成之群。
- 如請求項1之組合物,其中該脲基矽烷之部分或完全縮合物(a)之含量係由0.01重量%至80重量%,而該包含氧化鈰 粒子之膠狀氧化物溶膠(b)之含量係由0.001重量%至36重量%,以及該視需要之穩定劑(d)之含量係由0.00重量%至25重量%。
- 如請求項4之組合物,其中該穩定劑(d)係選自由下列所組成之群:乙醇、1-丙醇、2-丙醇、2-甲基-1-丙醇、2-甲基-2-丙醇、1-丁醇、2-丁醇、2-甲基-1-丁醇、2-甲基-2-丁醇、2,2-二甲基-1-丙醇、1-戊醇、2-戊醇、4-甲基-2-戊醇、丙二醇、1,3-丁二醇、1,4-丁二醇、2-甲基-1,3-丙二醇、2-甲基-2,4-戊二醇、二乙二醇、三乙二醇、四乙二醇、聚(乙二醇)、二丙二醇、三丙二醇、聚(丙二醇)、1,5-戊二醇、酯二醇204、2,2,4-三甲基戊二醇、2-乙基-1,3-己二醇、甘油、乙氧基化甘油、乙氧基化-共-丙氧基化甘油三元醇、丙氧基化甘油、異戊四醇、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、1-丙氧基-2-丙醇、1-丁氧基-2-丙醇、2-甲氧基乙醇、2-乙氧基乙醇、2-丙氧基乙醇、2-丁氧基乙醇、2-(2-甲氧基乙氧基)乙醇、2-(2-乙氧基乙氧基).乙醇、2-(2-丙氧基乙氧基)乙醇、2-(2-丁氧基乙氧基)乙醇、二(丙二醇)丁基醚、三(乙二醇)單甲基醚、三(乙二醇)單乙基醚、三(乙二醇)單丁基醚、聚(乙二醇)甲基醚、聚(乙二醇)丁基醚、聚(乙二醇)二甲基醚、聚(乙二醇-共-丙二醇)、聚(乙二醇-共-丙二醇)單丁基醚、聚(丙二醇)單丁基醚、二(丙二醇)二甲基醚、乙酸甲酯、乙酸乙酯、乳酸乙酯、2-甲氧基乙酸乙酯、2-乙氧基乙酸乙酯、2-丁氧基乙酸乙酯、2-(2-甲氧基乙氧基)乙酸乙酯、2-(2-乙氧基乙氧基)乙酸乙酯、 2-(2-丁氧基乙氧基)乙酸乙酯、二乙酸乙二醇酯、二乙酸三乙二醇酯、1-甲氧基-2-丙醇乙酸酯、丙二醇乙基醚乙酸酯、丙酮、甲基乙基酮、2,4-戊二酮及二丙酮醇。
- 如請求項1之組合物,其中該組合物無危險空氣污染物甲醇及/或揮發物。
- 一種處理金屬表面以於其上形成轉化或鈍化塗層之方法,其包含使該金屬表面與一組合物相接觸,該組合物實質上由下列所組成:(a)具有以下式(II)結構之脲基矽烷之部分或完全縮合物;
- 如請求項7之方法,其中該脲基矽烷(a)為γ-脲基丙基三甲 氧基矽烷或3-脲基丙基三乙氧基矽烷。
- 如請求項7之方法,其中該包含氧化鈰粒子之膠狀氧化物溶膠係選自由具有小於約100 nm之粒徑之氧化鈰硝酸鹽及氧化鈰乙酸鹽所組成之群。
- 如請求項7之方法,其中該脲基矽烷之部分或完全縮合物(a)之含量係由0.01重量%至80重量%,而該包含氧化鈰粒子之膠狀氧化物溶膠(b)之含量係由0.001重量%至36重量%,以及該視需要之穩定劑(d)之含量係由0.00重量%至25重量%。
- 如請求項7之方法,其中該穩定劑(d)係選自由下列所組成之群:乙醇、1-丙醇、2-丙醇、2-甲基-1-丙醇、2-甲基-2-丙醇、1-丁醇、2-丁醇、2-甲基-1-丁醇、2-甲基-2-丁醇、2,2-二甲基-1-丙醇、1-戊醇、2-戊醇、4-甲基-2-戊醇、丙二醇、1,3-丁二醇、1,4-丁二醇、2-甲基-1,3-丙二醇、2-甲基-2,4-戊二醇、二乙二醇、三乙二醇、四乙二醇、聚(乙二醇)、二丙二醇、三丙二醇、聚(丙二醇)、1,5-戊二醇、酯二醇204、2,2,4-三甲基戊二醇、2-乙基-1,3-己二醇、甘油、乙氧基化甘油、乙氧基化-共-丙氧基化甘油三元醇、丙氧基化甘油、異戊四醇、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、1-丙氧基-2-丙醇、1-丁氧基-2-丙醇、2-甲氧基乙醇、2-乙氧基乙醇、2-丙氧基乙醇、2-丁氧基乙醇、2-(2-甲氧基乙氧基)乙醇、2-(2-乙氧基乙氧基)乙醇、2-(2-丙氧基乙氧基)乙醇、2-(2-丁氧基乙氧基)乙醇、二(丙二醇)丁基醚、三(乙二醇)單甲基醚、三(乙二醇)單乙基醚、三(乙 二醇)單丁基醚、聚(乙二醇)甲基醚、聚(乙二醇)丁基醚、聚(乙二醇)二甲基醚、聚(乙二醇-共-丙二醇)、聚(乙二醇-共-丙二醇)單丁基醚、聚(丙二醇)單丁基醚、二(丙二醇)二甲基醚、乙酸甲酯、乙酸乙酯、乳酸乙酯、2-甲氧基乙酸乙酯、2-乙氧基乙酸乙酯、2-丁氧基乙酸乙酯、2-(2-甲氧基乙氧基)乙酸乙酯、2-(2-乙氧基乙氧基)乙酸乙酯、2-(2-丁氧基乙氧基)乙酸乙酯、二乙酸乙二醇酯、二乙酸三乙二醇酯、1-甲氧基-2-丙醇乙酸酯、丙二醇乙基醚乙酸酯、丙酮、甲基乙基酮、2,4-戊二酮及二丙酮醇。
- 如請求項7之方法,其中該表面上之轉化或鈍化塗層係大於0.5 mg/平方呎。
- 如請求項7之方法,其中該組合物無危險空氣污染物甲醇及/或揮發物。
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Also Published As
Publication number | Publication date |
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CN101248213B (zh) | 2012-09-05 |
RU2410468C2 (ru) | 2011-01-27 |
US10041176B2 (en) | 2018-08-07 |
BRPI0610448B1 (pt) | 2018-02-06 |
CA2603708C (en) | 2014-07-08 |
JP2008537980A (ja) | 2008-10-02 |
KR101510259B1 (ko) | 2015-04-08 |
RU2007141164A (ru) | 2009-05-20 |
MX2007012320A (es) | 2008-03-07 |
EP1871924A1 (en) | 2008-01-02 |
TW200700580A (en) | 2007-01-01 |
US20070090329A1 (en) | 2007-04-26 |
JP4958895B2 (ja) | 2012-06-20 |
US8609755B2 (en) | 2013-12-17 |
EP1871924B1 (en) | 2015-05-06 |
BRPI0610448A2 (pt) | 2010-06-22 |
CN101248213A (zh) | 2008-08-20 |
KR20070121041A (ko) | 2007-12-26 |
WO2006110328A1 (en) | 2006-10-19 |
CA2603708A1 (en) | 2006-10-19 |
US20060228470A1 (en) | 2006-10-12 |
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