TWI791757B - 飽和共聚酯樹脂及包含其之塗層組成物 - Google Patents

飽和共聚酯樹脂及包含其之塗層組成物 Download PDF

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TWI791757B
TWI791757B TW108104224A TW108104224A TWI791757B TW I791757 B TWI791757 B TW I791757B TW 108104224 A TW108104224 A TW 108104224A TW 108104224 A TW108104224 A TW 108104224A TW I791757 B TWI791757 B TW I791757B
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金炯坤
沈宗基
金舜琪
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南韓商Ｓｋ化學公司
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Abstract

本發明有關一種共聚飽和聚酯樹脂及包含其之塗層組成物。本發明提供一種共聚飽和聚酯樹脂及一種塗層組成物，其等可用於預塗金屬(PCM)以及罐頭之內外表面的塗佈，因為其等當形成塗膜時具有優異的耐腐蝕性及耐化學性，且具有良好的樹脂溶解度及加工性。

Description

飽和共聚酯樹脂及包含其之塗層組成物
發明領域 本發明有關一種共聚飽和聚酯樹脂及包含其之塗層組成物。更詳細地，本發明有關一種共聚飽和聚酯樹脂，其可用於保護金屬基材，因為其當形成塗膜時具有優異的耐腐蝕性及耐化學性，且具有良好的樹脂溶解度及加工性；及一種包含其之塗層組成物。
發明背景 用於保護金屬材料之塗層，主要用於防止水或酸性或鹼性水溶液之腐蝕。因此，塗膜需具有優異的耐腐蝕性及耐化學性。
包含高分子量飽和聚酯樹脂之塗層組成物具有優異的加工性。但是，因為其物理特性很容易因水或酸性或鹼性水溶液而變差，所以很難將其應用於需要耐腐蝕性之用途。
特別是，聚酯樹脂之物理特性的惡化，在高溫條件下會進一步加速。因此，不可避免的需改善在高溫下對水或酸性或鹼性水溶液之耐腐蝕性，以便能用聚酯樹脂塗佈金屬。
此外，為了使樹脂能應用於塗層組成物，其必須能夠穩定地溶解或分散於溶劑或水中。然而，通常為提高耐腐蝕性及耐化學性目的而改質之樹脂，往往在溶劑中具有低溶解度。
為了達到樹脂之此溶解度及耐腐蝕性之改善，傳統上是透過各種單體之組合研發高分子量聚酯樹脂。然而，目前為止所研發之聚酯樹脂無法同時滿足溶解度及耐腐蝕性。相反的可能會削弱加工性，其是高分子量飽和聚酯的固有優點。
技術問題 由聚酯樹脂形成之塗膜的特性因水或酸性或鹼性水溶液而變差之現象，已知主要是因為濕氣穿透且擴散至塗膜，導致聚酯樹脂水解所引起。為了抑制物理特性因濕氣而變差，黏合樹脂及固化劑組份必須化學鍵結以具有高固化密度，使得濕氣幾乎難以穿透及擴散進入塗層。
本發明進行研究結果發現，通過設計樹脂之結構使得濕氣難以接近酯鍵可以確保水解穩定性，而通過控制樹脂之玻璃轉移溫度從而抑制塗膜在高溫下之流動性可顯著地改善耐腐蝕性及耐化學性。此外，確定即使在通過控制樹脂之組份之高玻璃轉移溫度下，聚酯樹脂於溶劑中之溶解度及塗膜之加工性亦獲得改善。
據此，本發明之一目的是提供一種共聚飽和聚酯樹脂，其溶解度及加工性優異且能夠產生具有優異的耐腐蝕性及耐化學性之塗膜。
此外，本發明之另一目的是提供一種塗層組成物，其包含該共聚飽和聚酯樹脂。解決問題之技術方法
根據本發明之目的，提供一種共聚飽和聚酯樹脂，其由酸組份與醇組份之聚縮合形成，且具有60至120℃之玻璃轉移溫度、0.4至0.7dl/g之本質黏度、12,000至20,000g/mol之數量平均分子量，其中該酸組份包含(a-1) 90至99莫耳%之芳族二羧酸或其C1-2 烷酯及(a-2) 0.5至2莫耳%之三官能或更高官能羧酸或其酐，及該醇組份包含(b-1) 45至80莫耳%之脂環族多元醇及(b-2) 20至55莫耳%之具有C1-3 烷基側鏈之脂族多元醇。
根據本發明之另一目的，提供一種塗層組成物，其包含該共聚飽和聚酯樹脂。本發明之有利效果
該共聚飽和聚酯樹脂當形成塗膜時，具有優異的耐腐蝕性及耐化學性，且在溶劑中具有良好的加工性及溶解度。因此，其可用作為保護金屬基材之塗層。
因此，包含該共聚飽和聚酯樹脂之塗層組成物，特別可用於塗佈預塗金屬(PCM)以及罐頭之內外表面。
實施本發明之最佳模式 以下，將更詳細說明本發明。共聚飽和聚酯樹脂
本發明提供一種共聚飽和聚酯樹脂，其由酸組份與醇組份之聚縮合形成，且具有60至120℃之玻璃轉移溫度、0.4至0.7dl/g之本質黏度、12,000至20,000g/mol之數量平均分子量，其中該酸組份包含(a-1) 90至99莫耳%之芳族二羧酸或其C1-2 烷酯及(a-2) 0.5至2莫耳%之三官能或更高官能羧酸或其酐，及該醇組份包含(b-1) 45至80莫耳%之脂環族多元醇及(b-2) 20至55莫耳%之具有C1-3 烷基側鏈之脂族多元醇。 (a)酸性組份
該共聚飽和聚酯樹脂包含(a-1)芳族二羧酸或其C1-2 烷酯及(a-2)三官能或更高官能羧酸或其酐，作為酸組份。
該共聚飽和聚酯組成物由於酸組份(a-1)而在結構上流動性較低，因此可抑制濕氣的擴散。此外，由於該酸組份(a-2)形成支鏈結構，所以可獲得具有更緻密結構之塗膜。因此，能藉由有效地抑制濕氣之移動及擴散而提高耐腐蝕性及耐化學性。
該酸組份(a-1)可為至少一種選自於由下列所構成之群組：間苯二甲酸、對苯二甲酸、2,6-萘二羧酸及其C1-2 烷酯。
該酸組份(a-1)之含量(以總酸組份計)為90至99莫耳%。假如該酸組份(a-1)之含量小於90莫耳%，則該樹脂之玻璃轉移溫度會太低，從而使其很難保有適當的耐腐蝕性及硬度。更具體地，該酸組份(a-1)之含量(以總酸組份計)可為90至95莫耳%、93至99莫耳%、95至99莫耳%或93至97莫耳%。
此外，該酸組份(a-2)可為選自於苯三甲酸及其酐中之至少一種。
該酸組份(a-2)之含量(以總酸組份計)為0.5至2莫耳%。假如該酸組份(a-2)之含量小於0.5莫耳%，則 其很難獲得足夠的耐腐蝕性位準。假如該含量大於2莫耳%，則在樹脂之合成期間會發生凝膠化，或該樹脂之黏度會變得過高，從而降低塗層之加工性。更具體地，該酸組份(a-2)之含量(以總酸組份計)可為0.5至1.5莫耳%、1至2莫耳%、1.5至2莫耳%或0.5至1莫耳%。 (b)醇組份
該共聚飽和聚酯樹脂包含(b-1)脂環族多元醇及(b-2)具有C1-3 烷基側鏈之脂族多元醇，作為酸組份。
因為該共聚飽和聚酯樹脂包含該脂環族多元醇及該脂族多元醇組份，其使得濕氣變得難以接近酯鍵，從而保有耐水解性。
雖然該樹脂之支鏈結構對於提高耐腐蝕性及耐化學性非常有用，但會因此使得該樹脂之加工性變差。因此，可在該樹脂中使用具有脂環族結構之多元醇，以賦予可撓性及提高加工性。
較佳地，該共聚飽和聚酯樹脂包含三環癸烷二甲醇作為該醇組份(b-1)，如此可保有該飽和聚酯樹脂之溶解度及該樹脂之加工性。此外，其可進一步包含選自於環己烷二甲醇及異山梨醇中之至少一種。
即，該醇組份(b-1)可為三環癸烷二甲醇，或三環癸烷二甲醇與環己烷二甲醇及異山梨醇中之至少一種的混合物。
該醇組份(b-1)之含量(以總醇組份計)為45至80莫耳%。假如該醇組份(b-1)之含量在以上範圍內，則其能夠提高樹脂之玻璃轉移溫度及耐腐蝕性，以及良好的溶解度。假如該含量小於45莫耳%，則很難獲得足夠的耐腐蝕性及耐化學性。假如該含量大於80莫耳%，則很難進行樹脂之聚合反應或加工性會顯著地降低。
更具體地，該醇組份(b-1)之含量(以總醇組份計)可為45至75莫耳%、45至70莫耳%、45至65莫耳%或50至80莫耳%。
此外，該醇組份(b-2)可為至少一種選自於由下列所構成之群組：2-甲基-1,3-丙二醇、1,3-丙二醇及1,2-丙二醇。
特別是，構成該醇組份(b-2)之側鏈之碳原子的總合較佳地為3或更少。
假如作為側鏈之碳鏈很長，則當施用塗層組成物時，可能削弱耐化學性及耐熱水性。
該醇組份(b-2)之含量(以總醇組份計)是20至55莫耳%。假如該醇組份(b-2)之含量在以上範圍內，則可保有聚合反應性、溶解度、流動性及加工性。假如該含量小於20莫耳%，則聚合反應性會顯著地降低。假如該含量大於55莫耳%，則耐腐蝕性及耐化學性變低。
更具體地，該醇組份(b-2)之含量(以總醇組份計)可為25至55莫耳%、30至55莫耳%、35至55莫耳%或20至50莫耳%。
同時，該醇組份較佳地不含2,2-二甲基-1,3-丙二醇。
假如使用包含2,2-二甲基-1,3-丙二醇之聚酯樹脂形成塗膜，則當該膜與含醇之食物接觸時，會顯著地削弱塗膜之耐腐蝕性。共聚飽和聚酯樹脂之特徵
在本發明中，因該共聚飽和聚酯樹脂具有一特定位準之高分子量，所以其可在加工塗層基材時賦予可撓性。
該共聚飽和聚酯樹脂可具有0.4至0.7dl/g，更具體地0.45至0.60dl/g、0.45至0.65dl/g或0.4至0.6dl/g之本質黏度。
該共聚飽和聚酯樹脂具有12,000至20,000g/mol之數量平均分子量。假如該共聚飽和聚酯樹脂之數量平均分子量小於12,000g/mol，則加工性會變差。假如其大於20,000g/mol，則黏性增加，其用於油漆時，會削弱塗層加工性。
更具體地，該共聚飽和聚酯樹脂可具有14,000至19,000g/mol、16,000至19,000g/mol、14,000至17,000g/mol、12,000至17,000g/mol或16,000至20,000g/mol之數量平均分子量。
較佳地，該共聚飽和聚酯樹脂可具有在2.0至4.0範圍內之多分散性指數(PDI)。該多分散性指數計算為重量平均分子量對數量平均分子量之比(Mw/Mn)，其是決定支鏈結構是否能夠改善樹脂之耐熱水性的指標。假如該共聚飽和聚酯樹脂之多分散性指數在2.0至4.0之範圍內，則有利的是可獲得良好的耐腐蝕性及熔化黏度。
更具體地，該共聚飽和聚酯樹脂可具有在2.0至3.0、3.0至4.0、2.5至4.5、2.5至4.0或2.0至3.5範圍內之PDI。
該共聚飽和聚酯樹脂可具有在60至120℃之玻璃轉移溫度(Tg)。假如該共聚飽和聚酯樹脂之Tg為60至120℃時，則該樹脂塗膜在高溫下之流動性會受到抑制，從而提高耐腐蝕性及耐化學性。
更具體地，該共聚飽和聚酯樹脂可具有在60至110℃、60至100℃、70至110℃、80至110℃或65至105℃範圍內之Tg。用於製備共聚飽和聚酯樹脂之方法
本發明之共聚飽和聚酯樹脂可經由習用酯化及聚縮合方法製得。例如，將酸組份及醇組份載入反應器中，接著於其中添加酯化催化劑。之後，將溫度從室溫大幅地升高至約200至260℃。當排出諸如水或甲醇之副產物時，添加聚縮合催化劑及熱安定劑。將反應溫度提高至220至300℃，然後進行共聚合反應數個小時，至獲得具有適當本質黏度之聚酯樹脂。
在此情況下，所使用的酸組份及醇組份之例子如上。
此外，可將三官能或更高官能羧酸或其酐分開並添加於生產時之酯化反應步驟及聚縮合步驟中，以便適當地控制聚合物之結構。
具體地，可將該三官能或更高官能羧酸或其酐進料於該酯化步驟中，以便獲得支鏈結構。選擇性地，其可加至聚縮合步驟中，用以調整酸值以及適當位準的支鏈結構，從而增加塗膜之黏附性。
在該共聚飽和聚酯樹脂之生產期間，可進一步添加酯化催化劑、聚縮合催化劑、熱安定劑等等。該酯化催化劑之例子包括Ca、Ce、Pb、Mn、Zn、Mg、Sb或相似物之醋酸鹽及四丁氧基鈦。此外，該聚縮合催化劑之例子包括Sb2 O3 、 GeO2 、四丁氧基鈦等等。該熱安定劑之例子包括磷酸鹽、磷酸等等。
特別是，在本發明中，可通過與不含不飽和鍵(如雙鍵)之化合物(用作為該聚酯樹脂之聚合反應的單體之酸組份及醇組份)進行酯化及聚縮合反應，在其最終樹脂結構中提供不含不飽和鍵之共聚飽和聚酯樹脂。
如上所述，因為本發明之共聚飽和聚酯樹脂不含不飽和鍵，所以能防止物理特性因應熱、光等等而改變。此外，如上所述之共聚飽和聚酯樹脂可適合作為用於形成塗膜之熱塑性樹脂。塗層組成物
本發明亦提供一種塗層組成物，其包含該共聚飽和聚酯樹脂。
例如，該塗層組成物可包含共聚飽和聚酯樹脂、固化劑、溶劑、添加物等等。
在此情況下，該共聚飽和聚酯樹脂之組成及特徵如上所述。
該固化劑可為至少一種選自於由下列所構成之群組：酚醛樹脂、多官能聚異氰酸酯化合物、三聚氰胺-甲酫樹脂、苯代三聚氰胺(benzoguanamine)樹脂及其組合。較佳地，假如酚醛樹脂或苯代三聚氰胺樹脂用作為固化劑，則其有利於在耐腐蝕性及耐化學性方面獲得優異的物理特性。市售酚醛樹脂之例子包括Allnex之PR516、PR566、PR827及VPR1785及CYMEL659。
該共聚飽和聚酯樹脂對該固化劑之重量比可在95：5至40：60之範圍內，更具體地在90：10至50：50之範圍內。
該溶劑可為酯基、甘醇醚基、酮基、芳族烴基、脂族烴基或醇基溶劑。更具體地，適合的有二甲苯、丙二醇單醋酸乙酯及二元酯。
此外，該添加物之例子可包括顏料、蠟、潤滑劑、消泡劑、潤濕劑、催化劑等等。
該塗層組成物特別地可用於塗佈罐頭的內外表面及PCM，因為其在耐腐蝕性及耐化學性方面具顯著地改善且加工性優異。實行本發明之實施例 具體例及試驗例
以下，將參考範例詳述本發明，但本發明之範疇並不限於此。
下列範例中之測量及評估方法如下。
-本質黏度(IV)：使用Cannon-UbbeLodhe型黏度計，在35℃下用鄰氯苯酚溶劑測量。
-玻璃轉移溫度(Tg)：利用微差掃描熱量法(DSC)測量。
-數量平均分子量(Mn)及重量平均分子量(Mw)：將樣本溶於四氫呋喃中，然後使用凝膠滲透層析法(WATERS GPC 150-CV)測量。聚苯乙烯(Shodex SM-105, Showa Denko, Japan)用作為標準材料。
-樹脂溶解度：當將樣本溶於諸如甲基乙基酮之溶劑中時，假如維持透明均勻狀態，則評估為良好，假如相分離或發生混濁，則評估為不溶。
-耐溶劑性：將樣本塗佈在具有厚度0.3mm之鍍錫鋼板上，用210℃熱空氣乾燥10分鐘，以獲得塗層鋼板。將軟布用甲基乙基酮(MEK)浸泡並纏繞在手指上。用該布往復擦拭該塗層鋼板表面，計數往復擦拭之次數，直到塗層損壞。
-耐腐蝕性：將樣本塗佈在具有厚度0.3mm之鍍錫鋼板上，用210℃熱空氣乾燥10分鐘，以獲得塗層鋼板。對該塗層鋼板進行衝擊試驗(Dupont衝擊試驗)，之後將其浸到含有3%醋酸及3% NaCl之水溶液中。之後將其存放在高壓滅菌器中131℃下30分鐘，且浸到硫酸銅溶液中60分鐘。之後，將表面分成五個具有相同面積之區域，然後計數沒有腐蝕的區域數。即，當所有的區域均被腐蝕時評估為0/5，當沒有區域被腐蝕時評估為5/5。A. 共聚飽和聚酯樹脂之製備
將以下表1所示之組成物中的酸組份及醇組份載入設置溫度計、冷凝器、套筒、攪拌器和真空泵之2000ml四頸燒瓶中，接著於其中加入四丁氧基鈦作為酯化催化劑。當溫度大幅升高至240℃，產生理論數量的水及甲醇之副產物時，於其中加入作為聚縮合催化劑之四丁氧基鈦。使溫度升高至260℃，然後在真空下反應數個小時。結果獲得如以下表1所示，具有0.4至0.65dl/g之本質黏度及12,000至20,000g/mol之數量平均分子量的共聚飽和聚酯樹脂。 [表1]
Figure 108104224-A0304-0001
 B. 塗層組成物之製備
用溶劑Naphtha-100/二元酯(5/5，v/v)之混合溶劑稀釋每個實驗1至4及比較例1至4中製得之共聚飽和聚酯樹脂，製備具有40重量%固體含量之樹脂溶液。其進一步與以下表2所示之組份化合，最後製得具有35重量%固體含量之塗層組成物。 [表2]
Figure 108104224-A0304-0002
 C. 塗層之評估
將各個以上製得之塗層組成物塗佈在具有厚度0.3mm至厚度6至10µm之鍍錫鋼板上，使其在自動排出型烤箱中以210℃乾燥及固化10分鐘，獲得一塗膜。評估該塗膜之樹脂溶解度、耐溶劑性及耐腐蝕性。結果示於以下表3中。此外，圖1顯示經耐腐蝕試驗之塗層鋼板的照片。 [表3]
Figure 108104224-A0304-0003
如以上表3及圖1所示，當塗佈根據範例之各個共聚飽和聚酯樹脂時，該樹脂溶解度、耐溶劑性及耐腐蝕性均非常優異。
圖1顯示評估由範例1至4及比較例2與3之共聚聚酯樹脂所形成之塗膜之耐腐蝕性的結果。

Claims (7)

  1. 一種共聚飽和聚酯樹脂，其由酸組份與醇組份之聚縮合形成，且具有60至120℃之玻璃轉移溫度、0.4至0.7dl/g之本質黏度、12,000至20,000g/mol之數量平均分子量，其中該酸組份包含(a-1)90至99莫耳%之芳族二羧酸或其C1-2烷酯及(a-2)0.5至2莫耳%之三官能或更高官能羧酸或其酐，及該醇組份包含(b-1)45至80莫耳%之脂環族多元醇及(b-2)20至55莫耳%之具有C1-3烷基側鏈之脂族多元醇，及其中該醇組份(b-2)是選自於由下列所構成之群組之至少一者：2-甲基-1,3-丙二醇、1,3-丁二醇及1,2-丙二醇。
  2. 如請求項1之共聚飽和聚酯樹脂，其中該酸組份(a-1)是選自於由下列所構成之群組之至少一者：間苯二甲酸、對苯二甲酸、2,6-萘二羧酸及其C1-2烷酯；及該酸組份(a-2)是選自於苯三甲酸(trimellitic acid)及其酐中之至少一者。
  3. 如請求項1之共聚飽和聚酯樹脂，其中該醇組份(b-1)是三環癸烷二甲醇，或三環癸烷二甲醇與環己烷二甲醇及異山梨醇中至少一者之混合物。
  4. 如請求項1之共聚飽和聚酯樹脂，其中該酸組份(a-1)是選自於由下列所構成之群組之至少一者：間苯二甲酸、對苯二甲酸、2,6-萘二羧酸及其C1-2烷酯； 該酸組份(a-2)是選自於苯三甲酸及其酐中之至少一者；及該醇組份(b-1)是三環癸烷二甲醇，或三環癸烷二甲醇與環己烷二甲醇及異山梨醇中至少一者之混合物。
  5. 如請求項1之共聚飽和聚酯樹脂，其具有2.0至4.0之多分散性指數。
  6. 一種塗層組成物，其包含如請求項1至5中任一項之共聚飽和聚酯樹脂。
  7. 如請求項6之塗層組成物，其進一步包含一固化劑，其中該固化劑是選自於由下列所構成之群組之至少一者：酚醛樹脂、多官能聚異氰酸酯化合物、三聚氰胺-甲醛樹脂、苯代三聚氰胺(benzoguanamine)樹脂及其組合。
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