TWI822673B - 濕固型聚胺酯熱熔樹脂組成物 - Google Patents

濕固型聚胺酯熱熔樹脂組成物 Download PDF

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TWI822673B
TWI822673B TW107108962A TW107108962A TWI822673B TW I822673 B TWI822673 B TW I822673B TW 107108962 A TW107108962 A TW 107108962A TW 107108962 A TW107108962 A TW 107108962A TW I822673 B TWI822673 B TW I822673B
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adhesive composition
polyurethane hot
polyol
melt adhesive
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施鋭
白晨豔
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美商陶氏全球科技有限責任公司
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Abstract

本發明提供聚胺酯熱熔黏著劑組成物,其包含多元醇組分及異氰酸酯組分,其中所述多元醇組分包含具有兩個或更多個OH基團及氫橋聯基團之多元醇。

Description

濕固型聚胺酯熱熔樹脂組成物
本發明係關於濕固型聚胺酯熱熔樹脂組成物,其對於紙張/箔層合具有改進黏合強度及熱封強度。本發明亦關於黏著劑及使用此類組成物之製品。
習知反應性聚胺酯熱熔黏著劑用於包裝、紙張轉換、紙構造、裝訂、紙盒、紙箱密封、建築、汽車,及其類似者。反應性聚胺酯熱熔黏著劑形成極耐用之製品且特別適用於製作包裝及教科書。
習知反應性聚胺酯熱熔黏著劑為濕固型或濕交聯黏著劑,其在室溫下為固體但其以熔體形式應用。黏著劑之聚合組分含有胺基甲酸酯基團及反應性異氰酸酯基團。熔體之冷卻首先引起熱熔黏著劑之快速物理定型,隨後在環境中之濕氣情況下異氰酸酯基之化學反應仍存在從而形成交聯不溶黏著劑。
然而,當將習知反應性聚胺酯熱熔黏著劑應用於紙/箔層合時,存在一些對於此應用之限制。首先,習知反應性聚胺酯之較高黏度導致不佳潤濕能力及較低層合速度。同時,較高應用溫度(例如高於100℃)並不適用於紙/薄膜層合。此外,習知反應性聚氨酯顯示對箔結構之不佳黏合強度。特定言之,熱封後,完全固化的習知反應性聚胺酯黏著劑將很容易自箔剝離。
因此在本領域中需要具有包括黏合強度及熱封強度之改進性能、尤其適用於黏附箔及紙的新穎聚胺酯熱熔黏著劑。
本發明提供聚胺酯熱熔黏著劑組成物,其包含多元醇組分及異氰酸酯組分,其中所述多元醇組分包含具有兩個或更多個OH基團及氫橋聯基團之多元醇。
根據本發明之聚胺酯熱熔黏著劑組成物包含多元醇組分及異氰酸酯組分。 多元醇組分
聚胺酯熱熔黏著劑組成物包含多元醇組分,所述多元醇組分包含具有兩個或更多個OH基團及氫橋聯基團之多元醇以及選自由聚酯多元醇、聚醚多醇及其組合組成之群的視情況選用之多元醇。多元醇組分可視情況包括黏著促進劑以及二醇或三醇單體。
具有兩個或更多個OH基團及氫橋聯基團之多元醇為具有兩個或更多個末端OH基團(即在多元醇分子鏈末端)及分子鏈一側中之至少一個氫橋聯基團(即分支鏈基團)的多元醇。適合的氫橋聯基團之實例包括但不限於O=C-Oˉ、O=C-C-Oˉ及O=C-C=C-Oˉ,及其質子化形式。具有兩個或更多個OH基團及氫橋聯基團之所揭示多元醇進一步具有至少50 mg KOH/g且不超過200 mg KOH/g之酸值。另外,所揭示多元醇具有至少400 g/mol且不超過5,000 g/mol之分子量。再者,所揭示多元醇具有至少1.8且不超過3之羥基官能度(即1.8 ≤f ≤ 3)。在一些實施例中,具有兩個或更多個OH基團及氫橋聯基團之多元醇為聚酯多元醇。
在黏著劑組成物中具有兩個或更多個OH基團及氫橋聯基團之多元醇的量為按黏著劑組成物之重量計至少4wt%、或至少5 wt%、或至少6 wt%。在黏著劑組成物中具有兩個或更多個OH基團及氫橋聯基團之多元醇的量按黏著劑組成物之重量計並不超過45 wt%、或50 wt%、或80 wt%。
具有兩個或更多個羥基之化合物為「多元醇」。具有恰好兩個羥基之多元醇為「二醇」。具有恰好三個羥基之多元醇為「三醇」。在原子之相同直鏈中含有兩個或更多個酯鍵之化合物在本文中稱為「聚酯」。作為聚酯及多元醇之化合物在本文中已知為「聚酯多元醇」。所揭示聚酯多元醇之分子量不超過4,000 g/mol。另外,所揭示聚酯多元醇之羥基官能度為至少1.5且不超過3(即1.5 ≤f ≤ 3)。
根據本發明之適於使用的聚酯多元醇為已知的二醇以及視情況多元醇(例如三醇、四醇)之聚縮合物,且為二羧酸以及視情況多元羧酸(例如三羧酸、四羧酸)或羥基羧酸或內酯之聚縮合物。聚酯多元醇亦可衍生自對應多元羧酸酐或低級醇之對應多元羧酸酯,而非游離多元羧酸。
適合之二醇包括但不限於乙二醇、丁二醇、二乙二醇、三乙二醇、聚伸烷二醇(諸如聚乙二醇),以及1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,6-己二醇及新戊二醇。為了達成大於2之聚酯多元醇官能度,官能度為3之多元醇可視情況包括於黏著劑組成物(例如三羥甲基丙烷、甘油、赤藻糖醇、季戊四醇、三羥甲基苯或異氰脲酸參羥乙酯)中。
適合的二羧酸包括但不限於脂族酸、芳族酸及其組合。適合的芳族酸之實例包括鄰苯二甲酸、間苯二甲酸、對苯二甲酸及四氫鄰苯二甲酸。適合之脂族酸之實例包括六氫鄰苯二甲酸、環己二酸、己二酸、壬二酸、癸二酸、戊二酸、四氯鄰苯二甲酸、順丁烯二酸、反丁烯二酸、伊康酸、丙二酸、辛二酸、2-甲基丁二酸、3,3-二乙基戊二酸、2,2-二甲基丁二酸及偏苯三甲酸。如本文所使用,術語「酸」亦包括所述酸之任何酸酐。另外,單羧酸,諸如苯甲酸及己烷羧酸應自所揭示組成物減至最少或排除。飽和脂族或芳族酸為較佳的,諸如己二酸或間苯二甲酸。
在原子之相同直鏈中含有兩個或更多個醚鍵之化合物在本文中稱為「聚醚」。作為聚醚及多元醇之化合物為「聚醚多元醇」。所揭示聚酯多元醇之分子量不超過5,000 g/mol。另外,所揭示聚醚多元醇之羥基官能度為至少1.5且不超過4(即1.5 ≤f ≤ 4)。
根據本發明之適於使用的聚醚多元醇為環氧乙烷、環氧丙烷、四氫呋喃、環氧丁烷之加成聚合產物,以及其共加成及接枝產物,以及藉由多元醇之縮合所獲得的聚醚多元醇,或其混合物。適用於使用之聚醚多元醇之實例包括但不限於聚丙二醇(「PPG」)、聚乙二醇(「PEG」)、聚丁二醇及聚四亞甲基醚乙二醇(「PTMEG」)。
所揭示多元醇組分可視情況進一步包含生物類多元醇,諸如蓖麻油或其他已知的生物類多元醇。再者,所揭示生物類多元醇之羥基官能度為至少1.5且不超過4(即1.5 ≤f ≤ 4)。
所揭示多元醇組分可視情況進一步包含一些小分子量擴鏈劑,其包括但不限於二醇及三醇,諸如乙二醇、丁二醇、二乙二醇、三乙二醇;聚伸烷二醇,諸如聚乙二醇;以及1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,6-己二醇、新戊二醇、三羥甲基丙烷、甘油、赤藻糖醇、季戊四醇、三羥甲基苯及異氰尿酸三羥乙酯。 異氰酸酯組分
異氰酸酯組分包含至少一種多異氰酸酯。
如本文中所使用,「多異氰酸酯」為含有兩個或更多個異氰酸酯基團之任何化合物。「芳族聚異氰酸酯」為含有一或多個芳環之多異氰酸酯。「脂族多異氰酸酯」不含芳環。
根據本發明之適於使用的多異氰酸酯可選自由芳族多異氰酸酯、脂族多異氰酸酯及其組合組成之群。根據本發明之適於使用之芳族多異氰酸酯的實例包括但不限於二聚異氰酸亞甲基二苯酯(「MDI」)之異構體,所述二聚異氰酸亞甲基二苯酯諸如4,4-MDI、2,4-MDI及2,2’-MDI;甲苯-二聚異氰酸酯(「TDI」)之異構體,所述甲苯-二聚異氰酸酯諸如2,4-TDI、2,6-TDI;萘-二聚異氰酸酯(「NDI」)之異構體,所述萘-二聚異氰酸酯諸如1,5-NDI;及其組合。根據本發明之適用於使用之脂族多異氰酸酯的實例包括但不限於六亞甲基二聚異氰酸酯(「HDI」)之異構體、異佛酮二聚異氰酸酯(「IPDI」)之異構體、二甲苯二聚異氰酸酯(「XDI」)之異構體、氫化甲烷二異氰酸苯酯(「HMDI」)之異構體,及其組合。在一些實施例中,芳族多異氰酸酯包含MDI之異構體。
異氰酸酯組分可視情況包含一或多種催化劑。根據本發明之適用於使用之至少一種催化劑的實例包括但不限於二月桂酸二丁錫、乙酸鋅、2,2-二嗎啉基二乙基醚,及其組合。
在一些實施例中,異氰酸酯組分與多元醇組分之重量比為5:1或更低、或4.5:1或更高、或4:1或更低。在一些實施例中,異氰酸酯組分與多元醇組分之重量比為1:4或更高、或1:2或更高。
在一些實施例中,黏著劑組成物視情況包含黏著促進劑,諸如胺基矽烷。
聚胺酯熱熔黏著劑組成物之製備可以本領域中一般熟習此項技術者已知的任何方式進行,且包括縮合聚合。聚胺酯黏著劑組成物調配物揭示案之化學計量使得二異氰酸酯過量存在,且聚胺酯黏著劑組成物以NCO基團封端。在一些實施例中,聚胺酯黏著劑組成物之異氰酸酯含量(亦稱為NCO%,如藉由ASTM D2572所量測)為3%至10%,或4%至9%,或5%至9%。
在一些實施例中,聚胺酯黏著劑組成物之黏度如藉由ASTM D2196之方法所量測在25℃下為300 mPa-s至100,000 mPa-s。
亦揭示使用聚胺酯黏著劑組成物形成層合物之方法。在一些實施例中,聚胺酯黏著劑組成物呈液態。在一些實施例中,組成物在25℃下為液體。即使組成物在25℃下為固體,但視需要可接受加熱組成物以使其處於液態。聚胺酯黏著劑組成物之層可藉由塗佈滾筒應用於箔之表面或紙之表面,隨後將水添加至聚胺酯黏著劑組成物層上。「箔」為在一個維度中為6 µm至20 µm且在其他兩個維度中為1 cm或更大的結構。較佳地,箔由鋁製成。「紙」為在一個維度中為10 µm至200 µm且在其他兩個維度中為1 cm或更大的結構。「紙」由植物纖維或聚合物樹脂製成,且適合之實例包括牛皮紙、白色卡紙板、膠版紙、美術紙,及其類似者。紙表面(或箔表面)藉由壓輥與箔/黏著劑(或紙/黏著劑)複合物進一步層合從而形成箔/黏著劑/紙(或紙/黏著劑/箔)層合物。 實例
本發明現將藉由說明性實例及比較例(統稱為「實例」)進一步詳細解釋。然而,本發明之範疇當然不限於實例中所闡述之調配物。確切而言,實例對本發明僅為說明性的。 聚胺酯黏著劑組成物製備
用於製備實例之原材料藉由市售名稱及供應商在以下表1中確認。 表1:原材料
聚胺酯黏著劑組成物實例(說明性實例1至7(IE1-7)及比較例1至3(CE1-3))遵循以下程序而合成:步驟1)將一或多種異氰酸酯組分裝入反應器中且在氮保護之情況下將其保持在60℃下,步驟2)在約80℃之升高溫度下將一或多種多元醇組分緩慢裝入同一反應器中且保持直至「NCO%」達到所計算範圍為止。所製備聚胺酯黏著劑組成物接著用於與紙及鋁箔形成層合物以用於性能測試。 表2:聚胺酯黏著劑組成物實例CE1-3及IE1-7 層合物性能測試
黏著劑組成物以3.5 gsm塗佈重量應用於紙,與鋁膜結合在一起,且接著在50℃下固化24小時,從而形成層合物。當層合物形成時,進行測試以分析黏合強度及熱封強度, 1. 襯底撕裂度測試
固化後,將層合膜切割成15 mm寬度條帶以用於在Instron 5943機器中以250 mm/min十字頭速度進行T-剝離測試。測試三個條帶以獲取平均值。在測試期間,由手指略微牽拉條帶之尾部以確保尾部與剝離方向保持90度。在撕裂度測試後紙表面之損壞率記錄為層合牢度。 2. 熱封強度測試
層合物在可自Brugger Company獲得之HSG-C熱封機器中於220℃密封溫度及300 N壓力下熱封1秒,接著冷卻下來且切割成15 mm寬度條帶以用於使用可自Instron公司獲得之5940系列單柱台面系統(5940 Series Single Column Table Top System)在250 mm/min十字頭速度下進行熱封強度測試。測試各樣本之三個條帶且計算平均值。結果以N/15mm為單位。 3. 黏度測試
在測試前於100℃下將層合物置於之暖爐中幾小時。在Brookfield DV-II黏度計中使用27軸在100℃下量測黏度。旋轉速度為12 RM,且在穩定旋轉速度下測試層合物20分鐘。 表3:性能測試結果
相比於比較例,說明性實例呈現紙/箔層合之良好黏合強度及熱封強度。在多元醇HA-0135聚酯多元醇之含量增加情況下,在撕裂度測試後檢測到較高紙破損率。當DMPA™多元醇HA-0135聚酯多元醇之含量達到6.3%時,在撕裂度測試後紙破損率變得穩定且達到90%破損率。然而,當DMPA™多元醇HA-0135聚酯多元醇含量小於6.3%時,紙破損率為對於此應用不可接受之低。此外,在比較例之熱封後,檢測到穿透及分層。

Claims (6)

  1. 一種聚胺酯熱熔黏著劑組成物,其係由以下所組成:多元醇組分及異氰酸酯組分,其中所述異氰酸酯組分係由至少一種多異氰酸酯及選擇性的一或多種催化劑所組成,且該聚胺酯熱熔黏著劑組成物係以NCO基團封端,其中所述多元醇組分係由以下所組成:按所述黏著劑組成物重量計4wt%至45wt%之具有兩個或更多個OH基團及一種氫橋聯基團之聚酯多元醇,其中所述氫橋聯基團選自O=C-O-、O=C-C-O-及O=C-C=C-O-,及其質子化形式(pronated forms);選自於由聚醚多元醇及聚酯多元醇和聚醚多元醇之組合所構成的群組之多元醇;其中所述異氰酸酯組分具有3%至10%的NCO%,其中所述NCO%係依ASTM D2572所量測;以及選擇性的黏著促進劑及選擇性的二醇或三醇單體。
  2. 如請求項1所述之聚胺酯熱熔黏著劑組成物,其中具有兩個或更多個OH基團及一種氫橋聯基團之所述聚酯多元醇的酸值為至少50mg KOH/g且不超過200mg KOH/g。
  3. 如請求項1所述之聚胺酯熱熔黏著劑組成物,其中具有兩個或更多個OH基團及一種氫橋聯基團之所述聚酯多元醇的分子量為至少400g/mol且不超過5,000g/mol。
  4. 如請求項1所述之聚胺酯熱熔黏著劑組成物,其中所述至少一種多異氰酸酯係選自由芳族多異氰酸酯、脂族多異氰酸酯及其等之組合組成之群。
  5. 如請求項1所述之聚胺酯熱熔黏著劑組成物,其中該聚胺酯熱熔黏著劑組成物之異氰酸酯含量為3%至10%。
  6. 一種層合物,其用如請求項1所述之聚胺酯熱熔黏著劑組成物來黏附箔及紙張。
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