TWI802583B - 雙組分溶劑類黏合劑組合物及其製造方法 - Google Patents

雙組分溶劑類黏合劑組合物及其製造方法 Download PDF

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TWI802583B
TWI802583B TW107128769A TW107128769A TWI802583B TW I802583 B TWI802583 B TW I802583B TW 107128769 A TW107128769 A TW 107128769A TW 107128769 A TW107128769 A TW 107128769A TW I802583 B TWI802583 B TW I802583B
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polyol
weight
adhesive composition
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TW201912753A (zh
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陳高兵
白晨豔
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美商陶氏全球科技有限責任公司
美商羅門哈斯公司
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Abstract

本揭示案提供一種雙組分聚胺酯黏合劑組合物,其包括芳族多異氰酸酯組分及多元醇組分,所述多元醇組分包括至少一種聚酯多元醇以及具有兩個或更多個OH基團及一個氫橋基之多元醇。

Description

雙組分溶劑類黏合劑組合物及其製造方法
本揭示案係關於雙組分黏合劑組合物。更特定言之,本揭示案係關於用於層壓膜中之雙組分聚胺酯黏合劑組合物,以及製造所述組合物之方法。所述組合物具有改良之黏結強度、熱封強度及耐熱性。
黏合劑組合物適用於多種目的。舉例而言,黏合劑組合物用於將基材,諸如聚乙烯、聚丙烯、聚酯、聚醯胺、金屬、紙或塞璐芬(cellophane)黏結在一起以形成複合膜,亦即層壓材料。黏合劑在不同層壓最終使用應用中之用途為通常已知的。舉例而言,黏合劑可用於製造用於包裝工業,尤其用於食品包裝之膜/膜及膜/箔層壓材料。
習知之雙組分聚胺酯類層壓黏合劑包含包括多異氰酸酯之第一組分及包括一種或多種多元醇之第二組分。第一組分藉由使二異氰酸酯單體與多元醇反應來獲得。第二組分為聚酯多元醇或聚醚多元醇或其混合物。各組分可視情況包含一種或多種添加劑。在施用於膜/箔基材上之前,將兩種組分以預定比例組合,且隨後將所述組合層壓至另一個膜/箔基材上。
雙組分聚胺酯類層壓黏合劑通常含有溶劑以使黏度降低至應用目的所需之水準,且提供較高初始黏結及較高最終黏結強度。然而,熱處理之 後黏合劑的黏結強度及熱封強度有時不如預期的好。
期望開發即使在熱處理之後亦具有改良之黏結強度及熱封強度的黏合劑。
本揭示案提供一種雙組分聚胺酯黏合劑組合物,其包括芳族多異氰酸酯組分及多元醇組分,所述多元醇組分包括至少一種聚酯多元醇以及具有兩個或更多個OH基團及一個氫橋基之多元醇。
根據本揭示案之雙組分聚胺酯黏合劑組合物包括多異氰酸酯組分及多元醇組分。
多異氰酸酯組分
多異氰酸酯組分為芳族多異氰酸酯加合物或三聚物。
芳族多異氰酸酯加合物藉由使過量芳族二異氰酸酯與分子量小於400之低分子量二醇及多元醇反應來製備,所述二醇及多元醇諸如三羥甲基丙烷、丙三醇、1,2-二羥基丙烷及其混合物。可商購之芳族多異氰酸酯為來自科思創公司(Covestro)之Desmodur L75。
芳族多異氰酸酯三聚物藉由在催化劑存在下使芳族二異氰酸酯三聚化來製備。可商購之芳族多異氰酸酯為來自科思創公司之Desmodur L1470。
如本文所用,「二異氰酸酯單體」為每分子含有兩個異氰酸酯基之任何化合物。「芳族二異氰酸酯單體」為含有一個或多個芳族環之二異氰酸酯單體。
芳族二異氰酸酯單體的適合之實例包含但不限於亞甲基二苯基二異氰酸酯(「MDI」)之異構體,諸如4,4-MDI及2,4-MDI;甲苯二異氰酸酯(「TDI」)之異構體,諸如2,4-TDI、2,6-TDI,萘二異氰酸酯(「NDI」)之異構體,諸如1,5-NDI;及其組合。
分子量小於400之二醇及多元醇的適合之實例包含但不限於二甘醇、乙二醇、三甘醇、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、三甲基丙烷(TMP)、甘油及季戊四醇。
多異氰酸酯組分由參數「%NCO」表徵,其為以多異氰酸酯組分之重量計的按重量計之NCO基團量。參數%NCO根據ASTM D 2572-97(2010)來量測。本揭示案之多異氰酸酯組分的%NCO為至少7重量%、或至少9重量%、或至少11重量%。在一些實施方案中,異氰酸酯組分之%NCO不超過19重量%、或17重量%、或15重量%。
多異氰酸酯組分之平均NCO官能度為至少2.8且不超過5(亦即,2.8
Figure 107128769-A0305-02-0004-3
f
Figure 107128769-A0305-02-0004-4
5)。
多異氰酸酯組分之固體含量為至少50%,且使用乙酸乙酯或酮作為溶劑。
多異氰酸酯組分可視情況包括一種或多種催化劑。催化劑的適合之實例包含但不限於二月桂酸二丁基錫、乙酸鋅、2,2-二嗎啉基二乙基醚及其組合。
多元醇組分
雙組分聚胺酯黏合劑組合物進一步包括多元醇組分,其包括至少一種聚酯多元醇以及具有兩個或更多個OH基團及一個氫橋基之多元醇。
以多元醇組分之重量計,多元醇組分中的聚酯多元醇之量為按重 量計至少78重量%、或至少80重量%、或至少82重量%。以多元醇組分之重量計,多元醇組分中的聚酯多元醇之量為按重量計不超過99重量%、或97重量%、或95重量%。
適合用於多元醇組分之聚酯多元醇的分子量為至少4,000g/mol。另外,適合之聚酯多元醇的OH官能度為至少1.8且不超過3(亦即,1.8
Figure 107128769-A0305-02-0005-5
f
Figure 107128769-A0305-02-0005-6
3),且其OH數在2-45mg KOH/g之間。「OH數」由相當於一公克多元醇中羥基含量的氫氧化鉀之毫克數表徵。
適合用於本揭示案中之聚酯多元醇為已知的二醇之縮聚物以及視情況選用的多元醇(例如三醇、四醇)之縮聚物及二羧酸之縮聚物。聚酯多元醇亦可衍生自二羧酸、其相對應之酸酐或相對應之低級醇酯。
適合之二醇包含但不限於乙二醇、丁二醇、二乙二醇、二甘醇、三甘醇、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OH官能度大於2之聚酯多元醇,OH官能度為3之多元醇可視情況包含於黏合劑組合物中(例如三羥甲基丙烷、甘油、赤藻糖醇、季戊四醇、三羥甲基苯(trimethylolbenzene)或異氰脲酸參羥乙酯)。
適合之二羧酸包含但不限於脂族酸、芳族酸及其組合。適合之芳族酸的實例包含鄰苯二甲酸、間苯二甲酸、對苯二甲酸及四氫鄰苯二甲酸。適合之脂族酸的實例包含六氫鄰苯二甲酸、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、衣康酸、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。亦可使用此類酸之酸酐。此外,應自所揭示之組合物中最少化或排除單羧酸,諸如苯甲酸及己烷甲酸。飽和脂族或芳族酸,諸如己二酸或間苯二甲酸較佳。
多元醇組分進一步包括在多元醇分子鏈末端處具有兩個或更多個OH基團且在側分子鏈中具有至少一個氫橋基之多元醇。氫橋基的適合之實例包含但不限於O=C-O-、O=C-C-O-及O=C-C=C-O-,及其質子化形式。具有兩個或更多個OH基團及一個氫橋基之多元醇的酸值為至少50mg KOH/g且不超過200mg KOH/g。另外,此多元醇之分子量為至少600g/mol且不超過3,000g/mol。更進一步地,此多元醇之OH官能度為至少1.8且不超過3(亦即,1.8
Figure 107128769-A0305-02-0006-7
f
Figure 107128769-A0305-02-0006-8
3)。
以多元醇組分之重量計,多元醇組分中的具有兩個或更多個OH基團及一個氫橋基之多元醇的量為按重量計至少1重量%、或至少3重量%、或至少5重量%。以多元醇組分之重量計,多元醇組分中的具有兩個或更多個OH基團及一個氫橋基之多元醇的量為按重量計不超過22重量%、或20重量%、或18重量%。
多元醇組分與多異氰酸酯組分之重量比為100:15至100:40。
預期所揭示之雙組分聚胺酯黏合劑組合物的多異氰酸酯組分及多元醇組分可單獨製造,且必要時可單獨儲存,直至期望使用黏合劑組合物為止。在一些實施方案中,多異氰酸酯組分及多元醇組分在25℃下均各自為液體。當期望使用黏合劑組合物時,使多異氰酸酯組分及多元醇組分彼此接觸且混合在一起。預期當使此兩種組分接觸時,開始固化反應,其中異氰酸酯基與羥基反應以形成胺基甲酸酯鍵。藉由使兩種組分接觸而形成之黏合劑組合物可稱作「可固化混合物」。
亦揭示一種使用黏合劑組合物形成層壓材料之方法。在一些實施方案中,黏合劑組合物,諸如上文所論述之黏合劑組合物,處於液態。在一些實施方案中,組合物在25℃下為液體。即使組合物在25℃下為固體,視需要亦可接受加熱組合物以使其處於液態。將一層組合物施用於膜之表面。「膜」為 在一個維度中為0.5mm或更小且在其他兩個維度中均為1cm或更大的任何結構。聚合物膜為由聚合物或聚合物之混合物製成的膜。在一些實施方案中,可固化混合物之層的厚度為1至5μm。
在一些實施方案中,使另一個膜之表面與可固化混合物之層接觸以形成未固化之層壓材料。
隨後將可固化混合物固化或使其固化。未固化之層壓材料可經受壓力,例如藉由穿過夾輥,所述軋輥可經或可不經加熱。可以加熱未固化之層壓材料以加速固化反應。
適合之膜包含紙、織造及非織造織物、金屬箔、聚合物及經金屬塗佈之聚合物。膜視情況具有在其上用墨水印刷圖像之表面;所述墨水可與黏合劑組合物接觸。在一些實施方案中,膜為聚合物膜及經金屬塗佈之聚合物膜,更佳為聚合物膜。
實施例
本揭示案現將藉由說明性實施例及比較例(統稱為「實施例」)進一步詳細加以解釋。然而,本揭示案之範疇當然不限於實施例中所闡述之調配物。而是,實施例僅說明本揭示案。
組合物製備
用於製備實施例之原料描述於下文。
多異氰酸酯組分:
DESMODURTM L75為NCO官能度為3(f=3)之芳族多異氰酸酯;其在以EA為溶劑的情況下具有75%固體含量;且其可商購自科思創公司。
ADCOTETM CR750為NCO官能度為2(f=2)之芳族多異氰酸酯;其在以EA為溶劑的情況下具有75%固體含量;且其可商購自陶氏化學公司 (Dow Chemical company)。
DESMODURTM N3300為NCO官能度為2.8至5(2.8
Figure 107128769-A0305-02-0008-9
f
Figure 107128769-A0305-02-0008-10
5)之脂族多異氰酸酯;其具有100%固體含量;且其可商購自科思創公司。
多元醇組分:
ADCOTETM 563EA為OH=26mg KOH/g之聚酯多元醇,且在以EA為溶劑的情況下具有82%固體含量;其可商購自陶氏化學公司,DMPATM HA-0135為具有兩個或更多個OH基團及一個氫橋基之多元醇;其OH數為115mg KOH/g;其具有100%固體含量;且其可商購自GEO Speciality Chemicals。
為了製備說明性實施例及比較例,根據表1中說明之配對混合異氰酸酯組分及多元醇組分,以形成實施例之黏合劑組合物。
隨後使用實施例之黏合劑組合物形成包括聚乙烯及預層壓鋁箔(PET//箔)之層壓材料。將黏合劑組合物以3.0gsm乾塗層重量施用於鋁面上,使其與聚乙烯膜結合在一起,且隨後在50℃下固化48小時以形成層壓材料。一旦形成層壓材料,則進行測試以分析黏結強度、熱封強度及耐用水袋內蒸煮性。
Figure 107128769-A0305-02-0008-1
層壓材料性能測試
對由實施例之黏合劑組合物製備的層壓材料進行黏結強度測試(BS)。將層壓材料切割成15mm寬條帶,以使用購自英斯特朗公司(Instron Corporation)之5940系列單管柱桌面系統(5940 Series Single Column Table Top System)以250mm/min十字頭速度進行T型剝離測試。在測試期間,用手輕輕拉動各條帶之尾部,以確保尾部與剝離方向保持90°角度。對各樣品測試三個條帶,且計算平均值。結果以N/15mm為單位。相對較高值指示較好的黏結強度。
對由實施例之黏合劑組合物製備的層壓材料進行熱封強度測試(HS)。將層壓材料在可購自Brugger Feinmechanik GmbH之HSG-C熱封機中在140℃密封溫度及300N壓力下熱封1秒。隨後使層壓材料冷卻且將其切割成15mm寬條帶,以使用購自英斯特朗公司之5940系列單管柱桌面系統以250mm/min十字頭速度進行熱封強度測試。對各樣品測試三個條帶,且計算平均值。結果以N/15mm為單位。相對較高值指示較好的熱封強度。
對由實施例之黏合劑組合物製備的層壓材料進行耐袋內蒸煮性測試(BiB)。將層壓材料切割成8cm×12cm之片,且經由在袋內有水的情況下熱封來製成袋。隨後將袋放入沸水中持續30分鐘,確保在整個煮沸過程期間袋始終浸沒於水中。在完成煮沸過程後記錄袋之隧穿,分層及/或洩漏的程度。對於通過耐袋內蒸煮性測試之樣品,其必須未展示出隧穿、分層或洩漏之跡象。隨後將袋打開,倒空且切割成15mm寬條帶,以在5分鐘內藉由英斯特朗公司5943機器測試T型剝離黏結強度。測試三個條帶以取得平均值。
Figure 107128769-A0305-02-0009-2
IE1-5為使用官能度為3之芳族多異氰酸酯且含有具有氫橋基之多元醇的本發明之實施例,且IE1-5展示出改良之黏結強度,尤其在熱處理(袋內蒸煮)之後的熱封強度。而比較例5展示出熱處理之後的黏結強度及熱封強度較差,其使用官能度為3之芳族多異氰酸酯而無具有氫橋基之多元醇。CE1及CE2為使用官能度為2之芳族多異氰酸酯的實施例,其展示出更差之效能。CE3及CE4為使用官能度超過3之脂族多異氰酸酯的實施例,其亦展示出較差之效能。

Claims (8)

  1. 一種雙組分聚胺酯黏合劑組合物,其包括芳族多異氰酸酯組分及多元醇組分,所述多元醇組分包括至少一種聚酯多元醇以及一種在多元醇分子鏈末端處具有兩個或更多個OH基團及在側分子鏈中具有一個氫橋基之多元醇;其中所述芳族多異氰酸酯組分之平均NCO官能度為至少2.8且不超過5;其中所述芳族多異氰酸酯組分為芳族多異氰酸酯加合物或芳族多異氰酸酯三聚物,其係由選自亞甲基二苯基二異氰酸酯MDI之異構體、甲苯二異氰酸酯TDI之異構體、萘二異氰酸酯NDI之異構體及其組合的芳族二異氰酸酯單體所製備;所述聚酯多元醇之OH官能度為至少1.8且不超過3,且OH數在2至45mg KOH/之間;且所述在多元醇分子鏈末端處具有兩個或更多個OH基團及在側分子鏈中具有一個氫橋基之多元醇的酸值為至少50mg KOH/g且不超過200mg KOH/g,且OH官能度為至少1.8且不超過3;其中所述多元醇組分與所述芳族多異氰酸酯組分之重量比為100:15至100:40。
  2. 如申請專利範圍第1項所述之雙組分聚胺酯黏合劑組合物,其中所述芳族二異氰酸酯單體為甲苯二異氰酸酯TDI之異構體。
  3. 如申請專利範圍第1項所述之雙組分聚胺酯黏合劑組合物,其中所述芳族多異氰酸酯組分之%NCO為至少7重量%且不超過19重量%。
  4. 如申請專利範圍第1項所述之雙組分聚胺酯黏合劑組合物,其中以所述多元醇組分之重量計,所述聚酯多元醇之量為至少78重量%至小於99重量%。
  5. 如申請專利範圍第1項所述之雙組分聚胺酯黏合劑組合物,其 中所述氫橋基係選自O=C-O-、O=C-C-O-及O=C-C=C-O-,及其質子化形式。
  6. 如申請專利範圍第1項所述之雙組分聚胺酯黏合劑組合物,其中以所述多元醇組分之重量計,所述在多元醇分子鏈末端處具有兩個或更多個OH基團及在側分子鏈中具有一個氫橋基之多元醇的量為至少1重量%至小於22重量%。
  7. 一種可固化混合物,其包括如申請專利範圍第1項所述之多異氰酸酯組分及多元醇組分。
  8. 一種層壓材料,其包括如申請專利範圍第7項所述之可固化混合物。
TW107128769A 2017-09-05 2018-08-17 雙組分溶劑類黏合劑組合物及其製造方法 TWI802583B (zh)

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