TW202115145A - 胺甲酸乙酯預聚物、接著劑、積層體、及合成仿皮 - Google Patents

胺甲酸乙酯預聚物、接著劑、積層體、及合成仿皮 Download PDF

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TW202115145A
TW202115145A TW109129544A TW109129544A TW202115145A TW 202115145 A TW202115145 A TW 202115145A TW 109129544 A TW109129544 A TW 109129544A TW 109129544 A TW109129544 A TW 109129544A TW 202115145 A TW202115145 A TW 202115145A
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urethane prepolymer
adhesive
moisture
polyol
diisocyanate
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河村亮
山田利樹
佐佐木一弥
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日商大日精化工業股份有限公司
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Abstract

本發明之胺甲酸乙酯預聚物具有異氰酸酯基，100℃下之黏度為30～600 dPa・s，且濕氣硬化後之熱軟化溫度為75～155℃。

Description

胺甲酸乙酯預聚物、接著劑、積層體、及合成仿皮
本發明係關於一種胺甲酸乙酯預聚物、接著劑、及合成仿皮。
濕氣硬化型接著劑係末端具有異氰酸酯基之聚胺甲酸乙酯，其會與空氣中之水分(濕氣)反應，發生交聯反應，從而表現出作為接著劑之功能。通常，聚胺甲酸乙酯系接著劑係使用被稱為二液硬化系統之方法將多官能異氰酸酯調配於末端為羥基之聚胺甲酸乙酯而進行交聯。因此，上述濕氣硬化型接著劑具有無需調配即可進行塗佈之優點。然而，一般而言，交聯所導致之分子量之增大會使交聯後之軟化溫度高達170～200℃，故而雖耐久物性充分但硬化後無接著性。因此，自對一基材進行塗佈至對另一基材進行貼附之步驟需要連續地進行。
另一方面，所謂熱熔接著劑係利用熱使固體狀之接著劑熔融而將基材彼此接著之接著劑(例如參照專利文獻1、2)。該熱熔接著劑具有100℃左右下即可熔融從而使用便捷之優點，但因為組成或分子量之關係，又具有耐久物性(耐熱性、耐撓曲性、耐寒性、耐水解性等)較低之缺點。又，存在必須使用專用熔化器之情形，從而難以進行薄膜塗佈或凹版塗佈(點接著等)，加工自由度較低。
又，作為用於服飾、包、鞋之裝飾之接著劑，使用以可滿足上述耐久物性之方式調整組成或分子量所得之接著劑。然而，由於黏度較高而加工適性明顯較低之原因，一直使用溶解於有機溶劑之熱熔樹脂，但近年來，由於環境限制，開始推薦不使用溶劑。 先前技術文獻 專利文獻
專利文獻1：日本專利特開2000-336142號公報 專利文獻2：日本專利特開2005-126595號公報
[發明所欲解決之問題]
如上所述，濕氣硬化型接著劑於硬化後不再發揮接著性，又，熱熔接著劑之加工自由度較低。因此，若存在一種硬化後可如熱熔接著劑般熱壓接合之濕氣硬化型接著劑，則不僅可獲得優異之物性，而且可提高加工自由度，因此非常有意義，但於實際應用中尚未聽聞此種接著劑。 因此，本發明之目的在於，提供一種於濕氣硬化後可進行熱壓接合且黏度處於加工自由度較高之範圍內之胺甲酸乙酯預聚物。 [解決問題之技術手段]
本案發明人等為了解決上述問題進行了努力研究，結果發現：若使100℃下之黏度處於特定範圍內且使濕氣硬化後之熱軟化溫度處於特定範圍內，則可獲得於濕氣硬化後能夠進一步熱熔且加工自由度較高之胺甲酸乙酯預聚物；從而想到了本發明。即，本發明如下所述。
[1]一種胺甲酸乙酯預聚物，其具有異氰酸酯基，100℃下之黏度為30～600 dPa・s，且濕氣硬化後之熱軟化溫度為75～155℃。 [2]如[1]之胺甲酸乙酯預聚物，其中上述異氰酸酯基之相對於總莫耳數之10～55%由密封劑密封。 [3]如[1]或[2]之胺甲酸乙酯預聚物，其係聚異氰酸酯與多元醇之反應物，且上述聚異氰酸酯之異氰酸酯基相對於多元醇之羥基之當量比(NCO/OH)為1.2～2.5。 [4]一種接著劑，其包含如[1]至[3]中任一項之胺甲酸乙酯預聚物。 [5]一種積層體，其於基材膜上具有包含如[4]之接著劑之塗膜之濕氣硬化物層。 [6]一種合成仿皮，其於如[5]之積層體之上述濕氣硬化物層上具有基布之熱壓接合物。 [發明之效果]
根據本發明，可提供一種於濕氣硬化後能夠進行熱壓接合且黏度處於加工自由度較高之範圍內之胺甲酸乙酯預聚物。
以下，對本發明之實施形態(本實施形態)詳細地進行說明，但本發明並不限定於該實施形態。
[1.胺甲酸乙酯預聚物] 本實施形態之胺甲酸乙酯預聚物具有異氰酸酯基，100℃下之黏度為30～600 dPa・s，且濕氣硬化後之熱軟化溫度為75～155℃。
100℃下之黏度未達30 dPa時，對基布之滲入會變得明顯，因此加工變難，又，濕氣硬化後之質地會變硬。又，若超過600 dPa，則變得黏稠而難以加工。該黏度較佳為50～250 dPa，更佳為70～200 dPa。
又，濕氣硬化後之熱軟化溫度未達75℃時，難以獲得良好之物性，比如製成合成仿皮時容易滲入基布、質地會變硬等。若超過155℃，則此後之加工變難，加工自由度變低。該熱軟化溫度較佳為78～152℃，更佳為80～150℃。 上述黏度及熱軟化溫度可藉由實施例所記載之方法進行測定。
要使濕氣硬化前之100℃下之黏度處於上述範圍內，較佳為藉由多元醇之種類與NCO/OH比進行調整，要使濕氣硬化後之熱軟化溫度處於上述範圍內，較佳為例如藉由密封劑將胺甲酸乙酯預聚物中之一部分異氰酸酯基密封。藉由密封，可控制異氰酸酯基之物質量，可使軟化點降低，且亦可維持物性。利用密封劑進行密封時，例如與封端劑會因熱而解離之封端異氰酸酯不同，密封劑不易因熱而解離，因此容易將濕氣硬化後之熱軟化溫度控制於75～155℃之下。其結果，可獲得能夠進行濕氣硬化及熱壓接合且加工自由度較高之胺甲酸乙酯預聚物。
作為上述密封劑，可列舉：ε-己內醯胺、δ-戊內醯胺、γ-丁內醯胺等內醯胺；脂肪族胺(二甲胺、二異丙胺、二正丙胺、二異丁胺等)、脂環式胺(甲基己基胺、二環己基胺等)、芳香族胺(苯胺、二苯胺等胺)；甲醇、乙醇、2-丙醇、正丁醇、十六醇、異硬脂醇、油醇、山萮醇、月桂醇、羊毛脂醇、氫化羊毛脂醇、1-十六烷醇等脂肪族醇；苯酚、甲酚、乙基苯酚、正丙基苯酚、異丙基苯酚、正丁基苯酚、辛基苯酚、壬基苯酚、二甲苯酚、二異丙基苯酚、二-第三丁基苯酚等酚類；咪唑、2-甲基咪唑等咪唑類；吡唑、3-甲基吡唑、3,5-二甲基吡唑等吡唑類；伸乙基亞胺；丙二酸二甲酯、丙二酸二乙酯、丙二酸二異丙酯、乙醯丙酮、乙醯乙酸甲酯、乙醯乙酸乙酯等活性亞甲基；丙酮肟、甲基乙基酮肟、環己酮肟等肟類等。 其中，就反應性或合成之控制等觀點而言，較佳為脂肪族醇，更佳為碳數10以上之脂肪族醇。
基於使濕氣硬化後之熱軟化溫度處於所需範圍內之觀點，相對於異氰酸酯基之總莫耳數，較佳為其5～60%由密封劑密封，更佳為其10～55%被密封。要達成該密封率，只要考慮相對於異氰酸酯基之總莫耳數的密封劑之活性氫之莫耳數，以成為所需密封率之方式調配密封劑即可。
本實施形態之密封前之胺甲酸乙酯預聚物係聚異氰酸酯、多元醇、及視需要而添加之短鏈二醇或短鏈二胺等鏈伸長劑之反應物，上述聚異氰酸酯之異氰酸酯基相對於多元醇之羥基之當量比(NCO/OH)較佳為1.2～2.5。藉由使當量比(NCO/OH)為1.2～2.5，可確保加工性，從而可獲得質地良好之合成仿皮。當量比更佳為1.5～2.2。
以下，對本實施形態之聚異氰酸酯及多元醇、以及其他構成成分進行說明。
(多元醇) 作為多元醇，其數量平均分子量較佳為700～6000，更佳為1000～4000，例如可列舉如下示例。
(1)聚碳酸酯二醇 作為聚碳酸酯多元醇，可列舉：聚四亞甲基碳酸酯二醇、聚五亞甲基碳酸酯二醇、聚新戊基碳酸酯二醇、聚六亞甲基碳酸酯二醇、聚(1,4-環己烷二亞甲基碳酸酯)二醇、及該等之無規/嵌段共聚物等。
(2)聚醚多元醇 作為聚醚多元醇，可列舉將環氧烷(環氧乙烷、環氧丙烷、環氧丁烷等)及雜環式醚(四氫呋喃等)中之任一者聚合或共聚合所得者。具體可列舉：聚乙二醇、聚丙二醇、聚乙二醇-聚四亞甲基二醇(嵌段或無規)、聚四亞甲基醚二醇及聚己二醇等。
(3)聚酯多元醇 作為聚酯多元醇，可列舉使脂肪族系二羧酸類(例如丁二酸、己二酸、癸二酸、戊二酸及壬二酸等)、及芳香族系二羧酸(例如間苯二甲酸及對苯二甲酸等)中之至少任一者與低分子量二醇類(例如乙二醇、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、新戊二醇及1,4-雙羥甲基環己烷等)聚縮合所得者。 具體可列舉：聚己二酸乙二酯二醇、聚己二酸丁二酯二醇、聚己二酸己二酯二醇、聚己二酸新戊酯二醇、聚己二酸乙/丁二酯二醇、聚己二酸新戊/己酯二醇、聚己二酸-3-甲基戊酯二醇及聚間苯二甲酸丁酯二醇等。
(4)聚內酯多元醇 作為聚內酯多元醇，可列舉聚己內酯二醇及聚-3-甲基戊內酯二醇等。 (5)聚烯烴多元醇 作為聚烯烴多元醇，可列舉聚丁二烯二醇及聚異戊二醇、或其氫化物等。 (6)聚甲基丙烯酸酯二醇 作為聚甲基丙烯酸酯二醇，可列舉α,ω-聚甲基丙烯酸甲酯二醇及α,ω-聚甲基丙烯酸丁酯二醇等。 (7)聚矽氧烷多元醇 作為聚矽氧烷多元醇，較佳為二甲基聚矽氧烷。由於可賦予滑性，故而於用作塗佈劑之情形時尤其有用。
該等多元醇可單獨使用或2種以上組合使用，但就長期耐久性之觀點而言，較佳為包含聚碳酸酯二醇。 再者，數量平均分子量係聚苯乙烯換算之數量平均分子量，通常可藉由凝膠滲透層析法(GPC)之測定而求得。
(聚異氰酸酯) 作為聚異氰酸酯化合物，可列舉：甲苯-2,4-二異氰酸酯、4-甲氧基-1,3-苯二異氰酸酯、4-異丙基-1,3-苯二異氰酸酯、4-氯-1,3-苯二異氰酸酯、4-丁氧基-1,3-苯二異氰酸酯、2,4-二異氰酸酯二苯醚、4,4'-亞甲基雙(伸苯基異氰酸酯)(MDI)、伸四甲苯基二異氰酸酯、甲苯二異氰酸酯、苯二甲基二異氰酸酯(XDI)、1,5-萘二異氰酸酯、聯苯胺二異氰酸酯、鄰硝基聯苯胺二異氰酸酯及4,4'-二異氰酸基聯苄等芳香族二異氰酸酯；亞甲基二異氰酸酯、1,4-四亞甲基二異氰酸酯、1,6-六亞甲基二異氰酸酯及1,10-十亞甲基二異氰酸酯等脂肪族二異氰酸酯；1,4-環己二異氰酸酯、4,4'-亞甲基雙(環己基異氰酸酯)、1,5-四氫萘二異氰酸酯、異佛爾酮二異氰酸酯、氫化MDI及氫化XDI等脂環式二異氰酸酯等；或者使該等二異氰酸酯化合物與低分子量之多元醇或聚胺以末端成為異氰酸酯之方式進行反應所得之聚胺甲酸乙酯預聚物等。
(鏈伸長劑) (1)短鏈二醇 短鏈二醇係數量平均分子量未達500之化合物，可列舉：乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,6-己二醇及新戊二醇等脂肪族二醇類及其環氧烷低莫耳加成物(數量平均分子量未達500)；1,4-雙羥甲基環己烷及2-甲基-1,1-環己烷二甲醇等脂環式系二醇類及其環氧烷低莫耳加成物(數量平均分子量未達500)；苯二甲醇等芳香族二醇類及其環氧烷低莫耳加成物(數量平均分子量未達500)；雙酚A、硫代雙酚及碸雙酚等雙酚類及其環氧烷低莫耳加成物(數量平均分子量未達500)；以及C1～C18之烷基二乙醇胺等烷基二烷醇胺類等化合物。又，可使用包含羧基、磺基、磷酸基、胺基等離子性基之二醇。
(2)短鏈二胺 作為短鏈二胺，可列舉：乙二胺、三亞甲基二胺、六亞甲基二胺及八亞甲基二胺等脂肪族二胺化合物；苯二胺、3,3'-二氯-4,4'-二胺基二苯基甲烷、4,4'-亞甲基雙(苯基胺)、4,4'-二胺基二苯基醚及4,4'-二胺基二苯基碸等芳香族二胺化合物；環戊二胺、環己二胺、4,4-二胺基二環己基甲烷、1,4-二胺基環己烷及異佛爾酮二胺等脂環式二胺化合物；肼、甲二醯肼、己二酸二醯肼、癸二酸二醯肼、鄰苯二甲酸二醯肼等肼類等。
以上係較佳成分之例示，本發明並非限定於該等。因此，不僅可使用上述例示成分，而且其他任何目前正在市售而可容易地自市場獲得之化合物均可使用。 又，亦可於不影響本發明之效果之範圍內，將環氧樹脂、聚氯乙烯等與胺甲酸乙酯預聚物組合而使用。
(胺甲酸乙酯預聚物之製造方法) 本實施形態之胺甲酸乙酯預聚物例如可藉由如下方法製造：藉由一步(one-shot)法、或多階段法，於20～150℃(較佳為60～110℃)下，使多元醇、聚異氰酸酯及視需要添加之短鏈二醇或短鏈二胺等鏈伸長劑以異氰酸酯基與含有活性氫之基(羥基等)之當量比(NCO/OH)成為1.2～2.5之組成，進行反應直至產物成為理論NCO%為止，進而混合特定量之密封劑使其進行反應。
於上述製造方法中，可視需要使用觸媒。例如可列舉：二月桂酸二丁基錫、二月桂酸二辛基錫、辛酸亞錫、辛酸鉛、鈦酸四正丁酯等金屬與有機及無機酸之鹽、以及有機金屬衍生物、三乙胺等有機胺、二氮雜雙環十一烯系觸媒等。
胺甲酸乙酯預聚物較佳為不使用有機溶劑而無溶劑地反應。藉此，可製成無溶劑胺甲酸乙酯預聚物。
胺甲酸乙酯預聚物中亦可視需要加入添加劑。例如，可列舉抗氧化劑(受阻酚系、亞磷酸酯系、硫醚系等)、光穩定劑(受阻胺系等)、紫外線吸收劑(二苯甲酮系、苯并三唑系等)、氣體變色穩定劑(肼系等)、金屬減活劑等或該等兩種以上。
如上之本實施形態之胺甲酸乙酯預聚物尤其適用於接著劑、積層體、塗佈劑、合成仿皮等用途。
[2.接著劑] 本實施形態之接著劑包含本發明之胺甲酸乙酯預聚物。於本實施形態之接著劑中，亦可視需要適當調配熱塑性聚合物、黏著賦予樹脂、觸媒、顏料、抗氧化劑、紫外線吸收劑、界面活性劑、阻燃劑、填充劑、發泡劑等，較佳為包含聚胺甲酸乙酯預聚物。又，本實施形態之接著劑較佳為用於合成仿皮，即較佳為合成仿皮用接著劑。
本實施形態之接著劑可藉由塗佈於被黏著體表面而使被黏著體彼此容易地接著。作為被黏著體，除上述用於合成仿皮之基材以外，例如還可列舉金屬、非金屬(聚碳酸酯、玻璃等)之基材。
[3.積層體] 本發明之積層體於基材膜上具有包含本發明之接著劑之塗膜之濕氣硬化物層。 作為基材膜，除用於合成仿皮之基材膜以外，還可列舉光學膜及光學板、軟性印刷基板、玻璃基板、及將ITO(indium-tin-oxide，氧化銦錫)蒸鍍於該等基板所得之基板等。
利用逗號刀塗佈、刮塗、輥塗等公知之方法，將本發明之接著劑塗佈於基材膜上，並進行濕氣硬化藉此自塗膜製成濕氣硬化物層，由此獲得本發明之積層體。
[4.合成仿皮] 本發明之合成仿皮於本發明之積層體之濕氣硬化物層上具有基布之熱壓接合物。 作為基布，例如可列舉包含斜紋織物、平紋織物等之織物、使該織物之棉面料機械地起毛所獲得之起毛布、嫘縈布、尼龍布、聚酯布、克維拉布、不織布(聚酯、尼龍、各種乳膠)、各種膜、片材等。
合成仿皮例如能夠以如下方式製造。將基布積層於本發明之積層體之濕氣硬化物層上，並於75～155℃下使其等壓接。進而，視需要進行熟成等，從而獲得本發明之合成仿皮。 如上之合成仿皮適用於鞋、衣物、包、傢俱、車輛內裝材料(例如儀錶面板、門、控制台、座位)等。 實施例
其次，以實施例及比較例對本發明進一步詳細地進行說明，但本發明並不由實施例等限定。再者，數量平均分子量係藉由GPC(聚苯乙烯換算)進行測定。
[實施例1] 向附有攪拌機、溫度計、氣體導入口等之500毫升之玻璃製反應容器中，加入包含己二酸及1,4-丁二醇之數量平均分子量為2000之聚酯多元醇100質量份及4,4'-二苯甲烷二異氰酸酯(MDI)25質量份，進行加熱減壓並脫水處理後，封入氮氣並將內溫設為100℃，攪拌120分鐘，使其反應。再者，設為NCO/OH＝2.0。其後，使2.4質量份之1-十六烷醇作為密封劑進行反應，獲得胺甲酸乙酯預聚物。
[實施例2～5及比較例1、2] 將組成設為如表1所示，除此以外，以與實施例1相同之方式獲得胺甲酸乙酯預聚物。
對於各例中所製成之胺甲酸乙酯預聚物，如下所述，進行黏度、熱軟化溫度、接著強度之測定。
(黏度測定) 使用BM型黏度計(東京計器製造所)，於4號轉子/30 rpm/100℃之條件下，測定各胺甲酸乙酯預聚物之黏度。
(熱軟化溫度測定) (1)試樣之製作 將加溫至100℃之胺甲酸乙酯預聚物以膜厚成為50 μm之方式塗佈於離型紙上，於25℃/60 RH%之條件下使其熟成48小時以上後，將其自離型紙剝離，從而獲得寬度1.5 cm、長度6 cm之半透明膜。如圖1所示，於半透明膜10之上下安裝夾具12，利用Sellotape(註冊商標)進而固定夾具12，並安裝砝碼14而製成試樣16，上述砝碼14懸吊於一夾具12時施加450 g/cm2 之負重。再者，膜10之中央部長度方向2 cm未由Sellotape(註冊商標)覆蓋。
(2)測定 如圖2所示，將各例之上述試樣16之未安裝砝碼14之夾具12安裝於吉爾老化恆溫箱20之轉盤22。其後，一面使轉盤22以5 rpm旋轉，一面以3℃/min之速度使吉爾老化恆溫箱20內自室溫開始升溫。將膜10切斷時或者伸長至2倍時之溫度作為軟化點。
(接著強度) (1)膜準備 將加溫至100℃之胺甲酸乙酯預聚物以膜厚成為50 μm之方式塗佈於離型紙上，於25℃/60 RH%之條件下使其熟成48小時以上後，將其自離型紙剝離，從而獲得半透明膜。
(2)層壓 使用試驗用聚酯網格原材料之基布，上下夾住上述所得之膜，並自上部進行150℃/5秒之熱壓接合後，製成20 mm寬之短條狀之測定試樣。 (3)測定 利用Autograph AGS-J(島津製作所)以200 mm/min之速度進行拉伸，測定接著強度。根據該接著強度為0.3 kgf/cm以上，判斷密接性相較於使用上述基材方面實用上不存在問題之水準更佳。
[表1]
原材料 實施例1 實施例2 實施例3 實施例4 實施例5 比較例1 比較例2
聚酯多元醇 100 100 100 100 100 100 100
MDI 25 25 25 25 25 25 25
NCO/OH比 2.0 2.0 2.0 2.0 2.0 2.0 2.0
1-十六烷醇 2.4 4.8 6.1 - - 1.2 7.3
1-十二烷醇          2.8 -      
二丁胺             1.9      
密封率(莫耳%) 20 40 50 30 30 10 60
黏度(dPa･s) 90 120 130 110 80 85 155
熱軟化點(℃) 150 115 80 130 125 165 60
接著強度(kgf/cm) 0.3 0.7 0.5 0.4 0.6 0.1 0.1
(合成仿皮之製作) 將RESAMINE NE-8875-30M(大日精化工業(股))以膜厚成為40 μm之方式塗佈於離型紙上，以120℃/5分鐘使其乾燥，獲得表皮層。 另一方面，將實施例1所示之濕氣硬化型接著劑以膜厚成為100 μm之方式塗佈於離型紙上，於25℃/60 RH%之條件下使其熟成48小時，獲得接著層。 將所獲得之接著層自離型紙剝離，並由表皮層與試驗用聚酯網格原材料之基布夾住，表皮層之離型紙側使用熱源之封口機，於170℃/0.15 MPa/30秒之條件下進行層壓。最後將表皮層之離型紙剝離而製成合成仿皮。所獲得之合成仿皮質地良好。
10:膜 12:夾具 14:砝碼 16:試樣 20:吉爾老化恆溫箱 22:轉盤
圖1係對實施例之評估中所使用之試樣之形態進行說明之模式性說明圖。 圖2係對實施例之評估中所使用之吉爾老化恆溫箱之形態進行說明之說明。

Claims (6)

  1. 一種胺甲酸乙酯預聚物，其具有異氰酸酯基， 100℃下之黏度為30～600 dPa・s，且 濕氣硬化後之熱軟化溫度為75～155℃。
  2. 如請求項1之胺甲酸乙酯預聚物，其中上述異氰酸酯基之相對於總莫耳數之10～55%由密封劑密封。
  3. 如請求項1或2之胺甲酸乙酯預聚物，其係聚異氰酸酯與多元醇之反應物，且上述聚異氰酸酯之異氰酸酯基相對於多元醇之羥基之當量比(NCO/OH)為1.2～2.5。
  4. 一種接著劑，其包含如請求項1至3中任一項之胺甲酸乙酯預聚物。
  5. 一種積層體，其於基材膜上具有包含如請求項4之接著劑之塗膜之濕氣硬化物層。
  6. 一種合成仿皮，其於如請求項5之積層體之上述濕氣硬化物層上具有基布之熱壓接合物。
TW109129544A 2019-09-05 2020-08-28 胺甲酸乙酯預聚物、接著劑、積層體、及合成仿皮 TW202115145A (zh)

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