TW202022003A - 樹脂與熱熔膠 - Google Patents
樹脂與熱熔膠 Download PDFInfo
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Abstract
本揭露提供之樹脂,係由1莫耳份的多異氰酸酯基的核心與3至4.5莫耳份的二醇反應形成中間產物後,中間產物再與3至4.5莫耳份的第一二異氰酸酯反應而成。多異氰酸酯基的核心可為多異氰酸酯,其具有超過兩個異氰酸酯基。另一方面,多異氰酸酯基的核心可由第二二異氰酸酯與多羥基化合物反應而成,且多羥基化合物具有超過兩個羥基。
Description
本揭露關於熱熔膠與其樹脂組成。
在所有製鞋所使用的原材料中,連結各個零部元件、組裝成為鞋子產品的關鍵是接著劑。近年來各種商品皆以人類生存環境永續性為訴求,世界各國均積極推動環保法規,以限制產業生產製程中的VOC排放,即在製鞋過程中不得使用或減少使用有機溶劑。製鞋業發展已經明確走向需要環保製程、快速加工的材料,才能滿足市場快速變化及自動化生產要求。鞋用接著劑主要的技術發展方向為低污染及高功能化,低污染的接著劑以水性化樹脂及無溶劑化樹脂為主,後者發展出熱熔樹脂、粉體樹脂及UV樹脂等系統,其中PU (polyurethane,聚氨酯)熱熔膠具加快產速、降低成本之優勢。世界各鞋用樹脂特化品廠如Bayer、Henkel、Bostik等公司皆開發不含有機溶劑的高功能鞋用室溫交聯PU樹脂,初期強度達到3kgf/cm2
以上,成功的應用在高功能鞋材的貼合,將有機溶劑含量降低到接近零VOC的程度。但目前室溫交聯PU樹脂存在黏度高(100,000 cps以上@120℃)與流動性差的問題。綜上所述,目前亟需新的接著劑以同時符合無溶劑、高接著強度、與低黏度等特性。
本揭露一實施例提供之樹脂,係由1莫耳份的多異氰酸酯基的核心與3至4.5莫耳份的二醇反應形成中間產物後,中間產物再與3至4.5莫耳份的第一二異氰酸酯反應而成。
本揭露一實施例揭露之熱熔膠包括樹脂,且樹脂係由1莫耳份的多異氰酸酯基的核心與3至4.5莫耳份的二醇反應形成中間產物後,中間產物再與3至4.5莫耳份的第一二異氰酸酯反應而成。
本揭露一實施例提供樹脂的形成方法如下。首先,取3至4.5莫耳份的第二二異氰酸酯與1莫耳份的多羥基化合物於60℃至90℃之間的溫度下反應形成1莫耳份的多異氰酸酯基的核心,其具有超過兩個羥基。若形成多異氰酸酯基的核心的反應溫度過低,則造成多異氰酸基核心反應不完全。若形成多異氰酸酯基的核心的反應溫度過高,則造成多異氰酸基核心亂序架接造成樹脂黏度劇烈爬升。舉例來說,多羥基化合物之結構可為,n大於2,且R1
為C1-21
的直鏈或支鏈的烷基,或C3-12
的環烷基或烷基環烷基,且烷基環烷基上的烷基可為直鏈或支鏈的烷基。在一實施例中,R1
為C6-18
的直鏈或支鏈的烷基,或C6-12
的環烷基或烷基環烷基,且烷基環烷基上的烷基可為直鏈或支鏈的烷基。在一實施例中,R1
為C9-12
的直鏈或支鏈的烷基。在一實施例中,多羥基化合物不具有芳基,其可為三羥甲基丙烷(TMP)、三羥丙烷、甘油、季戊四醇、丁四醇、類似物、或上述之組合。舉例來說,第二二異氰酸酯的結構可為,其中R2
可為C3-8
的烷基或C3-17
的環烷基或烷基環烷基,且烷基環烷基上的烷基可為直鏈或支鏈的烷基。在一實施例中,第二二異氰酸酯不具有芳基,其可為二異氰酸異佛爾酮(isophorone diisocyanate, IPDI)、五亞甲基二異氰酸酯(pentamethylene diisocyanate,PDI)、六亞甲基二異氰酸酯(hexamethylene diisocyanate,HDI)、雙(異氰酸 4-環己酯)甲烷(Dicyclohexylmethane 4,4'-diisocyanate,H12
MDI)、類似物、或上述之組合。若第二二異氰酸酯的用量過低,則多羥基化合物的羥基無法完全反應,即減少多異氰酸酯基的核心之異氰酸酯基,使最終形成的樹脂黏度過高。上述多異氰酸酯基的核心之形成反應如下:
接著取1莫耳份的多異氰酸酯基的核心與3至4.5莫耳份的二醇反應形成中間產物。若二醇的用量過低,則會使樹脂分子間形成網狀結構,造成黏度劇烈爬升。若二醇的用量過高,則需額外步驟去除未與多異氰酸酯基的核心反應之二醇,以避免稀釋樹脂的濃度。上述形成中間產物的反應溫度介於約90℃至120℃之間。若反應溫度過低,則造成多異氰酸基核心反應不完全。若反應溫度過高,則造成多異氰酸基核心亂序架接造成樹脂黏度劇烈爬升。在一實施例中,二醇可為聚酯二醇、聚醚二醇、類似物、或上述之組合。上述二醇的重均分子量可介於2000至4000之間,例如大於2000且小於等於4000。若二醇的重均分子量過低,則形成的樹脂產物的初期強度不足。若二醇的重均分子量過高,則造成樹脂整體黏度過高無法操作。在一實施例中,二醇可為結晶性二醇。在一實施例中,二醇可為高結晶性二醇。舉例來說,聚酯二醇不具有芳基,其結構可為,其中x為重複單元的數目,x可為3至25,R3
為C2-8
的烷撐基或C3-8
的環烷撐基或烷基環烷撐基,且烷基環烷撐基上的烷基可為直鏈或支鏈的烷基。R4
為C3-8
的烷撐基或C3-8
的環烷撐基或烷基環烷撐基,且烷基環烷撐基上的烷基可為直鏈或支鏈的烷基。當二醇為聚酯二醇時,形成中間產物的反應如下:。
另一方面,當二醇為聚醚二醇,其不具有芳基,且結構可為,其中y為重複單元的數目,y可為8至75,而R6
為C3-8
的直鏈或支鏈烷撐基或C3-8
的環烷撐基或烷基環烷撐基,且烷基環烷撐基上的烷基可為直鏈或支鏈的烷基。當二醇為聚醚二醇時,形成中間產物的反應如下:。
接著取中間產物與3至4.5莫耳份的第一二異氰酸酯反應形成樹脂,可使所形成的樹脂的分子末端具有異氰酸反應官能基。若第一二異氰酸酯的比例過低,則會使樹脂分子間形成網狀結構,造成黏度劇烈爬升。若第一二異氰酸酯的比例過高,則需額外步驟去除未與中間產物反應之第一二異氰酸脂,以避免稀釋樹脂的濃度。在一實施例中,上述形成樹脂的反應溫度介於90℃至120℃之間。若反應溫度過低,則造成多異氰酸基核心反應不完全。若反應溫度過高,則造成多異氰酸基核心亂序架接造成樹脂黏度劇烈爬升。第一二異氰酸酯的結構可為,其中R5
可為C3-8
的烷基或C3-8
的環烷基或烷基環烷基,且烷基環烷基上的烷基可為直鏈或支鏈的烷基。在一實施例中,第一二異氰酸酯不具有芳基,其可為IPDI、PDI、HDI、雙(異氰酸 4-環己酯)甲烷(DICYCLOHEXYLMETHANE 4,4’-DIISOCYANATE, H12
MDI)、類似物、或上述之組合。第一二異氰酸酯可與前述之第二二異氰酸酯可相同或不同。換言之,上述之樹脂係由1莫耳份的多異氰酸酯基的核心與3至4.5莫耳份的二醇反應形成中間產物後,中間產物再與3至4.5莫耳份的第一二異氰酸酯反應而成,且多異氰酸酯基的核心可由多羥基化合物與第二二異氰酸酯反應而成。當用以形成前述中間產物之二醇為聚酯二醇時,形成樹脂的反應示例如下:。 當用以形成前述中間產物之二醇為聚醚二醇時,形成樹脂的反應示例如下:。
在一實施例中,可依序進行下述步驟:(1)取第二二異氰酸酯與多羥基化合物反應形成多異氰酸酯基的核心,(2)取多異氰酸酯基的核心與二醇反應形成中間產物,再(3)取中間產物與第一二異氰酸酯反應形成樹脂。在另一實施例中,可直接將二異氰酸酯(作為第一二異氰酸酯與第二二異氰酸酯)、多羥基化合物、與二醇直接混合(一鍋法),再經由調整混合物的溫度變化以確保依序進行上述反應。二異氰酸酯、多羥基化合物、與二醇的具體材料種類同前述,在此不另贅述。在一鍋法中,第一異氰酸酯與第二異氰酸酯的種類相同。在一鍋法中,前述「二異氰酸酯的莫耳數」與「多羥基化合物與二醇的莫耳數合計」的比例可為1.3:1至1.7:1,藉由莫耳數的比例控制,可製得末端具有異氰酸反應官能基之樹脂。
在另一實施例中,多異氰酸酯基的核心為多異氰酸酯,其具有超過兩個異氰酸酯基。舉例來說,多異氰酸酯的結構可為,n大於2,R1
為C1-10
的直鏈或支鏈烷基或C3-18
的環烷基或烷基環烷基,且烷基環烷基上的烷基可為直鏈或支鏈的烷基。在一實施例中,多異氰酸酯不具有芳基,其可為二異氰酸異佛爾酮(isophorone diisocyanate, IPDI)、五亞甲基二異氰酸酯(pentamethylene diisocyanate)、六亞甲基二異氰酸酯(hexamethylene diisocyanate,HDI)、雙(異氰酸 4-環己酯)甲烷(DICYCLOHEXYLMETHANE 4,4’-DIISOCYANATE, H12
MDI)、類似物、或上述之組合。在一實施例中,以多異氰酸酯作為多異氰酸酯基的核心,二醇為聚酯二醇,形成中間產物的反應示例如下:。在此實施例中,中間產物與第一二異氰酸酯形成樹脂的反應如下:。在另一實施例中,以多異氰酸酯作為多異氰酸酯基的核心,二醇為聚醚二醇,形成中間產物的反應示例如下:。在此實施例中,中間產物與第一二異氰酸酯形成樹脂的反應如下:。
在一實施例中,上述樹脂的結晶度大於70%,可有效提升樹脂之機械強度。一般而言,聚異氰酸酯系的樹脂結晶度小於70%,而樹脂無法在施工初期快速固化,使貼合後無法展現機械強度。
值得注意的是,本揭露藉由前述的方法所製得之樹脂的分子結構為樹枝狀結構,可降低樹脂的黏度。此外,藉由將高結晶性的二醇導入樹脂的分子結構中,可提升熱熔膠的初期接著強度。
本揭露一實施例提供之熱熔膠包括上述樹脂。在一些實施例中,熱熔膠不含溶劑,即樹脂可直接作為熱熔膠。在一些實施例中,樹脂在120℃下的黏度介於6000cps至15000cps之間。若樹脂的黏度過高,可能在塗佈於物件上之前即部份硬化。若樹脂的黏度過低,可能在硬化前流動至不需塗佈樹脂的部份而劣化產品。在一些實施例中,熱熔膠於20%至80%的相對濕度與10℃至30℃的溫度下硬化。舉例來說,可在常溫(如25℃)與一般濕度(RH=25%)下快速硬化上述熱熔膠。
為了讓本揭露之上述和其他目的、特徵、和優點能更明顯易懂,下文特舉數實施例配合所附圖示,作詳細說明如下:
實施例
實施例1 取3莫耳份的聚酯二醇7330 (Evonik Dynacoll 7330,重均分子量 3500)作為二醇、1莫耳份的三羥甲基丙烷(TMP)作為多羥基化合物、以及7莫耳份的六亞甲基二異氰酸酯(HDI)作為第一二異氰酸酯與第二二異氰酸酯混合。加熱上述混合物至80℃並反應1小時,使TMP與部份的HDI (第二二異氰酸酯)反應形成多異氰酸酯基的核心。接著加熱上述混合物至110℃並反應1小時,使多異氰酸酯基的核心與聚酯二醇7330反應形成中間產物。接著調整上述混合物至100℃並反應1小時,使中間產物與其餘部份的HDI (第一二異氰酸酯)反應形成樹脂。上述樹脂於120℃的黏度為14650cps (量測標準為ASTM-D3236)。以ASTM-D1876量測樹脂的初期接著強度與末期接著強度,分別為1.19kgf/cm2
與12.25kgf/cm2
。上述樹脂的結晶度為77.5%。
實施例2 取3莫耳份的聚醚二醇5602 (長興ETEROL-5602,重均分子量為3750)作為二醇、1莫耳份的TMP作為多羥基化合物、以及7莫耳份的HDI作為第一二異氰酸酯與第二二異氰酸酯混合。加熱上述混合物至80℃並反應1小時,使TMP與部份的HDI (第二二異氰酸酯)反應形成多異氰酸酯基的核心。接著加熱上述混合物至110℃並反應1小時,使多異氰酸酯基的核心與聚醚二醇5602反應形成中間產物。接著調整上述混合物至100℃並反應1小時,使中間產物與其餘部份的HDI (第一二異氰酸酯)反應形成樹脂。上述樹脂於120℃的黏度為32710cps (量測標準為ASTM-D3236)。以ASTM-D1876量測樹脂的初期接著強度與末期接著強度,分別為4.22kgf/cm2
與14.08kgf/cm2
。上述樹脂的結晶度為70.5%。
實施例3 取3莫耳份的聚酯二醇PBA3000 (永純化學,重均分子量為3000)作為二醇、1莫耳份的三聚HDI(科思創 Desmodur N3300)作為多異氰酸酯基的核心、以及3莫耳份的HDI作為第一二異氰酸酯混合。加熱上述混合物至100℃並反應1小時,使多異氰酸酯基的核心與聚酯二醇PBA3000反應形成中間產物。接著加熱上述混合物至110℃並反應1小時,使中間產物與HDI (第一二異氰酸酯)反應形成樹脂。
比較例1 取3莫耳份的聚酯二醇PBA(永純化學PBA,重均分子量為2000)作為二醇、1莫耳份的TMP作為多羥基化合物、以及7莫耳份的HDI作為第一二異氰酸酯與第二二異氰酸酯混合。加熱上述混合物至80℃並反應1小時,使TMP與部份的HDI (第二二異氰酸酯)反應形成多異氰酸酯基的核心。接著加熱上述混合物至80℃並反應1小時,使多異氰酸酯基的核心與聚酯二醇PBA反應形成中間產物。接著加熱上述混合物至110℃並反應1小時,使中間產物與其餘部份的HDI (第一二異氰酸酯)反應形成樹脂。上述樹脂於120℃的黏度為14650cps (量測標準為ASTM D3236)。以ASTM- D1876量測樹脂的初期接著強度與末期接著強度,分別為0kgf/cm2
與8.13kgf/cm2
。上述樹脂的結晶度為56.0%。由比較例1可知,若二醇的重均分子量過低,則樹脂的初期接著黏度不足。
比較例2 取2莫耳份的聚醚二醇5602(長興ETEROL-5602)作為二醇、1莫耳份的1,4-丁二醇作為二羥基化合物、以及2莫耳份的六亞甲基二異氰酸酯(HDI)作為第一二異氰酸酯與第二二異氰酸酯混合。加熱上述混合物至80℃並反應1小時,使1,4-丁二醇(二羥基化合物)與部份的HDI (第二二異氰酸酯)反應形成二異氰酸酯基的核心。接著加熱上述混合物至100℃並反應1.5小時,使二異氰酸酯基的核心與聚醚二醇5602反應形成中間產物。接著加熱上述混合物至110℃並反應1小時,使中間產物與其餘部份的HDI (第一二異氰酸酯)反應形成樹脂。上述樹脂於120℃的黏度為86900cps (量測標準為ASTM-D3236)。以ASTM-D1876量測樹脂的初期接著強度與末期接著強度,分別為7.15kgf/cm2
與7.22kgf/cm2
。上述樹脂的結晶度為51.8%。由比較例2可知,若樹脂的核心具有二異氰酸酯基而非多異氰酸酯基,則黏度過高而難以施加至欲接著的物件。
雖然本揭露已以數個實施例揭露如上,然其並非用以限定本揭露,任何本技術領域中具有通常知識者,在不脫離本揭露之精神和範圍內,當可作任意之更動與潤飾,因此本揭露之保護範圍當視後附之申請專利範圍所界定者為準。
無。
無。
無。
Claims (8)
- 一種樹脂,係由: 1莫耳份的一多異氰酸酯基的核心與3至4.5莫耳份的一二醇反應形成一中間產物後,該中間產物再與3至4.5莫耳份的一第一二異氰酸酯反應而成。
- 如申請專利範圍第1項所述之樹脂,其中該多異氰酸酯基的核心係一多異氰酸酯,其具有超過兩個異氰酸酯基。
- 如申請專利範圍第1項所述之樹脂,其中該多異氰酸酯基的核心係由3至4.5莫耳份的一第二二異氰酸酯與1莫耳份的一多羥基化合物反應而成,且該多羥基化合物具有超過兩個羥基。
- 如申請專利範圍第1項所述之樹脂,其中該二醇係聚醚二醇或聚酯二醇。
- 如申請專利範圍第1項所述之樹脂,其中該二醇的重均分子量介於2000至4000之間。
- 一種熱熔膠,包括一樹脂,且該樹脂係由1莫耳份的一多異氰酸酯基的核心與3至4.5莫耳份的一二醇反應形成一中間產物後,該中間產物再與3至4.5莫耳份的一第一二異氰酸酯反應而成。
- 如申請專利範圍第6項所述之熱熔膠,其不含溶劑。
- 如申請專利範圍第6項所述之熱熔膠,其於20%至80%的相對濕度的硬化溫度介於10℃至30℃之間。
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