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TWI781394B - 聚丙烯積層材料及其製法 - Google Patents

聚丙烯積層材料及其製法 Download PDF

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TWI781394B
TWI781394B TW109113494A TW109113494A TWI781394B TW I781394 B TWI781394 B TW I781394B TW 109113494 A TW109113494 A TW 109113494A TW 109113494 A TW109113494 A TW 109113494A TW I781394 B TWI781394 B TW I781394B
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layer
main body
anhydride
laminated material
modified polypropylene
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TW109113494A
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TW202140284A (zh
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林至逸
鄭國光
蔣其晉
鄭又謙
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三芳化學工業股份有限公司
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Priority to TW109113494A priority Critical patent/TWI781394B/zh
Priority to CN202010799246.5A priority patent/CN113524828A/zh
Priority to US17/237,374 priority patent/US20210331451A1/en
Publication of TW202140284A publication Critical patent/TW202140284A/zh
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Abstract

本發明提供一種積層材料，其包含一酸酐改質聚丙烯層、一主體層及一黏劑層直接接觸該酸酐改質聚丙烯層，並與該主體層貼合。本發明另提供該積層材料之製造方法。

Description

聚丙烯積層材料及其製法
本發明係關於一種聚合物材料，具體而言，係關於一種積層材料及其製法。
在表面材料之技術領域中，穩固結合兩不同材料，使其不致產生層間剝離為一大重點。不同材料間，因極性或是表面粗糙度的不同，彼此間不易貼合，尤其當貼合之對象為皮革或發泡材時，更難達成。
目前業界對於貼合不同材料，特別是貼合不同極性材料之時，需將其中一材料進行表面處理，例如於表面進行物理性之粗糙化或是化學性之表面處理劑改善其極性等程序，才能達到穩固結合的效果。然而前述處理不僅耗費人力、成本，且經表面處理後，仍有不均勻或再現性的問題。
舉例言之，目前業界習用之聚丙烯箔(polypropylene foil)欲進行貼合時，需先將聚丙烯箔之表面以底漆(primer)使其改質，以加強材料表面對其他層之貼合強度，再經過塗佈或噴塗膠層，方可與其他材料貼合。當欲製得包含發泡材料、聚丙烯箔及皮革複合材料時，其生產方法包含先製得聚丙烯箔、將聚丙烯箔表面塗佈底漆進行表面處理、於處理後 之表面上塗佈膠層、貼合至皮革，接著再將此聚丙烯箔及皮革複合材料加熱並使用陽模成型以獲得所欲之形狀，最後在此複合材料內形成一發泡材料。此步驟繁複，且涉及不同之加工領域，應用十分不便。
另一方面，表面處理劑通常使用化學溶劑或催化劑，所適用之膠層亦可能包含如氯之成分，對環境及生物體亦造成負面影響，並不符合現今之潮流。
因此，本揭示提供一種積層材料，其完全免除習知技術中貼合不同材料所需採行之表面處理，製程簡易，成本低廉，貼合力強，同時兼顧各材料間之物性，且不需使用對環境及生物體不友善之成分。
本揭示提供一種積層材料，其包含：一改質聚丙烯層，其包含酸酐接枝之聚丙烯，且包括一未經粗糙化之表面；一主體層；及一黏劑層，其直接接觸該改質聚丙烯層之該未經粗糙化之表面，並與該主體層貼合。
本揭示另提供一種製造前述積層材料之方法，其包含：(a)提供聚丙烯及酸酐；(b)共押出聚丙烯及酸酐，並形成片狀，以獲得該改質聚丙烯層；(c)提供該主體層；及(d)施加該黏劑層使其直接接觸該改質聚丙烯層之該未經粗糙化之表面，並與該主體層貼合。
1:積層材料
2:積層材料
11:改質聚丙烯層
12:主體層
13:黏劑層
21:改質聚丙烯層
22:主體層
23:黏劑層
111:未經粗糙化之表面
211:未經粗糙化之上表面
212:未經粗糙化之下表面
221:上主體層
222:下主體層
231:上黏劑層
232:下黏劑層
圖1顯示本揭示一具體實施例之積層材料剖面圖；及圖2顯示本揭示一具體實施例之積層材料剖面圖。
參看圖1，其係本揭示一具體實施例之一積層材料1，其包含：一改質聚丙烯層11，其包含酸酐接枝之聚丙烯，且包括一未經粗糙化之表面111；一主體層12；及一黏劑層13，其直接接觸該改質聚丙烯層11之該未經粗糙化之表面111，並與該主體層12貼合。
根據本揭示之積層材料係指具有不同材料層複合所形成之複合材料，其中該積層材料或各材料層之形狀包含但不限於片狀、層狀、塊狀、中空塊狀。
根據本揭示之改質聚丙烯層係指材料包含聚丙烯之材料，其中該聚丙烯包含酸酐接枝之聚丙烯，亦可包含未接枝之聚丙烯。根據本揭示之酸酐包含但不限於順丁烯二酸酐、丁二酸酐、鄰苯二甲酸酐、丁酸酐、醋酸酐；較佳係為順丁烯二酸酐。根據所需之性質，可調整酸酐改質之態樣及數量。於本揭示之一較佳具體實施例中，該改質聚丙烯層中，該酸酐之重量含量為自約1%至約10%；更佳係為自約5%至約8%。另一方面，於本揭示之一較佳具體實施例中，其中該聚丙烯中，該酸酐接枝之比例為自約0.2mol/kg至約2mol/kg；更佳係為自約1.0mol/kg至約1.8mol/kg。
雖不願為理論所限制，但咸信根據本揭示之該改質聚丙烯層係運用酸酐本身擁有的極性，於與聚丙烯接枝後，進一步賦予聚丙烯極性，而使該改質聚丙烯層具有酸酐官能基，使該改質聚丙烯層不需進行表面處理就能擁有同樣的貼合效果。
於本揭示之一具體實施例中，該改質聚丙烯層之材料係包含其他材料，以根據所欲之用途提供適當之物性，例如混練其他聚合物，以提供耐燃、導電、耐候、耐熱及耐衝擊等物性。於本揭示之一較佳具體實施例中，該改質聚丙烯層另包含熱可塑性聚烯烴。較佳地，該熱可塑性聚烯烴係為乙烯丙烯共聚物。根據所需之性質，可調整其他材料之態樣及數量。於本揭示之一較佳具體實施例中，該改質聚丙烯層中，該熱可塑性聚烯烴之重量含量為自90%至約99%；更佳係為自90%至約96%。雖不願為理論所限制，但咸信其中添加熱可塑性聚烯烴可賦予原本無彈性的聚丙烯材料較高之韌性，並且在成型加工的製程上能夠有較好的成型效果。
根據本揭示之改質聚丙烯層11包括一未經粗糙化之表面111。根據本揭示之粗糙化包含但不限於該改質聚丙烯層之表面以物理或化學方式改變其平坦度。舉例言之，以物理方式於該改質聚丙烯層之表面形成規則或不規則之孔洞、凹槽、刻痕，或以化學方式於該改質聚丙烯層之表面進行侵蝕。本揭示所言之平坦度係指凹凸高度相對理想平面的偏差，可藉由業界所習用之儀器或測量規範而界定。
根據本揭示之該主體層可為任何之固體材料，於本揭示之具體實施例中，該主體層係為一發泡層或一皮革層。
根據本揭示之發泡層較佳係為由一發泡樹脂提供。本揭示所言之「發泡樹脂」乙詞指含有熱塑樹脂及熱分解發泡劑之材料。該樹脂 較佳地包含選自由以下各物組成之群的至少一者：聚胺酯、聚烯烴、聚碳酸酯、聚乙烯醇、耐綸、彈性橡膠、聚苯乙烯、聚芳烴分子、含氟聚合物、聚醯亞胺、架橋聚胺酯、架橋聚烯烴、聚醚、聚酯、聚丙烯酸酯、彈性聚乙烯、聚四氟乙烯、聚(對苯二甲酸亞乙酯)、聚芳烴醯胺、聚芳烴、聚甲基丙烯酸甲酯、其共聚物、其嵌段共聚物、其混合物及其摻合物。
根據本揭示之發泡樹脂發泡之方法可為化學發泡或物理發泡，其中化學發泡係利用可進行化學反應以產生氣體之試劑，使其反應後所產生之氣體均勻分布於包含發泡樹脂中，以形成孔洞。另一方面，物理發泡係將氣體打入該發泡樹脂中，並藉由攪拌使打入之氣體均勻分布於該發泡樹脂中。於本揭示之另一較佳具體實施例中，該等孔洞係藉由於發泡樹脂中填充複數個聚合中空小球體而提供，該中空小球體之具體例為Expancel® 551DE40d42(重量平均直徑為30至50微米，Akzo Nobel公司製)或Expancel® 551DE20d60(重量平均直徑為15至25微米，Akzo Nobel公司製)。
根據本揭示之孔洞可為連通型孔洞或獨立型孔洞，本揭示所言之「連通型孔洞」係指至少二孔洞間係為連通，而形成類似蟻穴型之孔洞；本揭示所言之「獨立型孔洞」係指彼此為獨立不連通之孔洞，通常具有圓形或橢圓形之剖面，而為球狀或卵狀孔洞。
根據本揭示之皮革層可為天然皮革或人工皮革。該天然皮革係取自動物皮膚且經鞣製形成，其包括但不限牛皮、水牛皮、豬皮、山羊皮、綿羊皮、羔羊皮、鹿皮、袋鼠皮、雞皮、蛇皮、鴕鳥皮、鱷魚皮、魚皮等。該人工皮革係以聚合物加工，以模仿真皮外觀和觸感的人造材 料。根據本揭示之人工皮革包含但不限於單層人工皮革、多層人工皮革或複合人工皮革。於本揭示之一較佳具體實施例中，該皮革層係為人工皮革。
參看圖2，其係本揭示一具體實施例之一積層材料2，其包含：一改質聚丙烯層21，且包括一未經粗糙化之上表面211及一未經粗糙化之下表面212；一主體層22，包含一上主體層221及一下主體層222，使該改質聚丙烯層21夾設於該上主體層221及該下主體層222中；及一黏劑層23，包含一上黏劑層231及一下黏劑層232，其分別直接接觸該未經粗糙化之上表面211及該未經粗糙化之下表面212，並與該上主體層221及下主體層222貼合。
根據本揭示之該上主體層及下主體層之材料可為相同或不同，舉例言之，該上主體層可為皮革層，該下主體層可為發泡層；或是該上主體層與該下主體層皆為皮革層；或是該上主體層與該下主體層皆為發泡層。
根據本揭示之該上黏劑層及下黏劑層之材料可為相同或不同。
於本揭示之一較佳具體實施例中，該黏劑層包括但不限於感壓膠、一液型糊劑、二液型糊劑、壓克力樹脂、環氧樹脂、熱熔膠。感壓膠通常包含一載體膜，該載體膜包括(例如)聚酯，且在載體膜之上側及下側上具有具流動性之黏合層。一液型糊劑係指包含高分子量彈性體充當黏接劑之糊劑，較佳係包含聚胺酯，一液型糊劑包含油改質型塗料及濕氣 硬化型塗料，其中油改質型塗料採用天然油脂與二甘油脂等改質多醇類(polyol)與甲苯二對氰酸(toluene diisocyanate，TDI)反應而成；濕氣硬化型糊劑含有氫氧基的聚酯類(polyester)與聚醚類(polyether)，藉由過量的NCO基(NCO/OH>1)與甲苯二對氰酸、二苯基甲烷二異氰酸酯(diphenylmethane diisocyanate，MDI)、己二異氰酸酯(hexamethylene diisocyanate，HMDI)等之氫氧基反應，形成末端含有異氰酸酯(isocyanate)基的預聚合體，此官能基可與空氣中的濕氣產生胺類(amine)形成尿素結合，和雙縮尿素(biuret)成為硬化塗膜。二液型糊劑指包含彼此相互作用或交聯以實現黏合作用之兩種成分的糊劑，較佳係包含一彈性體及聚異氰酸酯，包含有觸媒硬化型，其主要是由聚乙二醇(polyethylene glycol)、聚丙二醇(polypropylene glycol)或多元醇(polyol)的酯化交換的單二酸甘油脂(mono diglyceride)的混合體與三級胺及金屬鹽類等觸媒反應使其硬化；多元醇硬化型PU塗料是由異氰酸酯預聚合物(isocyanate prepolymer)、聚醇類(polyol-ester)或聚醚類(polyether)，以及含有OH-之壓克力樹脂等多元醇之OH-反應形成。壓克力樹脂包含常溫硬化型及加熱硬化乾燥型；其中常溫硬化型主要為壓克力樹脂單體，加熱硬化乾燥型則是以壓克力樹脂聚合物為基本構造，於其中導入活性反應基，當加熱時該樹脂單獨或與含有反應基之樹脂以及交聯劑反應形成三次元之網狀結構。環氧樹脂可藉由加入交聯劑，形成三次元結構；熱熔膠包含熱可塑性樹脂，可藉由軟化或熔化該熱可塑性聚合物而黏合該主體層及該改質聚丙烯層。於本揭示之一較佳具體實施例中，該熱可塑性樹脂包含但不限於熱可塑性聚胺酯、熱可塑性聚酯彈性體、聚烯烴系彈性體或水性糊劑。
於本揭示之一具體實施例中，該黏劑層較佳係藉由塗覆、 轉寫、印刷或刮擦在該改質聚丙烯層之該未經粗糙化之表面上，使該黏劑層直接接觸該改質聚丙烯層之該未經粗糙化之表面，並視黏劑層之種類，使該改質聚丙烯層並與該主體層貼合。
根據本揭示之該改質聚丙烯層之表面不需施加化學性之表面處理劑，例如底漆，因而該改質聚丙烯層可直接與該黏劑層直接接觸，與習知技術相比製程簡易，成本低廉，貼合力強，同時兼顧各材料間之物性，且不需使用對環境及生物體不友善之表面處理劑成分。
本揭示再提供一種製造前述積層材料之方法，其包含：(a)提供聚丙烯及酸酐；(b)共押出聚丙烯及酸酐，並形成片狀，以獲得該改質聚丙烯層；(c)提供該主體層；及(d)施加該黏劑層使其直接接觸該改質聚丙烯層之該未經粗糙化之表面，並與該主體層貼合。
於本揭示之一具體實施例中，步驟(b)共押出之方法包含但不限於將所需共押出之聚丙烯原料、酸酐原料及視需要之其他材料進行乾燥，並熔融，使用如T-die之膜頭共押出，冷卻成膜後並控制所需之厚度。於本揭示之一具體實施例中，可於押出加熱時同時進行加壓，例如使用成型輪調整所需之厚度。
茲以下列實例予以詳細說明本發明，唯其並不意謂本發明僅侷限於此等實例所揭示之內容。
實例1：
乾燥條件：將約77%之聚丙烯、約10%之熱可塑性聚烯 烴、約10%之含順丁烯二酸酐之聚烯烴(順丁烯二酸酐：聚烯烴=1：9)及約3%之其他添加劑於60℃進行乾燥，使含水率控制至約300ppm以下。
押出機溫度條件：170℃、210℃、195℃
T-die膜頭溫度設定為190℃。
押出及經成型輪冷卻成膜，並控制成型輪之速度為8.0m/min，可得到總厚度為約0.3mm之膜，經1至2天熟成後，獲得改質聚丙烯層。
實例2：
乾燥條件：將約87%之聚丙烯、約10%之含順丁烯二酸酐之聚烯烴(順丁烯二酸酐：聚烯烴=1：9)及約3%之其他添加劑於60℃進行乾燥，使含水率控制至約300ppm以下。
押出機溫度條件：200℃、230℃、220℃
T-die膜頭溫度設定為210℃。
押出及經成型輪冷卻成膜，並控制成型輪之速度為8.0m/min，可得到總厚度為約0.3mm之膜，經1至2天熟成後，獲得改質聚丙烯層。
將經酸酐改質之改質聚丙烯層與未經酸酐改質之聚丙烯層進行物性測試，其結果如下表1：
Figure 109113494-A0305-02-0011-1
實例3：
將熱熔膠置於改質丙烯層上，並與一人工皮革進行熱壓貼合，壓力為5kg，時間為36秒，待1天熟成後，切割為1cm x 15cm之測試片，使用拉力試驗機測試其剝離強度。
其結果示於表2，未改質之聚丙烯層貼合強度最高僅為1.2N，而經酸酐改質聚丙烯層之貼合強度為2.0N以上。
Figure 109113494-A0305-02-0012-2
上述實施例僅為說明本發明之原理及其功效，而非限制本發明。本發明所屬技術領域中具通常知識者對上述實施例所做之修改及變化仍不違背本發明之精神。本發明之權利範圍應如後述之申請專利範圍所列。
1:積層材料
11:改質聚丙烯層
12:主體層
13:黏劑層
111:未經粗糙化之表面

Claims (9)

  1. 一種積層材料，其包含：一改質聚丙烯層，其包含酸酐接枝之聚丙烯，且包括一未經粗糙化之表面；一主體層；及一黏劑層，其直接接觸該改質聚丙烯層之該未經粗糙化之表面，並與該主體層貼合；其中該主體層包含至少一發泡層。
  2. 根據請求項1之積層材料，其中該改質聚丙烯層另包含熱可塑性聚烯烴。
  3. 根據請求項2之積層材料，其中該酸酐係選自由順丁烯二酸酐、丁二酸酐、鄰苯二甲酸酐、丁酸酐及醋酸酐所組成之群。
  4. 根據請求項1至3任何一項之積層材料，其中該改質聚丙烯層中，該酸酐之重量含量為自約1%至約10%。
  5. 根據請求項1至3任何一項之積層材料，其中該聚丙烯中，該酸酐接枝之比例為自約0.2mol/kg至約2mol/kg。
  6. 根據請求項2之積層材料，其中該改質聚丙烯層中，該熱可塑性聚烯 烴之重量含量為自90%至約99%。
  7. 根據請求項1之積層材料，其中該主體層包含一上主體層及一下主體層，使該改質聚丙烯層夾設於該上主體層及該下主體層中，該上主體層及該下主體層中之一者為發泡層，另一者為發泡層或皮革層。
  8. 根據請求項1之積層材料，其中該黏劑層包含熱可塑性樹脂。
  9. 一種製造根據請求項1至8任何一項之積層材料之方法，其包含：(a)提供聚丙烯及酸酐；(b)共押出聚丙烯及酸酐，並形成片狀，以獲得該改質聚丙烯層；(c)提供該主體層；及(d)施加該黏劑層使其直接接觸該改質聚丙烯層之該未經粗糙化之表面，並與該主體層貼合。
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