TW202023828A - 一種蔬果防霧包裝袋 - Google Patents

一種蔬果防霧包裝袋 Download PDF

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TW202023828A
TW202023828A TW107147006A TW107147006A TW202023828A TW 202023828 A TW202023828 A TW 202023828A TW 107147006 A TW107147006 A TW 107147006A TW 107147006 A TW107147006 A TW 107147006A TW 202023828 A TW202023828 A TW 202023828A
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layer
heat
vegetables
fruits
packaging bag
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TW107147006A
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TWI704054B (zh
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廖德超
馬登科
袁敬堯
鄭文瑞
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南亞塑膠工業股份有限公司
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Application filed by 南亞塑膠工業股份有限公司 filed Critical 南亞塑膠工業股份有限公司
Priority to TW107147006A priority Critical patent/TWI704054B/zh
Priority to CN201910456400.6A priority patent/CN111361246B/zh
Priority to US16/678,857 priority patent/US11427390B2/en
Priority to JP2019209822A priority patent/JP7018421B2/ja
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Abstract

一種蔬果包裝用防霧袋，以聚丙烯系樹脂多層膜為材料，經製袋機高速製袋加工後成為防霧袋，具有優異的透明度、防霧效果，且所製得的透明防霧蔬果包裝袋兼具良好開口性(slip property)及高熱封強度(Heat sealing strength)，可廣泛應用於蔬果包裝。

Description

一種蔬果防霧包裝袋
本發明涉及一種蔬果防霧包裝袋，特別是兼具優異透明度、防霧效果及良好開口性的蔬果防霧包裝袋。
包裝蔬菜及水果的包裝袋(下稱蔬果包裝袋)，為提高包裝內容物的保鮮度，減少植物熱能和熟成的破壞，需具備良好的透明度，以及減少水滴霧氣形成的條件。
為使蔬果包裝袋具有良好防霧性，現有技術是採用經過特殊防霧處理的防霧膜製成蔬果包裝袋。所述防霧膜除具備優異的防霧效果外，經過製袋機加工後，所製成的蔬果包裝袋需滿合下列特性：1.優異的透明度及防霧效果；提升光澤度、減少霧氣，防止水滴，幫助包裝食品透明和新鮮；3.高熱熔斷強度；促進製袋機在進行熱切割防霧膜加工製成蔬果包裝袋時更加順暢，提升製袋加工的產速；4.開口性佳；包裝時，蔬果包裝袋的袋口易打開，不沾黏，裝填內容物可順利地滑入 袋內，不會產生填充問題；5.高熱封強度；蔬果包裝袋的袋口，需要熱封時，具有高的熱封強度。
然而，現有技術中的防霧膜製袋加工，屬於低產速，每分鐘大約150袋為上限(≦150袋/分)。高速製袋下，現有技術中的防霧膜可能產生熱熔斷強度偏低，造成裝填內容物後，易有破袋現象。
有鑑於此，本發明的主要目的在於提供一種聚丙烯系樹脂多層膜，具有優異的透明度、防霧效果及高熱熔斷強度，不但適應製袋機在每分鐘150袋以上(≧150袋/分)的高速下製作透明防霧蔬果包裝袋。
本發明的另一主要目的在於提供一種蔬果防霧包裝袋，由三層疊層結構且厚度為15~80μm的聚丙烯多層膜製成，具有疊置在最下層的熱封層(A)、夾置在中間層的基材層(B)及疊置在最上層的表面層(C)或熱封層(A)中的一種，其中，該熱封層(A)以丙烯-乙烯-丁烯共聚物或丙烯-丁烯共聚物中的至少1種製成，且其表面經過電暈處理；該基材層(B)以丙烯或丙烯-丁烯共聚物中的至少1種製成，且基於所述基材層(B)的總重量，成分中有添加1.0~10wt%的防霧劑；該表面層(C)以丙烯、丙烯-乙烯-丁烯共聚物或丙烯-丁烯共聚物中的至少1種製成。
本發明的聚丙烯多層膜，其熱封層(A)的相對厚度，占總厚度的4~10%；其基材層(B)的相對厚度，占總厚度的80~92%%；其表面層(C)的相對厚度，占總厚度的4~10%。
本發明的蔬果防霧包裝袋，基於所述熱封層(A)的總重量， 所述熱封層(A)的成分中，具有最低熔點為70~90℃的樹脂，且該樹脂的添加量為1~10wt%。
本發明的蔬果防霧包裝袋，基於所述基材層(B)的總重量，所述基材層(B)的成分中，具有最低熔點為70~90℃的樹脂，且該樹脂的添加量為1~5wt%。
本發明的蔬果防霧包裝袋，基於所述表面層(C)的總重量，所述表面層(C)的成分中，具有最低熔點為70~90℃的樹脂，且該樹脂的添加量為1~10wt%。
本發明的蔬果防霧包裝袋，其中，所述防霧劑選自甘油脂肪酸酯類、山梨糖醇酐脂肪酸酯類、甘油單酸脂或山梨糖醇酐單酸酯的環氧乙烷加成物中的一種以上。
本發明的蔬果防霧包裝袋，其中，所述熱封層(A)的熱封強度≧3.5N/15mm。
本發明的蔬果防霧包裝袋，其中，所述熱封層(A)或表面層(C)的成分中，基於各自的熱封層(A)或表面層(C)的總重量，有添加1~7wt%的無機粒子，且選自粒徑介於0.2~10μm的二氧化矽、滑石或雲母中的一種以上。
本發明的蔬果防霧包裝袋的有益效果，包括具有優異的透明度、防霧效果，且所製得的透明防霧蔬果包裝袋兼具良好開口性(slip property)及高熱封強度(Heat sealing strength)，可廣泛應用於蔬果包裝。
30‧‧‧聚丙烯多層膜
31‧‧‧熱封層
32‧‧‧基材層
33‧‧‧表面層
34‧‧‧防霧劑
圖1為本發明的聚丙烯多層膜的斷面放大圖。
如圖1所示，本發明的聚丙烯多層膜30，為三層共擠壓雙軸延伸的聚丙烯多層膜，由疊置在最下層的熱封層(A)、夾置在中間層的基材層(B)、及疊置在最上層的表面層(C)或熱封層(A)中的一種，共同構成三層疊層結構。
其中，夾置在中間層的基材層(B)，可以選擇由一片或三片基材層(B)構成疊層結構。
本發明的聚丙烯多層膜30，具有優異的透明度、防霧效果及高熱熔斷強度，疊層結構的厚度為15~80μm，優選為20~40μm。其中，所述熱封層(A)的相對厚度，占總厚度的4~10%；所述基材層(B)的相對厚度，占總厚度的80~92%%；所述表面層(C)的相對厚度，占總厚度的4~10%。
製作蔬果包裝袋時，製袋機將兩張所述聚丙烯多層膜30熱封製成蔬果包裝袋。熱封條件為壓力0.1MPa，時間0.5秒，最佳熱封強度≧3.5N/15mm。熱封強度≧3.5N/15mm可確保包裝內容物後不易脫落。
尤其是，本發明的聚丙烯多層膜30，適應製袋機在每分鐘150袋以上(≧150袋/分)的高速下生產蔬果包裝袋，且所製得的蔬果包裝袋，具有優異的透明度及防霧效果，也兼具良好開口性(slip property)及高熱封強度(Heat sealing strength)，可廣泛應用於蔬果包裝。
如圖1所示，本發明的聚丙烯多層膜30，其熱封層(A)的表面，需具備防霧性，防止水氣凝結於所述熱封層(A)的表面上，幫助消費者 得以透視內容物，提升產品的光澤度和新鮮度。
所述熱封層(A)的聚丙烯樹脂組成，選自丙烯-乙烯-丁烯共聚物或丙烯-丁烯共聚物中的至少1種所構成。其中，丁烯與丙烯結構相近，相容性佳，故所述熱封層(A)的透明性高。
基於所述熱封層(A)的總重量，所述熱封層(A)的丙烯-乙烯-丁烯共聚物或丙烯-丁烯共聚物的成分中，具有最低熔點為70~90℃的樹脂，且該樹脂的添加量為1~10wt%。如果該樹脂的添加量小於1wt%(<1wt%)，熱封製成蔬果包裝袋後，因熱封層(A)與基材層(B)層間的強度不足，造成熱封強度低；如果該樹脂的添加量大於10wt%(>10wt%)，熱封製成蔬果包裝袋後，因熱封層(A)與基材層(B)層間的強度高，熱封強度強，但成本過高。
同時，為提升所製得的蔬果包裝袋具有良好的開口性，所述熱封層(A)的聚丙烯樹脂組成，基於所述熱封層(A)的總重量，可以適度添加無機粒子，添加量為1~7wt%。其中，所述無機粒子選自粒徑介於0.2~10μm的二氧化矽、滑石(talc)或雲母中的一種以上。
所述無機粒子的添加量及粒徑，如果小於1wt%(<1wt%)或小於0.2μm(<0.2μm)，所製得的蔬果包裝袋的開口性，沒有獲得提升；如果大於7wt%(>7wt%)或大於10μm(>10μm)，所製得的蔬果包裝袋的霧度過高，進而造成透明性不高，不利應用於蔬果包裝。
如圖1所示，本發明的聚丙烯多層膜30，其基材層(B)為所述聚丙烯多層膜30具備機械強度的來源，需具備一定耐熱性。
所述基材層(B)的聚丙烯樹脂組成，選自丙烯或丙烯-丁烯 共聚物中的至少1種所構成。
所述基材層(B)的整體熔點範圍為150~170℃。基於所述基材層(B)的總重量，所述基材層(B)的成分中，具有最低熔點為70~90℃的樹脂，且該樹脂的添加量為1~5wt%。如果該樹脂的添加量小於1wt%(<1wt%)，熱封製成蔬果包裝袋後，熱封層(A)與基材層(B)層間的強度不足，造成熱封強度低；如果該樹脂的添加量大於5wt%(>5wt%)，熱封製成蔬果包裝袋後，因熱封層(A)與基材層(B)層間的強度高，熱封強度強，但成本過高。
尤其是，為延長本發明的聚丙烯多層膜30的防霧性，所述基材層(B)的聚丙烯樹脂組成中，需添加防霧劑。本發明的聚丙烯多層膜30的防霧性機制，是借助所述熱封層(A)表面施予電暈處理後，產生親水基團，故添加於所述基材層(B)中的防霧劑親水基團，會遷移至所述基材層(B)的表面，從而將水滴覆著於所述基材層(B)表面後，形成水膜，光線不會產生折射或繞射，故可透視內容物。
基於所基材層(B)的總重量，所述防霧劑的添加量為1.0~10wt%，優選為1.5~4.5wt%。其中，所述防霧劑選自甘油脂肪酸酯類、山梨糖醇酐脂肪酸酯類、甘油單酸脂或山梨糖醇酐單酸酯的環氧乙烷加成物中的一種以上。
此外，所述基材層(B)可以適時添加用於提高生產性的加工助劑，例如熱安定劑、抗氧化劑等等。
如圖1所示，本發明的聚丙烯多層膜30，其表面層(C)的表面，需具備防霧性，防止水氣凝結於所述表面層(C))的表面上。因為，蔬 果包裝後層列於冷藏櫃中，如表面產生霧氣，將影響消費者的購買意願。
所述表面層(C)的聚丙烯樹脂組成，選自丙烯、丙烯-乙烯-丁烯共聚物或丙烯-丁烯共聚物中的至少1種所構成。其中，丁烯與丙烯結構相近，相容性佳，故所述熱封層(A)的透明性高。
基於所述表面層(C)的總重量，所述表面層(C)的成分中，具有最低熔點為70~90℃的樹脂，且該樹脂的添加量為1~10wt%。
同時，為促進所製得的蔬果包裝袋使用時不易沾黏，所述表面層(C)的聚丙烯樹脂組成，基於所述熱封層(A)的總重量，可以適度添加無機粒子，添加量為1~7wt%。其中，所述無機粒子選自粒徑介於0.2~10μm的二氧化矽、滑石(talc)或雲母中的一種以上。
所述無機粒子的添加量及粒徑，如果小於1wt%(<1wt%)或小於0.2μm(<0.2μm)，所製得的蔬果包裝袋的沾黏性，沒有獲得改善；如果大於7wt%(>7wt%)或大於10μm(>10μm)，所製得的蔬果包裝袋的霧度過高，進而造成透明性不高，不利應用於蔬果包裝。
本發明的聚丙烯多層膜30的製備方法，是使用三層或五層共押出機進行生產三層或五層共擠壓雙軸延伸的聚丙烯多層膜。其中，混練段依聚丙烯系樹脂熔點進行設定，溫度最高設定225~245℃，經T-Die後進行冷卻，冷卻區溫度控制25~40℃，再進行縱方向(MDO)延伸，延伸比控制在4~5倍。然後進行横方向(TDO)方向延伸，延伸比控制在8~9倍，横方向(TDO)回縮比控制7~12%，再經電暈處理後收捲。
下面以實施例更具體的說明本發明，雖然以較佳的實施例被露加以詳述，惟本發明之技術及權利範圍不受其所限制。此外，本發明 之各項物性評估係採行下列方法加以進行：
1.防霧性
1)低溫4℃防霧性：
秤取100ml水裝入250ml燒杯，將防霧膜覆蓋於燒杯上，然後放置於4℃冷藏庫5分鐘，取出觀察膜表面水滴覆著情形。
2)高溫40℃防霧性：
秤取40℃ 100ml水裝入250ml燒杯，將防霧膜覆蓋於燒杯上，然後靜置10秒，取出觀察膜表面水滴覆著情形。
3)防霧性評價等級：
○：水氣在膜表面形成水膜，無霧氣。
△：水氣在膜表面形成水膜，但經時後轉變成水滴狀，無法透視。
×：水氣在膜表面形成水滴狀，無法透視。
2.熱封強度
1)樣品製備：
準備樣品尺寸100mm*100mm，熱封層對熱封層堆疊後，以TESTER SANGYO TP-701-B熱封試驗機進行加工，溫度160℃，壓力0.1MPa，時間0.5秒。
2)熱封強度分析：
將熱封處以製具分裁15mm後，拉力機分析，條件速度300mm/min，角度180度，分析次數5次，取其平均值。
3)熱封強度評價等級：
○：≧3.5N/15mm。
△：2.5~3.4N/15mm。
×：<2.5N/15mm
3.製袋加工性及熱熔斷強度
1)防霧膜製袋：
捲樣幅寬600mm，以Totani HK 65V製袋機進行製袋加工，溫度400℃，袋數140、170、200袋/分，製袋過程觀察防霧袋是否可順利收集，成品尺寸300mm*200mm。
2)熱熔斷強度分析：
將防霧袋熔斷處以製具分裁15mm後，拉力機分析，條件速度300mm/min，角度180度，分析次數5次，取其平均值。
3)熱熔斷強度評價：
○：≧18N/15mm。
△：16~17.9N/15mm。
×：<15.9N/15mm。
4.開口性：
將防霧袋袋口以拇指與食指搓揉，檢視包裝袋袋口開口特性。
1)開口性評價：
○：包裝袋袋口易打開，不沾黏。
△：包裝袋袋口輕微沾黏。
×：包裝袋袋口沾黏。
5.透明性
將10個製袋產品重疊，將圖案外形置於下方，目視觀察清晰透明性。
1)透明性評價：
○：圖案外形清晰透明。
△：圖案外形微霧。
×：圖案外形模糊。
實施例及比較例中的樹脂成分，說明如下：
(PP-1)：均聚丙烯，中石化製造，品名PPR-FT03-S，MFR：3.1g/10分，熔點：165℃。
(PP-2)：無規共聚丙烯-乙烯-丁烯，住友製造，品名SP7731，MFR：7g/10分，熔點：132℃。
(PP-3)：無規共聚丙烯-丁烯，三井製造，品名XM-7070，MFR：7.0g/10分，熔點：75℃。
(AF-1)：防霧劑母粒，理研製造，品名PAT-381，載體樹脂MFR：7.5g/10分。
(AB-1)：無機SiO2開口劑，A.schulman製造，品名ABVT 20，尺寸：0.5~1μm。
(AB-2)：無機SiO2開口劑，Constab製造，品名AB 06095 PP， 尺寸：2μm。
(AB-3)：無機SiO2開口劑，Constab製造，品名AB 0619 PP，尺寸：4μm。
〔實施例1〕
製作厚度為20μm的聚丙烯多層膜30，由1μm的熱封層(A)、18μm的基材層(B)及1μm的表面層(C)構成三層疊層結構。各層的聚丙烯樹脂組成，如下：
1.熱封層(A)樹脂
基於無規共聚丙烯-乙烯-丁析樹脂(PP-2)的重量，添加1%無規共聚丙烯-丁烯(PP-3)，3.5%無機SiO2開口劑(AB-2)及1%(AB-3)。
2.基材層(B)樹脂
基於均聚丙烯樹脂(PP-1)的重量，添加1%無規共聚丙烯-丁烯(PP-3)，1.5%防霧劑母粒(AF-1)。
3.表面層(C)樹脂
基於無規共聚丙烯-乙烯-丁析樹脂(PP-2)的重量，添加1%無規共聚丙烯-丁烯(PP-3)，3.5%無機SiO2開口劑(AB-2)及1%(AB-3)。
2-4 製備聚丙烯多層膜
使用三層共押出機進行生產，於混練段，依聚丙烯系樹脂熔點進行設定，熱封層(A)/基材層(B)/表面層(C)厚度比=1/18/1，溫度最高設定245℃，經T-Die後進行冷卻，冷卻區溫度控制35℃，再進行MD方向延伸，延伸比控制4.4倍。然後進行TD方向延伸，延伸比控制9倍，回縮比控制8%，再經電暈處理後收捲。
測試所製成聚丙烯多層膜的物性，結果如表1所示。
〔實施例2〕
同實施例1的製法，但將實施例1的基材層(B)防霧劑母粒，增為2.5wt%。
測試所製成聚丙烯多層膜的物性，結果如表1所示。
〔實施例3〕
將實施例2熱封層(A)及表面層(C)PP-3增為5wt%，其餘的製作聚丙烯系樹脂多層膜條件皆與實施例2相同。
測試所製成聚丙烯多層膜的物性，結果如表1所示。
〔實施例4〕
將實施例3熱封層(A)及表面層(C)PP-3增為10wt%，其餘的製作聚丙烯系樹脂多層膜條件皆與實施例3相同。
測試所製成聚丙烯多層膜的物性，結果如表1所示。
〔實施例5〕
將實施例4基材層(B)PP-3增為5wt%，其餘的製作聚丙烯系樹脂多層膜條件皆與實施例4相同。
測試所製成聚丙烯多層膜的物性，結果如表1所示。
〔實施例6〕
將實施例5熱封層(A)及表面層無機開口劑皆為AB-2，其餘的製作聚丙烯系樹脂多層膜條件皆與實施例5相同。
測試所製成聚丙烯多層膜的物性，結果如表1所示。
〔實施例7〕
將實施例6熱封層(A)及表面層無機開口劑以1wt%AB-1取代，其餘的製作聚丙烯系樹脂多層膜條件皆與實施例7相同。
測試所製成聚丙烯多層膜的物性，結果如表1所示。
〔實施例8〕
將實施例7熱封層(A)及表面層無機開口劑AB-1增為2wt%，其餘的製作聚丙烯系樹脂多層膜條件皆與實施例7相同。
測試所製成聚丙烯多層膜的物性，結果如表1所示。
〔實施例9〕
將實施例8中MDO延伸比降為4.0，TDO回縮比增為10wt%其餘的製 作聚丙烯系樹脂多層膜條件皆與實施例8相同。
測試所製成聚丙烯多層膜的物性，結果如表1所示。
〔比較例1〕
實施例1不添加無規共聚丙烯-丁烯PP-3，其餘的製作聚丙烯系樹脂多層膜條件皆與實施例1相同。
測試所製成聚丙烯多層膜的物性，結果如表1所示。
〔比較例2〕
將實施例1中無機抗黏劑AB-2降為1.0wt%，AB-3增為3.5wt%，其餘的製作聚丙烯系樹脂多層膜條件皆與實施例1相同。
測試所製成聚丙烯多層膜的物性，結果如表1所示。
〔比較例3〕
將實施例1中防霧母粒增為4.0wt%，其餘的製作聚丙烯系樹脂多層膜條件皆與實施例1相同。
測試所製成聚丙烯多層膜的物性，結果如表1所示。
〔比較例4〕
將實施例4中無規共聚丙烯-丁烯PP-3增為10.0wt%，其餘的製作聚丙烯系樹脂多層膜條件皆與實施例5相同。
測試所製成聚丙烯多層膜的物性，結果如表1所示。
〔比較例5〕
將實施例9中無機抗黏劑AB-1及AB-2增量1.5倍，其餘的製作聚丙烯系樹脂多層膜條件皆與實施例9相同。
Figure 107147006-A0101-12-0016-1
Figure 107147006-A0101-12-0017-4
結論：
1.實施例1、2及比較例3中，隨防霧劑母粒添加量增加，聚丙烯系樹脂多層膜防霧效果提升，最適添加量為2.5wt%。
2.實施例2、3、4及比較例1中，隨熱封層(A)及表面層(C)無規共聚丙烯-丁烯添加量至10wt%，熱封強度≧3.5N/15mm。其原因為添加低熔點無規共聚丙烯-丁析，可縮短樹脂熔融時間，另丁烯與丙烯結構相近，相容性佳，故透明性高。
3.實施例4、5與比較例4中，隨表面層(C)無規共聚丙烯-丁烯添加量增加至10wt%，製袋加工性不佳，其原因為聚丙烯系樹脂多層膜挺性差所致。
4.實施例6、7、8中，在相同4.5wt%無機開口劑添加量，隨著小粒徑比例增加，製袋後熱熔斷強度有顯著提升(400℃*200袋)。
5.實施例8、9中，在相同4.5wt%無機開口劑添加量，隨著聚丙烯多層膜製程的縱方向(MDO)延伸倍率降為4倍，横方向(TDO)回縮比增為10%，可增加聚丙烯多層膜結晶定型。於製袋過程可降低收縮，熔斷處均一性佳，故熱熔斷強度高(400℃*200袋)。
30‧‧‧聚丙烯多層膜
31‧‧‧熱封層
32‧‧‧基材層
33‧‧‧表面層
34‧‧‧防霧劑

Claims (9)

  1. 一種蔬果防霧包裝袋，由三層疊層結構且厚度為15~80μm的聚丙烯多層膜製成，具有疊置在最下層的熱封層(A)、夾置在中間層的基材層(B)及疊置在最上層的表面層(C)或熱封層(A)中的一種，其特徵在於，該熱封層(A)以丙烯-乙烯-丁烯共聚物或丙烯-丁烯共聚物中的至少1種製成，且其表面經過電暈處理；該基材層(B)以丙烯或丙烯-丁烯共聚物中的至少1種製成，且基於所述基材層(B)的總重量，成分中有添加1.0~10wt%的防霧劑；該表面層(C)以丙烯、丙烯-乙烯-丁烯共聚物或丙烯-丁烯共聚物中的至少1種製成。
  2. 如申請專利範圍第1項所述的蔬果防霧包裝袋，其中，所述聚丙烯多層膜的熱封層(A)的相對厚度，占總厚度的4~10%；所述基材層(B)的相對厚度，占總厚度的80~92%%；所述表面層(C)的相對厚度，占總厚度的4~10%。
  3. 如申請專利範圍第1項或第2項所述的蔬果防霧包裝袋，其中，所述防霧劑選自甘油脂肪酸酯類、山梨糖醇酐脂肪酸酯類、甘油單酸脂或山梨糖醇酐單酸酯的環氧乙烷加成物中的一種以上。
  4. 如申請專利範圍第3項所述的蔬果防霧包裝袋，其中，基於所述熱封層(A)的總重量，所述熱封層(A)的成分中，具有最低熔點為70~90℃的樹脂，且該樹脂的添加量為1~10wt%。
  5. 如申請專利範圍第4項所述的蔬果防霧包裝袋，其中，所述熱封層(A)的熱封強度≧3.5N/15mm。
  6. 如申請專利範圍第3項所述的蔬果防霧包裝袋，其中，基於所述基材層(B)的總重量，所述基材層(B)的成分中，具有最低熔點為70~90℃的樹脂，且該樹脂的添加量為1~5wt%。
  7. 如申請專利範圍第3項所述的蔬果防霧包裝袋，其中，基於所述表面層(C)的總重量，所述表面層(C)的成分中，具有最低熔點為70~90℃的樹脂，且該樹脂的添加量為1~10wt%。
  8. 如申請專利範圍第1項所述的蔬果防霧包裝袋，其中，所述熱封層(A)的成分中，基於所述熱封層(A)的總重量，有添加1~7wt%的無機粒子，且選自粒徑介於0.2~10μm的二氧化矽、滑石或雲母中的一種以上。
  9. 如申請專利範圍第1項所述的蔬果防霧包裝袋，其中，所述表面層(C)的成分中，基於所述表面層(C)的總重量，有添加1~7wt%的無機粒子，且選自粒徑介於0.2~10μm的二氧化矽、滑石或雲母中的一種以上。
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