TWI392781B - Preparation of Natural Cellulose Nonwoven by Wet Spunbond Method - Google Patents

Preparation of Natural Cellulose Nonwoven by Wet Spunbond Method Download PDF

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TWI392781B
TWI392781B TW098146658A TW98146658A TWI392781B TW I392781 B TWI392781 B TW I392781B TW 098146658 A TW098146658 A TW 098146658A TW 98146658 A TW98146658 A TW 98146658A TW I392781 B TWI392781 B TW I392781B
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cellulose
woven fabric
natural cellulose
long
mucus
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TW098146658A
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TW201122173A (en
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Wen Tung Chou
Ming Yi Lai
Kun Shan Huang
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    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/05Filamentary, e.g. strands
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B1/00Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
    • C08B1/003Preparation of cellulose solutions, i.e. dopes, with different possible solvents, e.g. ionic liquids
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/06Wet spinning methods
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/12Stretch-spinning methods
    • D01D5/14Stretch-spinning methods with flowing liquid or gaseous stretching media, e.g. solution-blowing
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/013Regenerated cellulose series
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/10Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between yarns or filaments made mechanically
    • D04H3/11Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between yarns or filaments made mechanically by fluid jet
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/16Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic filaments produced in association with filament formation, e.g. immediately following extrusion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/88Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/919Thermal treatment of the stream of extruded material, e.g. cooling using a bath, e.g. extruding into an open bath to coagulate or cool the material

Description

使用濕式紡黏方式製備天然纖維素不織布的方法
本發明是關於一種「使用濕式紡黏方式製備天然纖維素不織布的方法」,尤指一種具有低製造成本及不會造成環境汙染的環保製程,其製得的不織布成品屬於長纖維型態,而具有良好的透氣性與吸水率等物性,可被應用於紡織品、醫療衛生材料、過濾材料、生物科技材料及光電晶圓擦拭等用途上。
目前人造合成纖維所製成的不織布,係由熔融的高分子聚合原料,以直接擠出法(spunlaid)經過擠出延伸形成連續的長纖維後,再將其堆疊成網形而成,因此該長纖維能賦予不織布具有良好的透氣性與吸水率等物性,故已大量地被廣泛應用在諸如衛生用品、擦拭材、醫療防護與過濾材等領域上;另前述直接擠出法所生產的不織布產量,其市佔率根據美國不織布工業協會(INDA)的統計,已從1994年的33.5%(第二位)成長至2009年的43.7%(第一位),整體的產量並達到每年2.7百萬噸,而其生產中所使用的最大量原料,依序為聚丙烯(PP)、聚酯(PET)、聚乙烯(PE)與尼龍(Nylon),共計佔總使用量的96%,故當這些大量人造合成纖維不織布經使用後成為廢棄物時,由於無法被自然環境分解,反而對環境產生巨大的不良衝擊結果,再者,這些人造合成纖維的原料亦非取之不盡,伴隨著石化原料的短缺,其取得的成本也會逐漸升高,近來生產不織布的業者,乃進而逐漸轉向使用天然原料來取代人造合成纖維原料,但卻又發現該天然素材所生產製造不織布的方式,因必須採用製程較長的濕式法或水針法才能達成,除成本較直接擠出法為高之外,其纖維型態又屬於短纖維,致使不織布產品之透氣性與吸水率等性能被減弱,因此,如何以天然纖維原料及低成本製程來製得長纖維型態的不織布產品,便成為急待突破之要務。
本發明之主要目的在提供一種「使用濕式紡黏方式製備天然纖維素不織布的方法」,其係以木漿(pulp)為原料而加入氧化甲基瑪琳(N-methylmorpholine N-oxide,簡稱NMMO)溶劑,使其相混合溶解成黏液(dope),再以紡黏方式(spunbond)將該黏液從紡口擠壓出來形成長纖維素絲束,使該長纖維素絲束先經由空氣隔距(air gap)冷卻拉伸而進入凝固液中凝固再生、再經氣流牽伸器高速拉伸後於收集網上堆疊成網形而成不織布,該不織布又經水洗、水針軋、乾燥及捲取等程序後,即可製得具有連續長纖維型態之天然纖維素纖維不織布,由於該製程短使得製造成本降低,且因使用無毒性的氧化甲基瑪琳作為溶劑並能充分循環使用,而成為不會對環境造成汙染的環保製程。
本發明之另一目的乃在提供一種「使用濕式紡黏方式製備天然纖維素不織布的方法」,依該方法所製得之天然纖維素纖維不織布,屬於連續長纖維型態,除具有與人造合成纖維不織布相同的良好透氣性與吸水率等物性外,其使用後成為廢棄物時,能在環境中自然分解,而不會對環境造成破壞。
為進一步說明本發明之製作流程與功效,茲佐以圖示及各試驗實例詳細說明如后:請參閱第一圖至第五圖所示,本發明「使用濕式紡黏方式製備天然纖維素不織布的方法」,其步驟包含:
a.以木漿(pulp)為原料;選用α-纖維素含量在65%以上之長、短纖維的木漿纖維素,其纖維素聚合度(degree of polymerization,簡稱DP)介於500~1200;
b.加入氧化甲基瑪琳溶劑(N-methylmorpholine N-oxide,簡稱NMM0,其化學結構如第二圖所示)及苯基噁唑安定劑(1,3-phenylene-bis 2-oxazoline,BOX)於木漿中,使其相混合溶解成黏液(dope);其係利用臥式調漿機,將該木漿纖維素、氧化甲基瑪琳溶劑及苯基噁唑添加劑一起置入後,以50℃~80℃低溫進行高速攪碎,並藉由氧化甲基瑪琳對纖維素膨潤性大、溶解性高及溶解速率快等功效,來達成快速相互混合溶解,再利用真空薄膜蒸發器以80℃~120℃加熱,在5分鐘內蒸發溶解混合後之水份排除至5~13%,即可形成黏液(dope);
c.以紡黏方式(spunbond)將該黏液從紡口擠壓出來形成長纖維素絲束,並將長纖維素絲束施以冷卻拉伸;如第三圖所示,該黏液D由齒輪泵1打入紡口模具2內,再經紡口3向外以空氣隔距(air gap)冷卻方式進行拉伸,其中,空氣隔距之距離為2公分~30公分,使用冷卻風之溫度為5℃~30℃,其相對濕度為60%~99%;
d.將冷卻拉伸後的長纖維素絲束進入凝固液中凝固再生;其中,凝固液之溫度為5℃~30℃,且其內部氧化甲基瑪琳之濃度為0~30wt%;及
e.經凝固液再生後之長纖維素絲束,又以氣流牽伸器進行牽伸速度為20m/min~3000m/min之高壓高速拉伸,並將其在收集網上堆疊成網形之不織布(如第三圖所示),再依序經水洗、水針軋、乾燥及捲取等程序(如第四圖所示),即製得具有連續長纖維型態之天然纖維素纖維不織布(如第五圖所示)。
其中,步驟b所加入之苯基噁唑安定劑(1,3-phenylene-bis 2-oxazoline,BOX)可降低纖維素黏液的色澤及聚合度的衰退,且該氧化甲基瑪琳為無毒性溶劑,於水洗過程中被洗出後,再經過濾、脫色及減壓濃縮蒸餾後可被回收再使用,其損耗率低且回收率可達99.5%以上,不但可降低製造成本,亦不會造成環境的汙染,完全符合環保製程之規範。
又步驟b中該黏液的纖維素含量為6wt%~15wt%,其黏液的黏度為1000~10000(poise),而黏液的透光指數為1.470~1.495以及黏液的熔融指數為100~1000。
另步驟e中氣流牽伸器進行拉伸速度為20m/min~3000m/min所使用的木漿亦可更為α-纖維素含量在65%以上之長、短纖維的紙漿。
為進一步證明本發明之特點及實施功效,乃進行完成各項試驗實例並說明如后:首先,如表一中樣品1至樣品15的黏液組成表所示,其係分別將聚合度為650~1050之木漿纖維素與氧化甲基瑪琳(NMMO)溶劑,於50℃~80℃下高速攪拌成漿液,然後利用真空薄膜蒸發器蒸發多餘之水份,以80℃~120℃加熱,10分鐘內排除水分至5%~13%,即可將纖維素溶解成黏液(dope),接著,以紡黏方式(spunbond)經紡口擠壓形成長纖維素絲束,經空氣隔距(air gap)冷卻拉伸後,長纖維素絲束進入凝固液中凝固再生、再經氣流牽伸器高速拉伸後於收集網上長纖維絲堆疊成網形成不織布,並依序進行水洗、水針軋、乾燥及捲取後,即完成表一中樣品1至樣品15之各黏液組成表。
接著,依照表一中的纖維聚合度及抗聚合度衰退添加劑添加比例,來做出不同不織布基重之樣品16至樣品30後,進行其不織布強度之試驗,其進行的方式根據CNS5610標準進行檢測,方法如下:分別將各樣品之機械方向(Mechanical Direction,MD)及垂直方向(Cross Direction,CD),取下拉伸測試試片各10塊,其試片長度至少為180mm,寬度為2.54mm,使用萬能強力試驗機作測試,設定夾距為76mm,拉伸速率300mm/min,樣品16至樣品30測試後所得的不織布強度乃如表二所示。
最後,再以不同的纖維聚合度及不織布基重做成樣品31至樣品48後,進行其不織布透氣度及吸水率之試驗,其進行的方式根據CNS5612標準進行檢測,係將樣品裁剪成26×26cm2 各四片,以透氣度試驗機:TEXTEST FX3300對26×26cm2 之試片進行透氣度測試,先將不織布切取5條縱向試片,每一試片之寬度為76mm,長度則視試片之質量(一條試片之質量為5.0±0.1g)而定,試片及網籃沉浸於水內,歷經10秒鐘,再抓牢網籃之開口端,將試片及網籃一起自水中取出,讓網籃開口端朝上,滴水10秒鐘,立即將該試片及網籃一起放入以知質量之玻璃杯內,稱取試片、網籃及玻璃杯之總質量,準確是0.1g。試片之吸水率值公式如下:
由上述表二中樣品16至樣品30及表三中的樣品31至樣品48所示,依本發明所完成的連續長纖維型態之天然纖維素纖維不織布,其不論機械方向(MD)或垂直方向(CD)的強度均非常理想,不同基重下的透氣度及吸水率表現,也均優於現有習知人造合成纖維不織布及天然纖維不織布,故完全符合紡織品、醫療衛生材、過濾材、生物科技材料及光電晶圓擦拭等用途上所需的要求條件。
綜上所陳,本發明由於製程短使得製造成本降低,且因使用無毒性的氧化甲基瑪琳作為溶劑並能充分循環使用,而成為不會對環境造成汙染的環保製程,確為具有高度產業利用性的創新發明,乃依法提出申請。
1...齒輪泵
2...紡口模具
3...紡口
D...黏液
第一圖:係本發明之製造流程方塊圖。
第二圖:係本發明所使用氧化甲基瑪琳溶劑(N-methylmorpholine N-oxide,簡稱NMMO)之化學結構圖。
第三圖:係本發明中紡黏長纖維素絲束之作動示意圖。
第四圖:係本發明之製造流程示意圖。
第五圖:係本發明所製得天然纖維素不織布之外觀示意圖。
本案的代表圖並無元件的代表符號。

Claims (16)

  1. 一種「使用濕式紡黏方式製備天然纖維素不織布的方法」,其步驟包含:a.以木漿為原料;b.加入氧化甲基瑪琳溶劑(N-methylmorpholine N-oxide,簡稱NMMO,其化學結構如第二圖所示)及苯基噁唑安定劑(1,3-phenylene-bis 2-oxazoline,BOX)於木漿中,以50℃~80℃低溫進行高速攪碎,再以80℃~120℃加熱在10分鐘內蒸發溶解混合後之水份排除至5~13%而形成黏液(dope);c.以紡黏方式(spunbond)將該黏液從紡口擠壓出來形成長纖維素絲束,並將該長纖維素絲束施以空氣隔距(air gap)冷卻拉伸;d.將冷卻拉伸後的長纖維素絲束進入凝固液中凝固再生;及e.經凝固液再生後之長纖維素絲束,以氣流牽伸器進行高壓高速拉伸,並使其在收集網上堆疊成網形之不織布,再依序經水洗、水針軋、乾燥及捲取等程序,即可製得具有連續長纖維型態之天然纖維素纖維不織布。
  2. 如申請專利範圍第1項所述之方法,其中,步驟a中該木漿原料係選用α-纖維素含量在65%以上之長、短纖維的木漿纖維素,其纖維素聚合度介於500~1200。
  3. 如申請專利範圍第1項所述之方法,其中,步驟b中該氧化甲基瑪琳溶劑的濃度為45%~75%。
  4. 如申請專利範圍第1項所述之方法,其中,該步驟b中黏液的纖維素含量為6wt%~15wt%。
  5. 如申請專利範圍第1項所述之方法,其中,該步驟b中黏液的黏度為1000~10000(poise)。
  6. 如申請專利範圍第1項所述之方法,其中,該步驟b中黏液的透光指數為1.470~1.495。
  7. 如申請專利範圍第1項所述之方法,其中,該步驟b中黏液的熔融指數為100~1000。
  8. 如申請專利範圍第1項所述之方法,其中,步驟c中該空氣隔距之距離為2公分~30公分,使用冷卻風之溫度為5℃~30℃,其相對濕度為60%~99%;
  9. 如申請專利範圍第1項所述之方法,其中,步驟d中該凝固液之溫度為5℃~30℃,且其內部氧化甲基瑪琳之濃度為0~30wt%
  10. 如申請專利範圍第1項所述之方法,其中,步驟e中該天然纖維素不織布的捲取速度為每分鐘2~200公尺。
  11. 如申請專利範圍第1項所述之方法,其中,步驟e中該天然纖維素不織布之基重為10g/m2~300g/m2。
  12. 如申請專利範圍第1項所述之方法,其中,步驟e中該天然纖維素不織布的機械方向(MD)拉伸強度為20kgf以上,而垂直方向(CD)的拉伸強度為12kgf以上。
  13. 如申請專利範圍第1項所述之方法,其中,步驟e中該天然纖維素不織布的纖維纖度為1~15um。
  14. 如申請專利範圍第1項所述之方法,其中,步驟e中該天然纖維素不織布的透氣度為100~3500(cm3/cm2/min)。
  15. 如申請專利範圍第1項所述之方法,其中,步驟e中該天然纖維素不織布的吸水率為300%~2000%。
  16. 如申請專利範圍第1項所述之方法,其中,步驟e中該氣流牽伸器進行之牽伸速度為20m/min~3000m/min。
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