TWI715041B - 可生物降解之織物、母料、及製造可生物降解之纖維的方法 - Google Patents
可生物降解之織物、母料、及製造可生物降解之纖維的方法 Download PDFInfo
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- TWI715041B TWI715041B TW108117095A TW108117095A TWI715041B TW I715041 B TWI715041 B TW I715041B TW 108117095 A TW108117095 A TW 108117095A TW 108117095 A TW108117095 A TW 108117095A TW I715041 B TWI715041 B TW I715041B
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Abstract
本發明揭示一種母料及其相關方法,以及可生物降解之長纖維、纖維、紗線及織品。該母料包括0.2至5質量% CaCO3
、在酯基之間的鏈中具有二至六個碳之重複單元的脂族聚酯,其限制條件為該鏈中之該2至6個碳不包括側鏈碳,及選自由以下組成之群的載體聚合物:PET、耐綸、其他熱塑性聚合物及其組合。
Description
本發明係關於一種適用於織物之聚合物組合物,且其與最常見聚合物相比,其在合理的有利的短時間間隔內亦為可生物降解的。
織物係人類文化的基礎,且人類製造及使用織物已有數千年。最早的織物係用諸如亞麻、羊毛、絲綢及棉花之天然纖維織成的,且將繼續如此。近年來,織物纖維、紗線及織品亦已在工業上由聚合物,諸如聚酯、耐綸、烯烴、其他熱塑性聚合物及其組合產生。可將許多現代聚合物製成幾乎所有形狀及具有吸引力、耐用性及防水性的產品。在許多情況下,此等合成纖維或紗線(視所需技術及最終產品而定)可與天然纖維摻合以獲得具有天然及合成材料兩者之所需特徵的最終產品。
儘管耐久性及防水性為所需的,但此等相同特性會引起二級環境問題。由聚合纖維製造之織物不會以與諸如棉及羊毛之天然纖維相同之方式自然地進行生物降解,且可在填埋場及水域(例如,湖、海洋)中保持數百年或更久。根據美國環保署的數據,每天約有4400萬磅的合成(聚合)織物轉至填埋場。另外,在廢水處理廠淤泥中捕獲衣物在洗滌循環期間所釋放之大量微纖維。淤泥最終變成生物固體,送至填埋場或用作肥料。此等聚合微纖維隨後積聚於土壤或其他地面環境中,且可甚至變得可移動的,最終使得其自陸地環境進入水生環境。據估計,每年約有50萬噸由織物洗滌產生的塑料微纖維釋放至海洋中。某些高表面積微纖維可吸收大量毒素負荷且類似於微觀的浮游生物,藉此在食物鏈中導致累計若干數量級之生物死亡。由於人類通常食用頂級食肉物種,因此此類微纖維污染亦可對人類健康帶來負面影響。
作為額外問題,諸如地毯及室內裝飾(住宅及商業兩者)之物件相對於衣物來說較笨重,且通常編入更大更笨重的紗線,且因此可佔據大量填埋場空間。
在非織情形下,現今普遍存在的所有類型之「紙巾」(通常為非織薄片或若干層薄片)同樣佔據大量空間,即使被認為是「可沖洗的」,亦具有堵塞城市污水系統之趨勢,考慮到使用低體積低流量便桶的用量增加時尤其如此。
鑒於此等環境問題,可生物降解之聚合物之創造一直是學術界及行業非常關注之話題。此等話題包括以下有代表性的而非全面的實例。
Shah等人在「Microbial degradation of aliphatic and aliphatic-aromatic co-polyesters,」 Appl. Microbiol. Biotechnol (2014) 98:3437-3447中進行了關於聚酯降解之文獻綜述,且評論稱,「大多數可生物降解之塑料均為具有潛在可水解酯鍵之聚酯,且此等聚合物容易為解聚酶所水解;」及脂族聚酯由於其可撓性聚合物鏈,與芳族酯相比更容易降解。作為本文所述之用於本發明中的術語,一些聚酯(諸如PET)不可生物降解。
許多專利已描述可生物降解之聚合組合物。舉例而言,在Rhodia Poliamida之WO 2016/079724中,對聚醯胺組合物進行改質以產生可生物降解之聚醯胺纖維。在此專利中,根據ASTM D5511檢驗標準來量測生物降解速率。在第8-9頁,論述用於生物降解之先前技術方法,其包括:光降解;降解助劑添加劑,諸如過渡金屬鹽;及可生物降解聚合物,其快速降解留下具有高界面面積及低結構強度之多孔結構;此等可生物降解之聚合物10作為包括基於澱粉之聚合物、聚乳酸、聚己內酯、聚丁二酸丁二酯、聚對苯二甲酸丁二酯共己二酸丁二酯及數種其他聚合物列出;然而,該專利申請案指出,「不幸的是,需要大量使用以使聚合物為可生物降解的,亦需要相容及塑化添加劑。」作為例示性生物降解劑,此專利係指Lake等人之美國公開專利申請案第2008/0103232 15號。生物降解劑有利地為母料,其包括至少六種添加劑:(1)化學引誘劑或向化性化合物;(2)戊二酸;(3)鏈長為5至18個碳之羧酸;(4)可生物降解之聚合物;(5)載體樹脂;及(6)膨脹劑。本發明之實例使用2%之商用生物降解劑Eco-One®之母料藉由熔融紡絲來製備聚醯胺纖維。經由ASTM D5511標準檢驗所得纖維且發現其在300天之後降解13.9%或15.5%。在相同的ASTM D5511檢驗下,無生物降解劑之纖維降解2.2%及2.3%。
LaPray等人在US 2018/0100060中產生由聚合物與基於碳水化合物之聚合物之摻合物製成的可生物降解之物品,諸如膜、包、瓶、蓋、薄片、盒子或其他容器、板或其類似物。根據諸如ASTM D-5511及ASTM D-6691 (模擬海洋條件)之已確立標準來檢驗可生物降解性。
Tokiwa等人描述包含可生物降解之樹脂及甘露聚糖(多醣)分解產物之可生物降解之樹脂組合物。Tokiwa等人列出可生物降解之甘露聚糖分解產物包括各種甘露糖寡醣。
Bastioli等人在美國專利第30 8,466,237號中描述由包含至少50%十三烷二酸(1,11-十一烷二羧酸)之51%至37%之脂族酸及49%至63%芳族羧酸製成的可生物降解之脂族-芳族共聚酯。可生物降解之聚合物可另外藉由添加澱粉或聚丁二酸丁二酯且與乳酸或聚己內酯共聚來改質。
Lake等人在美國專利第9,382,416號中描述用於聚合材料的可生物降解添加劑,其包含化學引誘劑化合物、戊二酸、5碳羧酸及膨脹劑。將呋喃酮化合物作為細菌之引誘劑來論述。
Wnuk等人在美國專利第5,939,467號中描述含有第二可生物降解聚合物(諸如聚己內酯)的可生物降解之聚羥基烷酸酯聚合物,實例為鑄造膜及吹製膜。
多種可生物降解之調配物為已知的,通常在不解決耐洗性問題之織物領域外,其中一些調配物可利用碳酸鈣。舉例而言,Yoshikawa等人在美國公開之專利申請案第2013/0288322號中,Jeong等人在WO/2005/017015中,Tashiro等人在美國專利第9,617,462號中,且Whitehouse在美國專利申請案2007/0259584中。
儘管已花費大量努力,但仍需要新穎方法及材料來提供耐用且防水但在廢水處理厭氧消化槽中、填埋場條件下及海洋環境下進行降解之合成織物。因此,產生既維持其所需特性又比習知合成織物材料在廢水處理期間、在厭氧消化槽中、在填埋場條件下及海洋環境下更快地降解之合成織物將為有益的。
在一個態樣中,本發明提供一種母料,其包含:0.2至5質量% CaCO3
;脂族聚酯,其包含在酯基之間的鏈中具有二至六個碳之重複單元,其中2至6個碳的鏈重複單元不包括側鏈碳;及載體聚合物,其包含PET、耐綸、烯烴、其他熱塑性聚合物及其組合。鏈重複單元中之2至6個碳不包括酯(COOR)部分中之碳,且若存在側鏈碳,則在重複基團中可存在超過6個碳(加上酯碳)。
在本發明態樣中之任一者之一些較佳實施例中,脂族聚酯包含在酯基之間的鏈中具有三至六個碳或2至4個碳之重複單元。在尤其較佳之實施例中,脂族聚酯包含聚己內酯。在一些較佳實施例中,母料進一步包含聚丁二酸丁二酯(PBS)、聚丁二酸己二酸丁二酯(PBSA)、聚乳酸(PLA)、聚醚碸(PES)、聚羥基丁酸酯(PHB)、聚(3-羥基丁酸-共-3-羥基戊酸酯) (PHBV)、聚己二酸對苯二甲酸丁二酯(PBAT)、聚丁二酸己二酸丁二酯(PBSA)、聚(丁二酸丁二酯-共-對苯二甲酸丁二酯) (PBST)、聚(丁二酸丁二酯/對苯二甲酸丁二酯/間苯二甲酸丁二酯)-共-(乳酸酯)PBSTIL及其組合。
較佳地,母料(及織物)基本上不包含醣類。
在另一態樣中,本發明提供一種熔融中間物,其包含:脂族聚酯(PET除外),其包含在酯基之間的鏈中具有二至六個碳之重複單元,其中2至6個碳的鏈重複單元不包括側鏈碳;0.01至0.2質量% CaCO3
;及至少90質量% PET、耐綸、烯烴、其他熱塑性聚合物及其組合。如本文所使用,措辭「PET除外」可表達為「聚對苯二甲酸乙二酯除外」或「其限制條件為脂族聚酯不為聚對苯二甲酸乙二酯」。
在另一態樣中,本發明提供一種包含以下之纖維:脂族聚酯(PET除外),其包含在酯基之間的鏈中具有二至六個碳之重複單元,其中2至6個碳的鏈重複單元不包括側鏈碳;0.01至0.2質量% CaCO3
;及至少90質量% PET、耐綸、烯烴、其他熱塑性聚合物及其組合。
在各種實施例中,織物可具有以下特性中之一者或任何組合:可生物降解性,使得在持續266天經受ASTM D5511條件時,織物分解至少40%、或至少50%、或在40%至約80%範圍內、或40%至約75%範圍內;其中來自ASTM檢驗之分解產物主要為甲烷及二氧化碳;尺寸穩定性,使得當經受Home Laundering Test AATCC 135-2015 1IIAii之條件(在80℉進行機器洗滌、滾筒乾燥、五個洗滌循環)時,織物維持其形狀且收縮小於10%、或小於5%、或小於3%;其中該織物著色且當經受AATCC 61-2013 2A (mod 105℉)或AATCC 8-2016或AATCC 16.3-2014(選項3,20 AFU)之條件時具有至少3級、或至少4級、或5級之染色牢度;使得當經受ASTM D3786/D3886M-13之條件時,具有至少20 psi、較佳至少50 psi、或至少100 psi、或在50至約200 psi、或50至約150 psi範圍內之破裂強度;及芯吸能力,使得當經受AATCC 197-2013;選項B之條件時,織物在2分鐘內芯吸水超過至少10 mm或至少20 mm,或在約10或約20 mm至約150 mm之範圍內之距離。
在又一態樣中,本發明提供一種製造纖維、紗線或織品之方法,其包含:將本文所述之母料摻合至包含以下之聚合物中:PET、耐綸、烯烴、其他熱塑性聚合物及其組合以形成熔融混合物;擠製混合物以形成長纖維;且冷卻長纖維。此等長纖維可締捲及針織(「長纖維紗線」),形成非織絲網,或切割成用於編織、非織及針織品應用之短纖維。或者,可擠製熔融混合物以形成顆粒,且該等顆粒可隨後再熔融,接著進行擠製混合物形成纖維的步驟。在另一態樣中,本發明提供一種織物,其包含:包含CaCO3
及至少90質量% PET、耐綸、烯烴、其他熱塑性聚合物及其組合之纖維;且具有生物可降解性,使得在持續266天經歷ASTM D5511之條件時,織物分解至少40%、或至少50%、或在40%至約80%範圍內、或40%至約75%範圍內;且其中該織物包含以下特性中之一或多者:尺寸穩定性,使得當經受Home Laundering Test 5 AATCC 135-2015 1IIAii之條件(在80℉下進行機器洗滌、滾筒乾燥、五個洗滌循環)時,織物維持其形狀且收縮小於10%、或小於5%、或小於3% ;其中該織物著色且當經受AATCC 61-2013 2A (mod 105F)或AATCC 8-2016或AATCC 16.3-2014(選項3,20 AFU)之條件時具有至少3級、或至少4級、或5級之染色牢度;當經受ASTM D3786/D3886M-13之條件時,具有至少20 psi、較佳至少50 psi、或至少100 psi、或在50至約200 psi、或50至約150 psi範圍內之破裂強度;及芯吸能力,使得當經受AATCC 197-2013,選項B之條件時,織物在2分鐘內芯吸水超過至少10 mm或至少20 mm,或在約10或約20 mm至約150 mm之範圍內之距離。
在一些較佳實施例中,本發明之優點可包括:增強了母料之每質量%的生物可降解性;相比於其他生物可降解性處理,纖維或織物之耐久性較大;更好地維持纖維或織物的特性。
基於結合附圖之以下詳細描述,本發明之前述及其他目的及優點以及實現上述目的及優點之方式將變得更清晰。
術語表
「脂族聚酯(aliphatic polyester)」含有烴鏈包含開(非芳族)鏈之重複酯單元。此等可為均聚物、僅含有脂族基之共聚物或含有脂族基團及芳基之共聚物。
「載體聚合物(carrier polymer)」為母料中之聚合物,其與母料所摻合之聚合物相同,或與之相容且可混溶。
丹尼(Denier,Dpf)為9,000公尺之個別長纖維的以公克為單位的重量。其可藉由用紗線丹尼除以紗線束中之長纖維之數目來計算。
出於本發明之目的,非可生物降解之聚合物為在根據ASTM D-5511檢驗266天後降解10%或更低之聚合物。
PET、耐綸及彈性人造纖維具有習知含義。耐綸為聚醯胺;一種較佳耐綸為耐綸6,6。彈性人造纖維為聚醚-聚脲共聚物。
聚合物為包含許多重複單元之大分子(分子量超過100道爾頓(Dalton),通常為數千道爾頓)。
織物為一類由天然及/或合成5種纖維、長纖維或紗線構成之材料,且可呈針織、編織或非織形式。
術語「非織織品(nonwoven fabric)」由一般技術者充分理解,且在本文中與此類包括諸如在Tortora、Phyllis G.及Robert S. Merkel之Fairchild's Dictionary of Textiles, 第7版, New York, NY: Fairchild Publications, 2009, 第387頁中之定義的理解一致。
因此,非織織品係「產自於纖維之由黏結或連結或兩者產生,藉由機械、化學、熱塑或溶劑手段及其組合實現之織物結構。」形成基礎絲網之例示性方法包括梳理纖維、氣流成網及濕式成型。可藉由使用包括散佈在絲網中之低熱熔纖維之黏著劑、用於適當熱塑性聚合物之熱量黏結、針刺、水刺(水刺法)及紡黏製程來緊固或黏結此等絲網。
熟習此項技術者理解,在織物技術中,「紡絲(spinning)」一詞具有兩種不同定義,兩者在上下文中皆清楚。在形成合成長纖維時,術語「紡絲」係指將熔融聚合物擠製成長纖維之步驟。
在天然纖維或締捲合成長纖維切割成的短纖維之情形下,術語「紡絲」最具歷史意義(可追溯到古代),用於將長纖維加撚成黏結紗線結構,織品可自其中編織而成。
作為一般參考,Phyllis G. Tortora及Robert S. Merkel於Fairchild's Dictionary of Textiles 7th Edition,
New York, Fairchild Publications 2009提供由一般技術者(熟習此項技術者)所辨識的許多其他定義。
ASTM及AATCC檢驗方案視為行業標準。此等方案通常不隨時間顯著改變;然而,若產生任何關於此等標準之日期的問題(未在本文中規定的),則選擇在2018年1月生效之標準。
除非相反地定義,否則術語「百分比(percentage)」或符號「%」係指質量百分比(「質量% (mass%)」),其在本說明書中具有與「重量百分比(weight percentage/percent by weight)」相同的含義。熟習此項技術者結合上下文充分理解此等用途。
能夠生物降解之母料調配物通常包含載體聚合物。載體聚合物較佳經調配以匹配基質(亦即不可生物降解之聚合物)。因此,在例示性實施例中,載體聚合物選自由以下組成之群:PET、耐綸、烯烴、其他熱塑性聚合物及其組合。如藉由該等實例所展現,與本發明之其他組分組合之PET及耐綸已顯示在可洗滌織物中引起優良的可生物降解性。
出人意料地,本發明者已發現,在母料中添加碳酸鈣實質上增加所得織物之可生物降解性,同時避免對耐洗性之負面影響。
儘管本發明不受碳酸鈣運作之機制限制,且儘管本發明者不希望受任何特定理論束縛,但以下假設似乎為合理的。在同質有機聚合基質中混合之碳酸鈣之微觀無機粒子之存在引入過多用於生物降解之成核點。此碳酸鈣與其他可生物降解成分同時給予,使得成核點非常接近此等成分。鈣離子可在細菌生長中起重要作用。存在於細菌中之鈣結合蛋白利於信號轉導,且可有助於細菌朝向較高濃度之化學物質移動之正趨化性的重要過程。
根據此假設,分散碳酸鈣之存在加速藉由厭氧性細菌之作用來水解酯鍵使聚合物分解成單體及寡聚物。二氧化碳(代謝副產物)之存在亦可增強存在於聚合物基質中之碳酸鈣之溶解作用。
細菌中之鈣及鈣結合蛋白可起到重要作用的另一機制係在群體感應中;亦即,細菌中針對族群生長最佳化之交流手段。個別細菌產生水凝膠,其由細菌及產生協同功能群集之額外細胞聚合材料構成。此宏觀結構放大細菌作用且有助於引起根據本發明之聚合物之生物降解,尤其可併入此類水凝膠中之高表面積微纖維。
母料調配物嵌入於聚合物基質內。作為假設之另一態樣,化學部分對聚合物鏈的水解侵蝕自內部開始。分散於基質內之母料產生用於侵蝕之成核點且指數增加纖維表面積。細菌酶自外部深入來進行侵蝕。處於1微米範圍內之細菌最初將自外部對織物纖維起作用,但隨著聚合物基質溶解及分解,新表面積暴露。在水凝膠中形成配位細菌群集之情況下,大聚合鏈分解為寡聚鏈且進一步分解為單體且分解為CO2
及CH4
。
因此,本發明之母料可視為分兩個階段起作用:在開始時為生理化學階段,分解為較少位元,及在後半時間段為生物化學階段,分解25種物質。
在一些實施例中,紗線或織物中之纖維具有在1至50或2至30範圍內,或高達1,000之每長纖維之丹尼(dpf)。不認為纖維之丹尼在可生物降解性中是關鍵的,因為纖維性織物通常將具有足夠的表面積來支持細菌生長。
在例示性實施例中,母料包含至少0.5質量%碳酸鈣,在一些實施例中至多10%碳酸鈣,在一些情況下約0.5與5%之間的碳酸鈣,且通常至少約1.0%碳酸鈣。本發明組合物較佳使用精細碳酸鈣粉末,其較佳具有15微米(μm)或以下,10μm或以下,在一些實施例中7μm或以下之質量平均粒徑,且可在0.1與10μm之間,或1與8 μm之間,或5與8 μm之間的質量平均粒度範圍內。如習知,粒徑可藉由商用光分析設備或其他習知手段來量測。碳酸鈣粉末之表面積為至少0.5平方公尺/公克(m2
/g);在一些情況下為至少1.0 m2
/g且在一些實施例中在0.5與10 m2
/g之間。如習知,表面積可藉由諸如用於計算固體之比表面積之ISO 9277標準的方法測定,該方法亦係基於布魯諾—埃梅特—特勒(Brunauer-Emmett-Teller,BET)理論。
在一些較佳實施例中,母料調配物含有以下中之一者或任何組合:聚己內酯(PCL)、聚羥基丁酸酯(PHB)、聚丁二酸丁二酯(PBS)、聚乳酸(PLA)及聚(己二酸四亞甲酯-共-對苯二甲酸四亞甲酯)。聚己內酯或包含PCL作為主要脂族聚酯組分之摻合物似乎為有利的,因為出人意料地發現PCL優於聚乳酸(PLA)、PHB及PBS。
因為織物需要具有耐久性,所以母料及織物組合物應避免對耐久性具有不利影響之組分。較佳地,組合物具有小於5質量%、更佳地小於2%、或小於1%之醣;或小於此等量之呋喃酮;或小於此等量之會在洗滌期間濾出之有機(基於碳之)組分。在一些實施例中,本發明組合物缺乏實質上降低洗滌耐久性之任何組分。
該等織物較佳具有尺寸穩定性,使得織物維持其形狀且收縮小於10%、或小於5%、或小於3%,如藉由Home Laundering Test AATCC 135-2015 1IIAii (在80℉下進行機器洗滌、滾筒乾燥、五個洗滌循環)所量測。
織物或纖維可著色(諸如紅色、藍色、綠色等)且較佳地具有如藉由AATCC 61-2013 2A (mod 105 F)或AATCC 8-2016或AATCC 16.3-2014 (選項3,20 AFU)所量測之至少3級或至少4級或5級的染色牢度。織物(例如,自襯衫或褲子切割之織品樣品)之薄片較佳具有至少20 psi、較佳至少50 psi、或至少100 psi、或在50至約200 psi、或50至約150 psi範圍內之破裂強度,其中根據ASTM D3786/D3886M-13量測破裂強度為30。
在一些較佳實施例中,織品沒有起球或起毛(根據ASTM D 3512M-16為5級)。
在一些實施例中,織物芯吸水;此在將汗液自穿戴者身上吸走的衣服中尤其合需要;在一些較佳實施例中,織品在2分鐘內芯吸水超過至少10 mm或至少20 mm,或在約10或約20 mm至約150 mm之範圍內之距離;如藉由AATCC 197-2013所量測。根據本發明之一些實施例製備的織物之量測示於效能檢驗比較表中(亦即,表1至表7)。
在一些情況下,纖維內之精確化學結構可能未知,且上文所論述之特性中之一者或組合為進行織物表徵之最準確及/或精確方式。將母料與諸如聚對苯二甲酸乙二酯、耐綸、烯烴、其他熱塑性聚合物及其組合之非可生物降解之聚合物摻合。出於本發明之目的,當聚合物不含添加劑時(換言之,在與母料摻合之前),在根據ASTM D-5511檢驗266天後,非可生物降解之聚合物為降解10%或更低(較佳5%或更低,在一些實施例中3%或更低,且在一些實施例中在2與10%或2與5%之間)的聚合物。纖維包含至少50質量%、更佳至少70%、再更佳至少90%或至少95%,且在一些實施例中至少99%之選自由以下組成之群的聚合物:聚對苯二甲酸乙二酯(PET)、耐綸、烯烴、其他熱塑性聚合物及其組合。
本發明包括包含此等纖維之織物,其呈單組分織物形式或呈與其他纖維之混合物形式。許多織物包含纖維之混合物(摻合物),例如含有彈性人造纖維之織物通常包括棉纖維。在一些實施例中,織物包括至少10%、或至少20%、或至少50%、或至少80%、或至少90%、或100%由聚對苯二甲酸乙二酯(PET)、耐綸、烯烴、其他熱塑性聚合物及其組合製成的纖維。
自母料產生之纖維通常包括至少90質量%之不可生物降解之聚合物。因為母料較佳地以0.5至5%,較佳至少1%,在一些實施例中1與5%之間,在一些實施例中2與5%之間的量添加,且由於母料全部存在於所得組合物中,因此所得纖維將含有相應量之材料。
本發明亦包括摻合中間物、纖維、紗線及織物。根據本發明之成品之實例包括:針織品、編織品、非織品、服裝、室內裝飾、地毯、諸如床單或枕頭套之寢具、用於農業或建築之工業用織品。服裝的實例包括:襯衫、褲子、胸罩、內褲、帽子、內衣、外套、裙子、女裝、緊身褲、彈力褲以及圍巾。
當然,將碳酸鈣粒子研磨成適用於本發明之尺寸。在功能表現上,經研磨之粒子可儘可能小,且極小的粒子無任何不足之處。
然而,粒徑之上限部分地由丹尼界定,業外人士將依據直徑描述該丹尼。在彼等術語中,平均碳酸鈣粒徑應不大於擠製長纖維之直徑的10%,且最大粒徑應不大於擠製長纖維之直徑的20%,因為大於長纖維直徑之約10%的粒徑在所有產生及使用階段更有可能導致斷裂。
如上文所指出,下限為非關鍵性的,其中主要考慮因素為產生更小粒子之難度及成本的增加。
因此,作為實際實例,一丹尼(1 D)聚酯纖維之直徑為10微米(µ),其意謂碳酸鈣粒徑不應超過約1 µ。熟習此項技術者將能夠基於此一般10%之關係選擇相關粒徑。
在類似關係中,母料組合物可以固體碎粒形式產生以用於儲存及運輸。終端使用者可隨後針對其特定最終用途之應用而將碎粒研磨成所需大小。
在一些實施例中,經研磨之母料粒子隨後與液體混合,該液體又將與所需最終聚合物混溶。作為一實例(但非限制),聚乙二醇或乙醇適用於聚酯製程。
作為進一步考慮,可在替代生產階段將所製備之母料添加至目標聚合物中。作為一種選擇,可在聚合物已製成之後將母料添加至聚合物生產線,但同時聚合物保持熔融狀態。
替代地,可在目標聚合物之聚合期間將母料添加至連續聚合物產線中。在此類配置中,若與最後聚合階段混溶,例如在連續產線之高聚合器中,則母料起到很好的作用。
彈性人造纖維。在本發明之情形中,彈性人造纖維可為母料製程之目標聚合物,其限制條件為彈性人造纖維為可熔融紡絲的。熟習此項技術者認識到,彈性人造纖維之變化為溶劑紡絲而非熔融紡絲,且本發明與熔融紡絲型式一起使用。
貫穿本說明書之實例並不打算為限制性的,但在各種實施例中,本發明可藉由任何所選特徵組合來表徵。在一些實施例中,組合物可藉由某些組分之不存在來部分界定。在一些實施例中,該等組合物避免包括澱粉或醣類;該等組分可大量溶解且產生缺乏足夠耐久性之織物。諸如聚丁二酸丁二酯之添加劑較佳不與非可生物降解之聚合物共聚,但在組合物內形成可降解相。
在一些實施例中,本發明之組合物避免脂族芳族聚酯。
本發明之纖維、紗線及織品可藉由其物理特性來表徵,諸如藉由實例中所描述之ASTM及/或AATCC檢驗來表徵。舉例而言,纖維、紗線及織品可藉由根據ASTM檢驗基於纖維中之生物降解劑之質量%的降解程度來定義。前驅物、中間物及最終產物之分子組合物可藉由習知方法,諸如凝膠滲透層析法,更佳藉由對聚合物摻合物進行梯度分析來測定。
當然,熟習此項技術者應理解,一旦母料與主要聚合物結合使用,則組成數目將與添加至主要聚合物之母料的相對量成比例變化。
熟習此項技術者亦將理解,當本發明在其實施例中視為熔融中間物時,熔融物可在最常見織物應用中以顆粒或長纖維形式擠出。擠製及急冷呈顆粒形式之熔融物在不同位置(例如在用戶位置)處提供儲存、運送及再熔顆粒之機會。
當使用熟習此項技術者所充分理解之技術來締捲自組合物急冷之長纖維時,隨後織品可直接由締捲長纖維(「長纖維紗線」)形成,或締捲長纖維可切割成短纖維。此類短纖維可繼而紡製成紗線,最常見地在開放式系統中,但顯然亦為環錠紡。紗線繼而可形成織品(編織、針織、非織)或可與另一聚合物(例如人造絲)或與天然纖維(棉或羊毛)摻合以形成摻合紗線,該摻合紗線繼而可製成具有摻合纖維之表徵的織品。
來自表1之任何配方可用於本文所提及之長纖維、顆粒、短纖維、締捲短纖維、締捲長纖維或織品中之任一者中。
如本文所用,術語「絨毛(nap)」及「有絨毛的(napping)」或「有絨毛的(napped)」係指用於所製造織物(例如Tortora,在上述第378至79頁)之充分理解的精整步驟。在此情形下,本發明亦適用於搖粒絨;亦即通常由聚酯製成之柔軟起絨的絕熱織品。
當形成適當長纖維時,預期根據本發明之組合物填充絕熱衣物極為奏效。
熟習此項技術者充分理解絕熱衣物的本質、結構及許多變化。基本上,絕熱材料封入輕質殼內,通常為低丹尼耐綸,常包括可經受至少一些沈澱之防水處理。
當然,羽絨為基於重量對重量的可壓縮性、放開性及溫度與重量比率之最佳絕熱材料,但諸如本發明之合成填充物在潮濕時提供較低成本及較佳絕熱特性,儘管其略重且壓縮性略低。
作為另一實例,預期根據本發明之長纖維、纖維及紗線作為可生物降解之地毯或此類地毯之部分表現極好。如熟習此項技術者所充分理解,地毯為通常由附著至襯底之堆積紗線或編束紗線形成的織物覆地板物。在合成材料出現之前且目前仍在使用,典型絨面係由羊毛製成,且襯底係由編織織品製成,其中紗線可編織、編束或以其他方式附著至該編織織物中。
熟習此項技術者通常可互換地使用術語「地毯(carpet)」或「地墊(rug)」,但在一些情形下,「地毯(carpet)」覆蓋整個房間(「滿鋪地毯(wall-to-wall carpeting)」),且「地墊(rug)」覆蓋小於整個房間之區域。
因為諸如耐綸、聚丙烯、聚酯及此等物質與羊毛之摻合物的合成材料為有用的地毯材料,所以由本發明形成之纖維或紗線完全適當且適用於地毯。熟習此項技術者認識到多種多樣的襯底材料、襯底結構及將絨面或毛圈附著至襯底之手段。重複所有此類可能性將為冗餘的而非明瞭的,且熟習此項技術者可在任何給定情形下且在無不當實驗時採納必需材料及步驟。
實例
將此等母料摻合於聚對苯二甲酸乙二酯(通常為1%母料)中且在封閉迴路中用重力式計量進料器饋入至安裝有雙螺桿之熔融擠製機。在250℃下混合添加劑批料且經由拉絲模頭擠出至水浴或等效急冷設備中。在分類器移除處於顆粒尺寸分佈之最末端處的粒子後,將顆粒乾燥及裝袋。
檢驗中所用碳酸鈣之質量平均粒徑為6.5微米且表面積為約1.5平方公尺/公克。
在59天時獲取初始讀數;在此極早讀數處,似乎配方13(表1)示出3.9%降解,而配方14呈現完全未開始降解。然而,基於資料中之氣壓操作及雜訊,來自配方13及14之資料似乎係不可靠的且不可再現的。另外,此低降解讀數過於接近待依賴之基線(針對無添加劑之PET,3%降解),且停止此等配方之檢驗。
以上示出之結果展現優於先前技術之優越性。在此等填埋場之條件下,PET纖維降解成甲烷及二氧化碳。266天後,該表中用1質量%母料配方#2、3、6、7及11製得之PET樣品分別降解43.6、66.1、56.5、21.3及38.3%。未改質之PET在相同條件下降解3.2%。最高降解自含有49%聚己內酯及10%聚羥基丁酸酯之母料發生,而最低降解自含有39%聚己內酯及20%聚丁二酸丁二酯之母料發生。由49%聚己內酯及10%聚羥基丁酸酯製成之材料與經含有39%聚己內酯、10%聚羥基丁酸酯及10%聚丁二酸丁二酯之1%母料改質之PET相比亦實質上更好地降解。
以上結果可與WO 2016/079724 (「表1—300天後之結果」)中所報導之結果相比較,其中聚醯胺纖維係使用商用之降解劑Eco-One®in之2%母料之熔融紡絲(https://ecologic-llc.com/about/eco-one-video-tour;2019年2月11日獲取)。經由ASTM D5511標準來檢驗所得纖維且在300天後發現其降解13.9%(「PA 6.6」)或15.5%(「PA 5.6」)。在相同ASTM D5511檢驗下,不具有生物降解劑之WO 2016/079724纖維降解2.2及2.3%。
基於未改質纖維,且忽略266與300天之間的差異,習知PET(本文中之表2)之降解量似乎比WO 2016/079724中之聚醯胺纖維之降解量高3.2/2.25=1.42x。相比之下,根據本發明之改質PET之降解量為WO 2016/079724中之經改質之聚醯胺纖維之降解量的21.3/15.5=1.37x與66.1/15.5=4.26x之間。針對WO 2016/079724中之聚醯胺纖維經兩倍之母料(2%相對1%)改質之事實進行校正,根據本發明之PET的可降解量高2.74x至8.52x。針對未改質聚酯與聚醯亞胺之間的2.74/1.42差異進行校正,本發明展現高1.92x至3.00x的可生物降解性。
ASTM D5210-在污水淤泥存在下之厭氧降解
ASTM D6691-厭氧降解模型5 海洋環境
實例-非毒性
使用ASTM E1963方法檢驗組合物,該方法為使用諸如蠶豆、玉米及豌豆之陸生植物物種來進行植物毒性檢驗以確定測試物質對植物生長及發育之作用的方案。豌豆為良好的指示物,因為其對土壤條件極其敏感。含有自配方2中之ASTM D5511檢驗之殘餘土壤的淋溶液用於此ASTM E 1963檢驗。圖7示出來自ASTM E 1963檢驗之結果。
檢測背景(第1行)及樣品(第3行)中植物的生長情況,展現相關副產物樣品中的淋溶液對植物生長無抑制作用。
經細菌分解之纖維之顯微分析
根據ASTM D5511中之發明,經細菌分解之纖維的纖維電子顯微成像顯示於圖6之SEM影像中(SEM HV:15 kV;視野173微米;SEM放大率1.5;Tescan™ Vega3™鎢熱離子發射SEM系統(https://www.tescan.com/en-us/technology/sem/vega3);2019年2月12日獲取),且在暴露於細菌>1年之後,示出在根據本發明之聚酯原胚纖維之表面上的細菌拓殖。
在圖式及說明書中,已闡述本發明之較佳實施例,且儘管已採用特定術語,但其僅用於一般及描述性意義且並非出於限制之目的,本發明之範疇界定於申請專利範圍中。
圖1至5為本發明之若干實施例以及纖維素材料與習知聚合物之對照實例之生物降解百分比(%)與經過的時間(以天數表示)的曲線圖。
圖6為根據本發明之經部分分解之纖維的SEM顯微圖。
圖7為說明本發明之植物檢驗之一系列相片。
Claims (10)
- 一種母料,其包含:在0.9與1.1質量%之間的CaCO3;39至49重量%聚己內酯;及其餘部分聚酯。
- 如請求項1之母料,其進一步包含選自由以下組成之群的聚合物:PBS、PLA、PBSA、PES、PHB、PHBV、PBAT、PBST、PBSTIL及其組合。
- 如請求項1之母料,其進一步包含量為9至11質量%之量的聚丁二酸丁二酯。
- 一種聚酯組合物,其基本上由1重量(質量)%之如請求項3之母料及其餘部分聚對苯二甲酸乙二酯組成。
- 如請求項1之母料,且其進一步包含選自由以下組成之群的組合物:5至10重量% PLA、5至10重量% PHA、5至10重量% PBAT、10至20重量% PBS、1重量%二氧化矽及此等組合物之組合。
- 一種熔融中間物,其包含:如請求項1至3及5中任一項之母料;及 至少90質量%之聚合物,其選自由以下組成之群:聚對苯二甲酸乙二酯、耐綸及其他熱塑性聚合物及其組合。
- 一種經急冷的具有尺寸特徵之複數個聚合物顆粒,其由如請求項6之熔融中間物形成。
- 一種經急冷之聚合物長纖維,其由如請求項6之熔融中間物形成。
- 如請求項6之熔融中間物,其進一步包含聚丁二酸丁二酯。
- 如請求項6之熔融中間物,其進一步包含選自由以下組成之群的組合物:0.05至0.1重量% PLA、0.05至0.1% PHA、0.05至0.1% PBAT、0.10至0.20重量% PBS、0.01重量%二氧化矽及此等組合物之組合。
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