彭麗萍 周克華 沈岳
摘 要:聚乳酸(PLA)纖維是一種綠色環(huán)保的聚合高分子材料,開(kāi)發(fā)PLA纖維產(chǎn)品已成為當(dāng)今生態(tài)紡織產(chǎn)品的開(kāi)發(fā)方向之一。以PLA纖維為原料,緯編毛巾組織為基礎(chǔ),采用小元寶針織結(jié)構(gòu),在大圓機(jī)上編織、氣流染色機(jī)上染色,制備了一種雙面剪毛絨針織面料。介紹了PLA雙面剪毛絨面料的特點(diǎn)和生產(chǎn)工藝,闡述了該面料的織造、染色、還原清洗、拉毛、梳毛、剪毛和定型等工序及技術(shù)關(guān)鍵,以期為同類產(chǎn)品的開(kāi)發(fā)提供參考。
關(guān)鍵詞:聚乳酸纖維(PLA);雙面剪毛絨;氣流染色機(jī);面料織造;染整工藝
中圖分類號(hào):TS155;TS195 文獻(xiàn)標(biāo)志碼:A 文章編號(hào):1009-265X(2023)06-0167-07
隨著人們生活水平的提高,生活方式更加多樣化,對(duì)環(huán)境保護(hù)的意識(shí)也日益加強(qiáng),曾經(jīng)被“冷落”的聚乳酸(Polylactic acid,PLA)纖維,近幾年又被重視和利用起來(lái)[1]。PLA纖維俗稱玉米纖維,是以玉米、小麥等淀粉為原料,經(jīng)發(fā)酵轉(zhuǎn)化成乳酸,再經(jīng)聚合紡絲制得的一種合成纖維[2]。PLA纖維“來(lái)自于自然,回歸于自然”,具有較好的生物可降解性,可循環(huán)利用,符合當(dāng)今綠色環(huán)保的時(shí)代需求,被眾多專家推薦為“21世紀(jì)的環(huán)境循環(huán)材料”,是一種極具發(fā)展?jié)撡|(zhì)的綠色纖維[3]。PLA纖維制成的紡織面料具有手感柔軟、抗皺耐用、穿著舒適等優(yōu)點(diǎn),其產(chǎn)品使用后進(jìn)行降解處理時(shí)容易分解為低分子物,不會(huì)造成環(huán)境污染,是一種低碳環(huán)保紡織產(chǎn)品[4],也可應(yīng)用于生物醫(yī)療和塑料生產(chǎn)等領(lǐng)域[5]。
PLA纖維已有20余年的工業(yè)化開(kāi)發(fā)歷程[6],但其在紡織領(lǐng)域并沒(méi)有大規(guī)模推廣應(yīng)用,主要原因是PLA纖維的染色性、耐熱性和耐水解性較差,限制了其規(guī)?;瘧?yīng)用[7]。為克服PLA纖維的缺點(diǎn),近年來(lái)研究人員通過(guò)纖維混紡開(kāi)發(fā)了一些性能優(yōu)異的紡織產(chǎn)品。例如,陳歡歡等[8]開(kāi)發(fā)了一種綠色環(huán)??山到獾木廴樗?百里酚抗菌纖維;周克華等[9]開(kāi)發(fā)了一種Provscose/PLA交織高密斜紋面料;徐海兵等[10]采用PLA/PHBV與棉纖維共混紡紗的方式開(kāi)發(fā)了一種生物可降解抗菌針織面料;劉超等[11]總結(jié)分析了粘膠與聚乳酸纖維混紡交織色織物的生產(chǎn)技術(shù);鄧文韜等[12]測(cè)試分析了聚乳酸玉米纖維/氨綸混紡織物的服用性能;肖云超等[13]將聚乳酸纖維長(zhǎng)絲與亞麻/黏膠單紗直接并合加捻,開(kāi)發(fā)了一種性能優(yōu)良的聚乳酸吸濕排汗運(yùn)動(dòng)面料。上述文獻(xiàn)報(bào)道了一些PLA交織混紡產(chǎn)品,但沒(méi)有關(guān)于PLA纖維起絨產(chǎn)品的開(kāi)發(fā)。為豐富PLA纖維紡織面料的產(chǎn)品種類,滿足人們美好生活的需要,本文開(kāi)發(fā)了一種PLA雙面絨針織面料,該面料以緯編毛巾組織為基礎(chǔ),采用小元寶針織結(jié)構(gòu),在大圓機(jī)上進(jìn)行編織,在氣流染色機(jī)上進(jìn)行染色。該面料的開(kāi)發(fā)可為同類產(chǎn)品的生產(chǎn)提供參考。
1 面料設(shè)計(jì)
用滌棉纖維生產(chǎn)的雙面剪毛絨是一個(gè)老產(chǎn)品[14-15],滌棉等常規(guī)纖維雙面剪毛絨產(chǎn)品不僅具有成熟的工藝,而且有完全配套的設(shè)備和穩(wěn)定的內(nèi)外在質(zhì)量[16]。但選用PLA纖維生產(chǎn),卻是一個(gè)全新的產(chǎn)品。本文開(kāi)發(fā)的PLA雙面剪毛絨是一款新型環(huán)保型秋冬保暖產(chǎn)品,其面料具體參數(shù)為:幅寬160 cm;成分100% PLA;面密度320~330 g/m2;長(zhǎng)絲規(guī)格為外圈150D/144F(內(nèi)圈150D/144F),連接100D/72F。
開(kāi)發(fā)的PLA雙面剪毛絨面料的制備流程為:
織造上機(jī)→調(diào)機(jī)→下布→染廠配布→立式剖幅→理布→縫頭→洗滌去油→染色→缸加起毛劑→脫水→烘干→低溫定型(拉幅)→正面拉毛→反面拉毛→正面梳毛→反面梳毛→正面剪毛→反面剪毛→定型→打卷→包裝。
2 生產(chǎn)工序技術(shù)要求
2.1 織造
a)設(shè)備參數(shù):設(shè)備 L-PLD2型雙面毛巾機(jī);機(jī)號(hào) 22針/25.4 mm;路數(shù) 60F;筒徑 34"(864 mm);總針數(shù) 2080枚;車速 20 r/min。
b)穿紗方式: 外圈穿入PLA 150D/144F長(zhǎng)絲,連接路穿入PLA 100D/72F長(zhǎng)絲,內(nèi)圈穿入PLA 150D/144F長(zhǎng)絲。
c)編織示意圖:PLA雙面剪毛絨面料的編織示意如圖1所示。
2.2 染色
2.2.1 染色設(shè)備
所開(kāi)發(fā)生產(chǎn)的PLA雙面剪毛絨面料單位米克重較高,不宜選用溢流染色機(jī)染色。因?yàn)橐缌魅旧珯C(jī)中張力要大于氣流染色機(jī),易造成織物的擦傷和變形。為了使生產(chǎn)出來(lái)的面料布面平整、無(wú)折痕,同時(shí)考慮到節(jié)約水、染化料、助劑和能源,實(shí)現(xiàn)節(jié)能減排和綠色環(huán)保,選用800 kg高溫氣流染色機(jī)(德國(guó)Thies公司)。PLA雙面剪毛絨坯布在氣流缸中借助含有濕氣或者水蒸汽的氣體通道進(jìn)行循環(huán),無(wú)需染液或水介質(zhì)輸送,始終處于松弛狀態(tài),所受張力較小,得色均勻、手感柔軟蓬松。
2.2.2 洗滌去油
PLA纖維屬于脂肪族聚酯纖維,分子鏈中存在較多的酯基和一些有等距排列的甲基,不存在強(qiáng)極性基團(tuán),其分子結(jié)構(gòu)如圖2所示,因此分子間作用力弱;分子鏈中酯基容易水解,且端羧基對(duì)其水解有催化作用,因此,PLA纖維耐堿性比較差,在高溫堿性條件下會(huì)發(fā)生嚴(yán)重的水解,造成纖維的損傷[17]。同時(shí),100%PLA雙面剪毛絨坯布中無(wú)天然雜質(zhì),前處理只要洗除織物上沾污的油漬即可,因此PLA雙面剪毛絨的洗滌去油只需要在氣流染色機(jī)中采用溫和條件下進(jìn)行洗滌去油。具體工藝條件為:加入1~2 g/L的乳化精練劑,浴比1∶8,快速升溫至60 ℃,處理15 min,冷卻至45 ℃排液,過(guò)冷水3遍。
2.2.3 染色過(guò)程
PLA纖維是由乳酸基團(tuán)單體經(jīng)直接聚合或丙交酯的開(kāi)環(huán)聚合合成的一種線型大分子高聚物,纖維結(jié)晶度高,分子結(jié)構(gòu)較緊密,因此宜選擇擴(kuò)散性能好、分散穩(wěn)定且分子呈直線型和共面性較強(qiáng)的分散染料[18]。PLA纖維對(duì)分子中存在酯基、羥基、鹵素原子等極性基團(tuán)的染料有較高的親和力,可選用有具有較好相容性和染色同步性的中低溫型分散染料對(duì)PLA纖維織物進(jìn)行染色,該類染料染液的pH值、溫度、時(shí)間等因素變化對(duì)其染色影響相對(duì)較小,重現(xiàn)性好,并具有優(yōu)良的分散性、勻染性及遮蓋性,耐洗牢度及耐曬牢度也較好[19]。經(jīng)生產(chǎn)實(shí)踐,選用幾種染料對(duì)PLA和PET纖維進(jìn)行染色,呈現(xiàn)的顏色結(jié)果如表1所示。經(jīng)對(duì)比,日本化藥株式會(huì)社的PL-HC型分散染料更適合于PLA雙面剪毛絨的氣流染色機(jī)染色。
PL-HC型分散染料對(duì)PLA雙面剪毛絨染色過(guò)程中,提高溫度可以促進(jìn)染料上染,提高染色深度。保溫20 min不同染色溫度對(duì)斷裂強(qiáng)力、斷裂伸長(zhǎng)率的影響如表2所示,可見(jiàn)當(dāng)染色溫度超過(guò)120 ℃后,織物強(qiáng)力幾乎呈直線下降,因些染色溫度不宜超過(guò)120 ℃。在高溫濕熱狀態(tài)下,長(zhǎng)時(shí)間的保溫會(huì)引起PLA纖維結(jié)晶增加,改變其染色性能,降低上染速率和最高上染率,所以染色保溫時(shí)間不宜過(guò)長(zhǎng)。故需嚴(yán)格控制升溫速率和時(shí)間,在確保PLA雙面剪毛絨強(qiáng)力的同時(shí)提高染色深度和重現(xiàn)性。
PLA雙面剪毛絨面料在70 ℃以下幾乎不上色,達(dá)到80 ℃后,隨溫度上升上染速率急劇提高,故在染色溫度達(dá)到80 ℃后需要減緩升溫速度,調(diào)整為0.5 ℃/min。為了加強(qiáng)移染,提高勻染程度,在85 ℃時(shí)保溫約10 min;然后以1 ℃/min的速度升溫至最高溫度120 ℃并保溫20 min;再按2 ℃/min降溫速度降溫,直至50 ℃左右,最后排液并進(jìn)行洗滌和還原清洗。以染黑色為例,分散染料染液配方:KP Rubine PL-HC 0.15%(o.w.f)、KP Yellow Brown PL-HC 0.21%(o.w.f)、KP Black PL-HC 5.50%(o.w.f)、分散劑0.80%(o.w.f)、pH值4.5~5.5、浴比1∶8,染色工藝曲線如圖3所示。
用PL-HC型分散染料對(duì)PLA雙面剪毛絨染色時(shí),pH值對(duì)上染率的影響如表3所示。可見(jiàn),用醋酸調(diào)節(jié)染液的pH值為4.5~5.5,可以提高分散染料對(duì)PLA纖維的親和力,提高上染率,得到理想的深黑顏色。
2.3 后整理
2.3.1 還原清洗
PLA纖維染色后的還原清洗是一個(gè)十分重要的后整理加工環(huán)節(jié)。經(jīng)洗滌會(huì)仍會(huì)有部分染料和氧化后的染料吸附在纖維的表面,影響色光、水洗牢度、摩擦牢度,因此需要對(duì)面料進(jìn)行還原清洗,適當(dāng)?shù)倪€原清洗將有助于提高各項(xiàng)色牢度。由于PLA纖維不耐強(qiáng)堿,在強(qiáng)堿和保險(xiǎn)粉的作用下會(huì)發(fā)生嚴(yán)重的水解,引起PLA纖維的損傷和染料的褪色、變色。為了避免強(qiáng)堿條件下還原清洗對(duì)PLA纖維損傷及其顏色深度的影響,經(jīng)反復(fù)試驗(yàn),溫度控制在60~65 ℃,堿劑用純堿,對(duì)面料進(jìn)行還原清洗兩遍,每次20 min。通過(guò)兩遍純堿/保險(xiǎn)粉的低溫還原清洗,可以獲得理想的各項(xiàng)色牢度。具體工藝條件:純堿1.5 g/L;保險(xiǎn)粉2.0 g/L;浴比1∶20;溫度60 ℃;時(shí)間20 min。
2.3.2 烘干、拉幅(低溫定型)
PLA纖維的耐濕熱性較差,采用直接接觸式高溫烘干,手感會(huì)產(chǎn)生硬挺現(xiàn)象,這種現(xiàn)象不可逆轉(zhuǎn),因而PLA雙面剪毛絨面料在烘干時(shí)宜采用從定型機(jī)跳過(guò)夕林在針板上直接用熱風(fēng)烘干;同時(shí)通過(guò)升幅,可以將在染色過(guò)程中形成的折皺消除,并使面料形態(tài)基本穩(wěn)定,防止在刷毛、剪毛過(guò)程中產(chǎn)生不可回逆的毛面質(zhì)量問(wèn)題。由于PLA纖維對(duì)溫度非常敏感,經(jīng)實(shí)踐,烘干、拉幅的溫度必須嚴(yán)格控制在120 ℃以下,這樣可以防止接觸式烘干時(shí)因局部受高溫,造成面料的局部板結(jié)、手感變硬、強(qiáng)力損失等現(xiàn)象。定型30 s時(shí)不同溫度對(duì)面料手感、強(qiáng)力的影響如表4所示。
2.3.3 拉毛
PLA雙面剪毛絨坯布雖經(jīng)織造、洗滌去油、染色、烘干、拉幅等工序,但布面還沒(méi)有毛絨感,需要對(duì)其正反面進(jìn)行拉毛處理,經(jīng)拉毛處理后可賦予雙面絨的效果,同時(shí)也可使面料蓬松、質(zhì)輕、柔軟、保暖、親膚。拉毛在拉毛機(jī)上進(jìn)行,拉毛機(jī)將織物組織中用于起絨的紗線的纖維勾出,被勾起的纖維在織物表面形成絨毛而成。拉毛的原則是多道輕拉,經(jīng)實(shí)踐,此面料在36輥拉毛機(jī)上正面2道反面2道,再正面2道反面2道,然后再正面2道反面2道,布速15~18 m/min,拉毛機(jī)壓力輥的壓力控制在9 kg,主轉(zhuǎn)筒速度控制在130~200 r/min,先慢后快,視布面絨毛效果調(diào)整轉(zhuǎn)速;為保證反面拉毛后的毛向與正面毛向一致,正面拉毛2道結(jié)束后需要進(jìn)行倒布,反復(fù)進(jìn)行3次。
2.3.4 梳毛
拉毛后的半成品通過(guò)梳毛機(jī)上針輥,把雜亂的毛絨梳開(kāi)拉直,倒毛站立,梳掉絨毛里的斷毛,可以使梳毛后布面絨毛變得蓬松、順直。梳毛張力設(shè)定為5 kg,大錫林轉(zhuǎn)速100 r/min,正面梳毛、倒布、反面梳毛,接著再重復(fù)1次,基本上就可以達(dá)到梳毛的效果。
2.3.5 剪毛
PLA雙面剪毛絨坯布經(jīng)織造、染色、烘干、拉幅、拉毛后表面毛絨纖維長(zhǎng)短不一,需要將絨毛剪短成為直立、整齊、平坦的絨面。剪毛時(shí)需要根據(jù)絨面的效果,調(diào)節(jié)三角刀與圓刀的角度,使剪出來(lái)的絨毛直立、無(wú)倒伏。此面料采用逆向上機(jī)剪毛,正面剪毛、倒布、反面剪毛,這樣可以使織物兩面均獲得均勻、蓬松、密集、豐滿的絨面,達(dá)到理想的效果。
2.3.6 定型(低溫拉幅)
PLA雙面剪毛絨織物經(jīng)織造、染色、拉毛、梳毛、剪毛等一系列工序后,面料的幅寬、左中右的克重參差不齊,因而需要在低于120 ℃熱風(fēng)條件下將門幅拉伸至規(guī)定單位克重的門幅;為了保證經(jīng)向縮水率達(dá)到要求并基本一致,需要通過(guò)超喂來(lái)減小或消除經(jīng)向的縮水率,并視具體縮水率數(shù)值,合理調(diào)整針板上針裝置的超喂量,同時(shí)其他裝置的超喂量要與之相匹配;在定型機(jī)上對(duì)PLA雙面剪毛絨面料進(jìn)行拉幅、超喂、矯歪時(shí),其針板的上風(fēng)需要略大于下風(fēng),避免產(chǎn)生“脫針”現(xiàn)象;調(diào)節(jié)好風(fēng)口,確保高速暖風(fēng)氣流能均勻地吹到布面上,從而使面料獲得優(yōu)異的手感和膨松效果,降低殘余縮率;經(jīng)實(shí)踐,熱風(fēng)溫度必須小于120 ℃,作用時(shí)間小于30 s,否則手感會(huì)變硬、膨松感變差;為了避免落布溫度偏高,造成難以去除的壓折印,面料出針板后需要經(jīng)過(guò)冷卻輥進(jìn)行冷卻,確保布面溫度小于40 ℃;成品定形不能經(jīng)過(guò)軋輥定形,否則會(huì)影響雙面剪毛絨的蓬松感。
3 成品性能
以PLA纖維為原料,經(jīng)過(guò)上述織造和染整工序,制得的面料單位克重:328 g/m 斷裂強(qiáng)力:128 cN,斷裂伸長(zhǎng)率:18.2 %,面料的耐水洗牢度4~5級(jí)。成品正反面形成了蓬松、厚實(shí)、柔軟和富有彈力的毛絨,其絨毛能鎖住中間的許多空氣,增加纖維與纖維之間的靜止空氣層,減緩與外界空氣的對(duì)流。產(chǎn)品具有質(zhì)輕、保暖、透氣,以及親膚、抑菌的特點(diǎn)。
4 結(jié) 語(yǔ)
本文選用PLA纖維為原料,以緯編毛巾組織為基礎(chǔ),采用小元寶針織結(jié)構(gòu),在大圓機(jī)上編織、氣流染色機(jī)上染色,開(kāi)發(fā)了一種PLA雙面剪毛絨針織面料。經(jīng)生產(chǎn)實(shí)踐發(fā)現(xiàn),該面料織造染整過(guò)程中需注意:
a)面料染色時(shí)宜選用低張力的氣流染色機(jī),保證布面平整、無(wú)折痕;采用溫和條件下進(jìn)行洗滌去油,防止水解造成纖維的損傷;宜選用中低溫型分散染料對(duì)PLA纖維織物進(jìn)行染色,染色溫度不宜超過(guò)120 ℃;面料在還原清洗時(shí),為克服強(qiáng)堿條件下還原清洗對(duì)PLA纖維損傷及其顏色深度的影響,宜采用純堿/保險(xiǎn)粉的低溫還原清洗兩遍。
b)面料在烘干時(shí),宜采用從定型機(jī)的針板上直接用熱風(fēng)烘干,可以防止接觸式烘干時(shí)局部受高溫,造成面料的局部板結(jié)、手感變硬等現(xiàn)象。面料在拉毛、梳毛、剪毛過(guò)程中,須視布面效果,合理調(diào)整工藝參數(shù);為防止“嗆”毛,并使正反面毛向一致,需要進(jìn)行倒布;剪毛須采用逆向上機(jī)剪毛,這樣可以使織物兩面都獲得均勻、蓬松、密集、豐滿的絨面,達(dá)到理想的效果。
c)面料在拉幅時(shí),須合理調(diào)整上下風(fēng)量、針板超喂的超喂量;為避免手感變硬、膨松感變差、落布溫度偏高而造成的壓折印,熱風(fēng)溫度須小于120 ℃、作用時(shí)間小于30 s、落布布面溫度小于40 ℃;成品拉幅不能經(jīng)過(guò)軋輥,避免對(duì)雙面剪毛絨蓬松感的影響。
PLA纖維是21世紀(jì)的天然可再生高分子材料,其產(chǎn)品的開(kāi)發(fā)利用符合當(dāng)前綠色環(huán)保的要求,具有良好的社會(huì)與經(jīng)濟(jì)價(jià)值,有助于中國(guó)綠色紡織技術(shù)的高質(zhì)量發(fā)展。在起絨織物開(kāi)發(fā)中除了應(yīng)用類似PLA的新型纖維材料外,納米技術(shù)、低溫等離子技術(shù)、微膠囊技術(shù)、數(shù)碼噴射印花等新技術(shù)也可應(yīng)用到起絨織物的開(kāi)發(fā)生產(chǎn)中,結(jié)合新材料和新技術(shù),實(shí)現(xiàn)起絨織物產(chǎn)品的升級(jí)換代,推動(dòng)起絨織物向原料多元化、風(fēng)格多樣化、使用功能化方向發(fā)展,使傳統(tǒng)的起絨織物煥發(fā)出新的活力。
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Preparation and production technology of PLA knitted fabric with double-sided sheared plush
PENG Liping1, ZHOU Kehua2,? SHEN Yue3
Abstract: The PLA fiber is a natural recyclable polymer material in the 21st century, and the development and utilization of its products meet the current requirements of green, environmental protection and renewability. It has good social and economic value, which is conducive to the high-quality development of green textile technology in China. With PLA fibers as raw material, based on weft woven towel tissue, a knitted fabric with double-sided sheared plush was developed by weaving on a large circular knitting machine with a small ingot knitting structure.
The PLA fabric with double-sided sheared plush has the advantages of fluffiness, warmth, breathability, softness, skin-friendliness,bacteriostasis, mildew-proofing, and zero irritation to human skin, so it is an ideal fiber fabric for clothing. To ensure that the fabric surface is smooth and without creases, and save water, dyeing materials, additives and energy, aits nd truly achieve energy saving, emission reduction, green and environmental protection, airflow dyeing machine should be used for printing and dyeing processing. For the PLA fabric with double-sided sheared plush strong alkali cannot be used in the process of washing and degreasing and dyeing, reduction and cleaning, otherwise serious hydrolysis of PLA fiber and strong damage of PLA fiber will occur, resulting in short hair, hair loss and other phenomena. In order to overcome the influence of reduction cleaning on PLA fiber damage and its color depth under strong alkali conditions, it is advisable to use the process of low temperature reduction cleaning of soda ash/fuse powder twice, and the ideal color fastness can be obtained. PLA double-sided shearing plush should be dried directly with hot air from the needle board of the stenter machine, which can prevent local hardening of the fabric, hardening of the hand and other phenomena at local high temperature during contact drying. In the process of brushing, combing and shearing of PLA fabric with double-sided shearing plush, the process parameters need to be reasonably adjusted according to the effect of the cloth. To prevent "choking" the hair and make the front and back sides of the hair consistent, it is necessary to reverse the cloth; during shearing, the use of reverse upward machine shearing is required, which can achieve a uniform, fluffy, dense and plump suede on both sides of the fabric to achieve the desired effect. When PLA double-sided shearing plush fabric is pulled, it is necessary to reasonably adjust the upper and lower air volume and the overfeeding volume of needle board overfeeding. To avoid the creasing caused by hardening of the hand feeling, poor bulking sensation and high drop cloth temperature, the hot air temperature must be less than 120 ℃, the action time less than 30 seconds, and the drop cloth surface temperature less than 40 ℃; the finished stenter should not pass through the roll to avoid the effect on the fluffy feeling of double-sided sheared plush.
This paper focuses on the characteristics of PLA fibers, the characteristics of PLA fabrics with double-sided sheared plush and elaborates the production process and technical key of PLA products with double-sided sheared plush such as weaving, dyeing,reduction cleaning, brushing, combing, shearing and shaping, so as to provide reference for the development of similar products.
Keywords: PLA fiber; double-sided sheared plush; air flow dyeing machine; fabric weaving; dyeing technology
收稿日期:20230707 網(wǎng)絡(luò)出版日期:20230807
基金項(xiàng)目:企業(yè)橫向合作開(kāi)發(fā)項(xiàng)目(NTSR2021)
作者簡(jiǎn)介:彭麗萍(1975—),女,江西景德鎮(zhèn)人,講師,主要從事新型紡織面料開(kāi)發(fā)利用方面的研究。
通信作者:周克華,E-mail:zhoukehua@sunrisechina.com.cn