微乳化與細乳化系統於紡織品噴墨印花用墨水與高分子製備之研究

Microemulsion and Miniemulsion in Ink and Polymer Preparation for Textile Ink Jet Printing

張曉瑩(Shiau-Yin Peggy Chang)

指導教授 ： 趙豫州

國立臺北科技大學/工程學院/有機高分子研究所/博士(2011年)

https://doi.org/10.6841/NTUT.2011.00589

摘要

紡織品噴墨印花技術隨著噴墨頭微積電系統演進使得開發快速反應與製程數位化解決方案為未來數十年發展重點，如何將目前市占率最大之分散性染料墨水的熱動力安定化與功能性高分子可附加化，以增進其噴印效能及簡化傳統製程，是本論文研究宗旨。 本論文包括三項主題： 一、 利用微乳化配方來調製分散性染料墨水，探討熱動力安定性與噴印效果之提昇；先將酞青色、洋紅色與黃色之不同結構分散性染料純化、研磨後再用乳化三相圖找出最大染料包覆於水包油微胞中，可 得到低於100 奈米的染料乳液,本質可耐長時噴印特性而不阻塞噴頭, 分散劑種類、染料結構與墨水含染料濃度值可供未來深入探討墨水 於噴頭產生流變學之參考。 二、 以細乳化聚合來合成氟素壓克力－豆膠共聚物並探討其吸墨性與撥水度而克服市售聚酯布前處理劑遇水產生水痕與色斑問題。採用十六烷基三甲基溴化銨與聚環氧乙烷類界面活性劑可與氟素壓克力單 體、其他單體及改質豆膠所形成核聚合物而附著於上；在較高單體 轉化率、最小膠體顆粒與較低豆膠改質率條件下所形成共聚合物之 前處理劑，可使聚酯織物在噴印昇華製程上表現良好色強度、線條 尖銳度、雙透性與適度撥水性。 三、 採用微乳化聚合反應所獲得Ｎ－（異丁氧基甲基）丙烯醯胺與苯乙烯等單體之共聚合物可結合棉纖維形成架橋之網狀結構而讓分散性染料固著發色；比較傳統用環保型界面活性劑，發現可聚合型馬來 酸鹽界面活性劑併用陰離子界面活性劑可大幅降低微胞與膠體粒徑、減少界面活性劑用量與提高固成份，且應用於市售墨水不改變黏度及噴印經時順暢性。將氧化還原劑用於第二階段起始反應可加速單體完全轉化與奈米粒徑分佈均一化，因此該微膠乳混合墨水不僅不阻塞噴頭且於昇華固色後之色強度及色牢度增加，噴印棉布之手感亦保持柔軟。

關鍵字

微乳化聚合 ； 細乳化聚合 ； 分散性染料可聚合界面活性劑 ； 噴墨印花 ； 棉 ； 聚酯 ； 布前處理劑 ； 接著劑

並列摘要

This study describes the inkjet ink preparation by
microemulsion formulation, in-situ binder formation by microemulsion polymerization and primer preparation via miniemulsion polymerization for ink jet printing on textiles. As we prepared microemulsion inks, the thermal dynamic stability of disperse dye particle was achieved in the approach to form oil-in-water microemuslion. Different species and amounts of dyes and surfactants were selected and optimized according to effective particle size reduction and size stabilization. The formed microemulsion inks in cyan, magenta and yellow met the requirement of inkjet printing with specific pH value, surface tension, viscosity and storage stability to provide both good printing quality and excellent printing consistency without clogging in the nozzle. The low efficiency of dye particle size reduction can be attributed to the compatibility between disperse dye and dispersant structures as well as particle aggregation. The lightfastness would be enhanced with smaller particle size, but decreased with dye content. The printing performance was found to be closely correlated with the disperse dye structure and ink concentration.

In order to provide the polyester fabric with partial water repellency and printability after inkjet printed with disperse dye inks (i.e., sublimation inks), a novel pretreatment paste was synthesized via miniemulsion polymerization of fluoroalkyl acrylates, styrene, 2-ethylhexyl acrylate and modified guar gum in the presence of 2,2’-Azobisisobutyronitrile as initiator, Cetyltrimehtylammonium bromide and polyoxyethylene polyaryl ether as surfactants under suitable reaction conditions. In the analysis of monomer conversion and particle size, the highest polymerization rate with smallest particle size was obtained with increasing concentration of surfactants and initiator but the decreasing degree of substitution of guar gum to imply stronger interactions between fluoroacrylate monomers, hydroxyl groups of modified guar gum and EO units of nonionic surfactants. The optimum fluorinated paste formulation treated on the 75 denier polyester fabric presented the print pattern with highest color strength, satisfactory edge acuity and least color difference between front and back sides of the fabric to show more transparency or ink penetration. The water repellency was graded at 80 to not only permit disperse dye ink droplets rapidly and evenly absorbed into polyester fiber i.e., even color without mottle effect, but also to prevent water stain after sublimation process.

For direct ink-jet printing of cotton fabrics with sublimation inks, the microlatex of Styrene / 2-ethylhexylacrylate / 2-hydroxyethylmethacrylate / N-(isobutoxymethyl) acrylamide copolymer was synthesized as a novel in-situ binder to provide soft hand feel and good color fastness after heat-press. In the optimized microemulsion composition with highest monomer mixture amount, polymerizable maleate surfactants with moderate EO value attained smaller microemulsion droplet size in mono distribution and lower dosage than conventional surfactants in combination with anionic surfactants. With adopted semi-continuous process in microemulsion copolymerization, the polymerizable surfactants stabilized the growth of microlatex particle size within 70nm and attained 100% monomer conversion with two initiator systems.

The microlatex particle size of two surfactant systems increased with higher conversion rate and reaction temperature, which synchronized with initiator concentration. High polymer solid content was contributed mainly by N-(isobutoxymethyl) acrylamide monomer ratio requiring higher amounts of anionic surfactants and 2-hydroxyethylmethacrylate as a co-surfactant in particle stabilization. The optimum inks prepared from the microemulsion with high N-(isobutoxymethyl) acrylamide content could tolerate printing durability without nozzle clogging. The printed cotton fabric by the above mentioned inks attained color fixation via sublimation to present good edge acuity, nearly zero color fading, high color strength, soft hand touch, and excellent color fastness at grade 4.

並列關鍵字

microeulsion polymerization ； miniemulsion polymerization ； dispere dye ； ink jet printing ； cotton ； polyester ； polymerizable surfactant ； binder ； primer

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