TW200535300A - Method of dyeing polypropylene fiber with long chain alkyl azo dye - Google Patents

Abstract

This invention relates to a method of dyeing polypropylene fiber with long chain alkyl azo dye. Effective Van der Waal's force will form between dye and fiber because of the good planar structure of dye and chain parallel of each other. In another aspect, better fastness can be obtained as dyeing process was completed and large dye molecules were trapped within fibers. In particular, by performing dyeing using fluids having the effect of supercritical CO2 with high permeability can cause dye molecules to be trapped in the polypropylene fiber with highly dense crystalline, by dyeing polyprolene with long chain disperse alkyl dyes so as to have good dyeing results, and wash fastness of 3 to 4 grade.

Description

200535300 玖、發明說明： 【發明所屬之技術領域】 本發明係關於一種聚丙烯纖維的染色 方法， 特別 種使用長鏈烷基偶氮型染料來對聚丙烯纖維纖維逛〜 疋 的方法者。 染色 【先前技術】 細丹尼聚丙烯纖維具有良好的手感、蕊吸 敦應 和導濕 透氣性，可用於針織軍用服、防寒 、 予 有發展前徐 的舒適衣用纖維。但是由於聚丙烯纖維結晶度高， 子結構中不含有極性基團和化學活性基團，因此不2其分 染料的分子團結合，所以有染色上 易和 男木色上的困難，用顏料對 烯纖維進制液$ & n解決地 κ 。丄系用聚丙埽等 丹尼數、大噸位產品的染色問題，對於細丹尼 、’、且 進打原液染色，則面臨容易斷絲的困境，從 纖維在衣著服裝上的應用和發展。 聚丙烯纖維 而限制聚丙烯 除了原液染色外，對聚丙烯纖唯 戰卓木色的研究主要是對 聚丙烯纖維改質後再使用各 木枓木色，例如：（a)1983 年’ Shah和Jain以次氣酸鈉氣化及 予’臭化處理改質聚 丙烯纖維來與陽離子染料染色， 、人 '义的聚丙稀纖維和染 料產生共價力’耐洗、漂白、耐海水和 ’、 喊煮牢度提升， 纖 200535300 維回潮率提高，但強度下降，且需做後處理才可改善曰光 牢度；【C.D.Shah and D.K.Jain，" Dyeing of Modified200535300 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to a method for dyeing polypropylene fibers, and particularly to a method of using polypropylene with a long-chain alkyl azo dye to bleed through the fibers. Dyeing [Previous technology] Fine denim polypropylene fiber has good hand feeling, core absorption, moisture permeability and breathability, and can be used in knitted military clothing, cold protection, and comfortable clothing fibers that have been developed before. However, due to the high crystallinity of polypropylene fibers, the substructure does not contain polar groups and chemically active groups, so it does not combine molecular groups of dyes. Therefore, it is difficult to dye and male wood color. Fiber Base Solution $ & n Solve Ground κ. For the dyeing of products with denier and other large tonnages such as polypropylene, for fine denier, ′, and advanced stock solution dyeing, they face the problem of easy thread breakage, from the application and development of fibers in clothing. Restriction of polypropylene fibers in addition to dope dyeing. In addition, the research on the color of polypropylene fibers is mainly based on the modification of polypropylene fibers and then using the wood color. For example: (a) 1983 'Shah and Jain uses sodium hypogas to vaporize and pre-odorize modified polypropylene fibers to dye with cationic dyes. Human polypropylene fibers and dyes produce covalent forces 'washing, bleaching, seawater resistance,', The fastness of shouting is improved, and the moisture regain of fiber 200535300 is increased, but the intensity is reduced, and post-processing is required to improve the light fastness; [CDShah and DKJain, " Dyeing of Modified

Polypropylene: Cationic Dyes on ChlorinatedPolypropylene: Cationic Dyes on Chlorinated

Polypropylene ” Text. Res 〇\.53 ,No .5 , ρ274·281， 19 83 ； C.D.Shah and D.K.Jain，“ Dyeing of ModifiedPolypropylene ”Text. Res 〇 \ .53, No .5, ρ274 · 281, 19 83; C.D.Shah and D.K.Jain,“ Dyeing of Modified

Polypropylene: Cationic Dyes on BrominatedPolypropylene: Cationic Dyes on Brominated

Polypropylene 7>χί./?α·7·，ν〇1·54，Νο·11， p742-748, 1984】（b)利用丙烯酸酯系列的化合物，以射線照射共聚合 聚丙烯製造出適合鹽基性染料、酸性染料及分散性染料染 色的共聚合物；【Α· K· Mukher jee and B· D· Gupta, “ Disperse Dyeing of Methacry1ic Acid GraftedPolypropylene 7 > χί ./? Α · 7 ·, ν〇1 · 54, No. 11, p742-748, 1984] (b) Copolymerization of polypropylene with ray irradiation using acrylic compounds to produce suitable bases Co-polymers dyed with basic dyes, acid dyes and disperse dyes; [Α · K · Mukher jee and B · D · Gupta, "Disperse Dyeing of Methacry1ic Acid Grafted

Polypropylene Fibres” JSDC, Vol.104, No.3, pl30- 133, 1988 ； I.K. Mehta, B.N.Misra and G. S. Chauhan, “ Study of Thermal and Dyeing Behavior ofPolypropylene Fibres ”JSDC, Vol.104, No.3, pl30- 133, 1988; I.K. Mehta, B.N.Misra and G. S. Chauhan,“ Study of Thermal and Dyeing Behavior of

Isotactic Polypropylene Fiber Graft Copolymerized with Aery late Monomers Using PreirradiationIsotactic Polypropylene Fiber Graft Copolymerized with Aery late Monomers Using Preirradiation

Method ” J. Appli. Poly. Sci. , Vol. 54, No. 8, p!171- 1 1 78, 1 994 】（c)Akrman et al.在聚丙烯纖維上增加一些極 性的添加劑且紡成可酸性染色的纖維；【Jiri Akrman and Marie Kaplanova， “ The Coloration of 200535300Method ”J. Appli. Poly. Sci., Vol. 54, No. 8, p! 171- 1 1 78, 1 994】 (c) Akrman et al. Added some polar additives to polypropylene fibers and spun into Acid dyeable fibers; [Jiri Akrman and Marie Kaplanova, "The Coloration of 200535300

Polypropylene with Acid Dyes” JSDC, Vol.Ill,No.5, pl59-163, 1995 ; Jiri Akrman and Josef Prikryl， “ Dyeing Behavior of Polypropylene BlendPolypropylene with Acid Dyes ”JSDC, Vol.Ill, No.5, pl59-163, 1995; Jiri Akrman and Josef Prikryl,“ Dyeing Behavior of Polypropylene Blend

Fiber. I I. Ionic Exchange Mechanism of Dyeing ” 人如;?人尸〇//· Sc人，Vol· 66, No· 3， p543-550， 1 997 】與 (d)Seves和Akrman也試著用氫化寡環五烯（hydrogenated oligocyclopentadiene)或者以羊毛對聚丙烯纖維混紡並討論 其結果【A.Seves， T〇De Marco and A.Siciliano, "Blending Polypropylene with Hydrogenated Oligocyclopentadiene: A New Method for the Production of Dyeable Fibers Dyes and Pigment, Vol, 28, No. 4, P19-29， 1995 ； Jiri Akrman, Josef Prikryl andFiber. I I. Ionic Exchange Mechanism of Dyeing "such as; human corpse 〇 // · Sc, Vol · 66, No · 3, p543-550, 1 997】 and (d) Seves and Akrman also tried to use Hydrogenated oligocyclopentadiene or blending wool with polypropylene fibers and discussing the results [A. Seves, T〇 De Marco and A. Siciliano, " Blending Polypropylene with Hydrogenated Oligocyclopentadiene: A New Method for the Production of Dyeable Fibers Dyes and Pigment, Vol, 28, No. 4, P19-29, 1995; Jiri Akrman, Josef Prikryl and

Ladislav Burgert, ^ Dyeing of Polypropylene/Wool Blend in a Single Bath” jSDC9 Vo 1. 114,No.7, p209-^ 215，1 998】；然而，上述之數種方法卻同樣會造成聚丙 烯纖維對光的敏感性及機械性質的降低，最重要的是改質 所需的高成本，使聚丙烯纖維不利於商業用途。由於聚丙 烯纖維改質將影響其原有的優良的物理化學性能，且染色 成本增加，不具市場競爭力，因此不能從根本上解決聚丙 稀纖維染色困難的問題，特別是對於細丹尼聚丙稀纖維之 200535300 纖度細、表面積大，在染色過程中易彦 至生色差、不易得到 均勻的染色效果及耐水洗染多哆宗声、去 于 ^牛又建不到要求等問題， 一直仍然缺少解決的方法。 【發明内容】 有鑑於上述聚丙烯纖維在毕斧 *隹木a万面所面臨的困難，本 發明人特別研究出一種使用呈旦⑼ρ甘 便用具長鏈烷基之偶氮染料，以期 減輕或克服習用聚丙烯纖維染整方法的缺點。Ladislav Burgert, ^ Dyeing of Polypropylene / Wool Blend in a Single Bath ”jSDC9 Vo 1. 114, No. 7, p209- ^ 215, 1 998]; however, the above-mentioned methods will also cause polypropylene fibers to face light. The reduction of the sensitivity and mechanical properties of the polypropylene is most importantly the high cost of modification, which makes polypropylene fibers unfavorable for commercial use. Since the modification of polypropylene fibers will affect its original excellent physical and chemical properties, and dyeing Increased cost and lack of market competitiveness, so it cannot fundamentally solve the difficult problem of polypropylene fiber dyeing, especially for the fine denier polypropylene fiber 200535300. The fineness is large and the surface area is large. The problem of obtaining uniform dyeing effect and water-resistant washing and dyeing, and the lack of requirements for the construction of the cow, has not been solved. [Summary of the Invention] In view of the above polypropylene fiber in Biax * Tochigi a The difficulties faced by all facets, the inventors have specially developed an azo dye using a long-chain alkyl group which is a denier, in order to reduce or overcome the conventional polypropylene. The method of dyeing fibers disadvantage.

本^月之主要目的係在於提供一種使用長鏈燒基偶氮 染料對聚丙烯纖維染色 卞巴的方法，其可以達到容易染色、均 勻的染色效果及優肖^ 文良的耐水洗染色堅牢度之目的。 為達到上述的目的 鏈烷基偶氮染料來斜聚 ，本發明之主要技術手段為使用長 丙烯纖維進行染色，其中所使用的 染料之結構如 (A) 下列通式所示：The main purpose of this month is to provide a method for dyeing polypropylene fibers using a long-chain calcined azo dye, which can achieve easy dyeing, uniform dyeing effect, and excellent color fastness to washing. purpose. In order to achieve the above-mentioned purpose, the main technical means of the present invention is to use long acrylic fibers for dyeing. The structure of the dye used is as shown in the following general formula:

10 20053530010 200535300

RR

(F)(F)

RR

其中，R 可以為-C4H9，-C8Hi7或，-Ci2H25’ -C 1 6 11 3 1 11 200535300 本舍月利用長鏈院基之偶氮染料中長鏈狀分子結構與 纖維線性高分子相似、且染料分子較大且其平面性良好， 可使染料分子與纖維分子鏈間產生強大的凡得瓦爾力，增 加染料與聚丙烯分子間的結合力，以提高染色堅牢度。 【實施方式】 本發明之使用長鏈烷基偶氮染料對未改質聚 、π碑纖維 染色的方法，其中該長鏈烷基偶氮型染料之通式 · ★ 钓·萘酚、 燒苯基偶氮（naphthol-alkylphenyl azos)化合物及 久其衍生 物，其中包含有下列結構式之化合物： (A)Among them, R can be -C4H9, -C8Hi7 or -Ci2H25 '-C 1 6 11 3 1 11 200535300 The long-chain molecular structure of the azo dye used in the long-chain courtyard is similar to the fiber linear polymer, and The dye molecules are large and have good planarity, which can generate strong van der Waals force between the dye molecule and the fiber molecular chain, increase the binding force between the dye and polypropylene molecules, and improve the fastness of dyeing. [Embodiment] The method for dyeing an unmodified poly, π-steel fiber using a long-chain alkyl azo dye according to the present invention, wherein the general formula of the long-chain alkyl azo dye · · fishing · naphthol, burning benzene Naphthol-alkylphenyl azos compounds and their derivatives, including compounds of the following structural formula: (A)

OHOH

(C) 12 200535300(C) 12 200535300

RR

ii

EE

OHOH

COOH (F)COOH (F)

R t 在上述A-F的所有結構式中，R可以為-C4H9，-C8H17 ’ -C12H25 ’ 或-C16H31。。 此外，本發明之另一項特點在於使用超臨界二氧化碳 流體染色。使用超臨界二氧化碳流體染色的原理在於：由 於二氧化碳為非極性，沸點很低，臨界溫度是31 · 1 °C，加 13 200535300 壓容易液化。由於分子是非極性的，對低極性和非極性物 質有輕南的溶解能力。當二氧化碳超過臨界溫度（3 1 1 t ) 和臨界壓力（7. 39Mpa)，則轉變為超臨界流體狀態，透過 控制壓力，它可以達到和液體一樣大小的密度，即在 0· 3〜0· 9g/cm3左右。它的粘度極低，分子間作用力小，對 物體有很強的滲透作用’對物質的溶解能力比氣體大得 多’其擴散係數是氣體的百分之一左右，但比液體大數十 倍，染料在其中的擴散阻力小，有利於染料滲透和發生移 染’進而大大提高了均染和透染程度，因此，超臨界二氧 化碳流體可以溶解非水溶性染料，擔負起染色作用之媒 介，而且染色完成後只需要降壓就可使二氧化碳氣化分 離，結束染色過程。 本發明中以自行合成之長鏈烷基偶氮染料，在超臨界 二氧化碳流體的條件下染細丹尼聚丙烯纖維，染料之烷基 數目可以為4個碳數烷基至16個碳數烷基；偶合劑部分則 以系環為主，再依所帶有之基團不同而分類，在低溫下以 鹽酸法合成此長鏈烷基偶氮染料。染料合成後，經純化過 魟’以超臨界染色裝置在適當的壓力及溫度對細丹尼聚丙 烯纖維進行染色。_色後的聚丙稀纖維分別作染色堅牢度 試驗’評估以超臨界染色及使用長鏈烧基偶氡染料對細丹 14 200535300 烯木色性之影響，並與商業用分散性染料於超臨界 二氧化碳機制染色及以溶解度參數與聚丙烯纖維相近的甲 ^ K 丙烯·約為 8.0 cal1/2/cm3/2 ，甲苯：8·9ΐ )作為溶劑進行水/溶劑染色做交叉對照。 為了進步瞭解本發明之操作與原理，以具體操作之 實施例說明如下： &lt;合成染料部份&gt; 本發明中所列之具長鏈烷基之偶氮染料製法與過程大 才同在此以對-十二烧基苯胺（户-dodecy 1 ani 1 ine)與 #工基 4 奈甲酸（2一hydroxy —4_naphth〇ic acid)之合成 程序為例。 首先進行重氮化反應，第一步加入 mole)的對-十二烷基笨胺與4〇ml的蒸餾水於5〇〇匕匕燒 杯中，再加入20ral ( 35w/w%)鹽酸利用磁石充分攪拌並加 熱，得到充分混合之粉紅色懸浮溶液，再藉由加入少量冰 塊，和外圍冰浴將溫度冷卻至〜5。〇，徐徐加入38克 (0·055 mole)亞硝酸鈉水溶液1〇ml以形成重氮鹽，溫 度以使溶液保持在5°C以下為宜，並持續攪拌，並以下列 幾項檢測掌握重氮化的進行。 (a)檢測莩握重氣化的進行：將2 -經基—4 -萘甲酸（2 - 15 200535300 hydroxy-4-naphthoic acid)溶液與反應液滴在濾紙上， 如果重疊部分有呈現紅色的顏色產生，則表示有重氮鹽的 存在。 (b) 檢測重氮化是否完全··可用4 -N，N-二乙胺基甲醛 (4 —N，N — Diethylaminobenzaldehyde)與反應液滴在 濾紙上，若重疊部份產生黃色則表示反應未完全，應繼續 反應或追加亞确酸鈉，若無黃色產生則表示重氮化反應完 成。 (c) 檢測亞硝酸是否殘留：以碘化鉀（π )試紙檢驗 反應液中是否殘留亞硝酸，若有殘留則可加入氨基磺酸或 尿素予以消除。如此即可得到暗黃色之澄清重氮液，若重 氮液中含有固體雜質，須予以濾除，並酌量在接下來的偶 合反應步驟中減少偶合劑之份量，以減少反應十的不純物 產生。 接著進行偶合反應，將9· 40g ( 〇· 05 mole )的2-經 基-4-萘曱酸（2-hydroxy-4-naphthoic acid)加入 8 〜10 克氫氧化鈉和150ml蒸餾水的混合液中，攪拌使之完全溶 解，再將此混合液冷卻至VC—5t，持溫攪拌，並於一小 守内將上述之重氮液緩緩滴入此偶合混合液中，以碎冰塊 包覆於燒杯外，務必使溫度維持在51以下，滴畢後，溫 16 200535300 度仍須保持在5 °C以下 P Η值維持在1 q — 1 2，充分授掉2 小日$後’再將pH值調整至5 — 7，甘+以、网、会 芏b 7亚予以過濾、水洗、烘乾 後可仔到2G. 94 g (產率約為81%)之深紅色染料。 染料製作過程中，可能因為反應條件控制不當或中間 體未反應完全’而有不純物或副產物的“，如此將影響 日後有機光譜賴的結果，所以在染料合成後需再進行純 化。 純化步驟如下:將染# 2克加入適量乙醇當中，加熱 使其溶解，並輔以冷凝裝置以避免乙醇揮發。溶解後即靜 使其再度結晶。由於不純物僅佔少量，且結構相近者 、、口在起，因此純的染料分子會先形成結晶而析出。 把結晶部份取出，將其置入萃取裝置中，將染料結晶置入 圓筒型濾紙中，以2〇0ml試藥級丙酮不停的進行染料循環 个取，直到沒有染料被萃取出來為止。含有染料的丙酮會 不斷藉由虹吸的方式進入萃取器下方的燒瓶中，再將萃取 液置入通風櫥中，於室溫下乾燥數天，以得到較純的染 料。最後利用薄層色層分析法（TLC )測試其純度，其展 開劑配方為甲苯：乙酸乙酯：醋酸=8 : 2 : 1。此步驟持 續進行，直到取得純染料為止。 〈染色操作實施例〉 17 200535300 染色流程操作請配合第一 m 、 〆 口弟圖苓考說明如下，將高壓二 氧化私先經過針閥及過、、卢卩 過濾閥，再經過冷卻系統（〇 t：以 下）’以超臨界不錄鋼暂、者4 小为綱幫浦加堡，加壓的流體流經裝有染 料的染料瓶溶解部分染料， ^ 木枓亚，入染色槽（D)對細丹尼聚 丙稀針織物進行染色。毕声 木色t外部裝有加熱線與絕緣裝 置’藉此加熱器及超臨界不鉉钿蜇 ^小綉鋼幫浦控制溫度及壓力，以 溫度探針⑺及壓力計⑽貞測染色系統中的溫度及壓力。 實驗先在室溫下注入二氧化碳’同時升溫升麗，升昼速率 略低於升溫速率’待系統整體到達染色條件(染色壓力 4000 psi，染色溫度 11〇 。） )開啟循玉衣控制器，循環器 是藉由磁力控制活塞的運動，活塞上下運動，擠壓二氧:: 碳流體，讓超臨界的二氧化碳流體流動，因為在染色時， 流體的流動可以使染色織物達到均染效果，織物在染色槽 中玉無張力狀態。循環時持溫持壓，等待染色時間、纟士束 以分段式洩壓，五段逐步釋壓（每次約釋R t In all the structural formulas of A-F above, R may be -C4H9, -C8H17 '-C12H25' or -C16H31. . In addition, another feature of the present invention is the use of supercritical carbon dioxide fluid dyeing. The principle of using supercritical carbon dioxide fluid dyeing is that because carbon dioxide is non-polar and has a low boiling point, the critical temperature is 31 · 1 ° C. It is easy to liquefy when added to 13 200535300. Since the molecule is non-polar, it has the ability to dissolve lightly polar and non-polar substances. When the carbon dioxide exceeds the critical temperature (3 1 1 t) and critical pressure (7. 39Mpa), it transitions to a supercritical fluid state. By controlling the pressure, it can reach a density the same as that of a liquid, that is, 0 · 3 ~ 0 · About 9g / cm3. Its viscosity is very low, the intermolecular force is small, and it has a strong penetrating effect on the object. 'The ability to dissolve matter is much greater than that of gas.' Its diffusion coefficient is about one percent of that of gas, but it is dozens of times greater than that of liquid. Times, the diffusion resistance of the dye in it is small, which is conducive to the penetration and migration of the dye, and thus greatly improves the level of dyeing and transfection. Therefore, the supercritical carbon dioxide fluid can dissolve the water-insoluble dye and act as a medium for dyeing. In addition, after the dyeing is completed, the carbon dioxide can be gasified and separated only by reducing the pressure, thereby ending the dyeing process. In the present invention, a self-synthesized long-chain alkyl azo dye is used to dye fine denier polypropylene fibers under the condition of supercritical carbon dioxide fluid. The number of alkyl groups of the dye can be 4 to 16 carbons. The coupling agent part is mainly based on the ring system, and then classified according to the different groups. The long-chain alkyl azo dye is synthesized by the hydrochloric acid method at low temperature. After the dyes are synthesized, the fine denier polypropylene fibers are dyed using a supercritical dyeing device at a suitable pressure and temperature using a supercritical dyeing device. _Colored polypropylene fibers are tested for dyeing fastness respectively. 'Evaluate the effects of supercritical dyeing and the use of long-chain sintered acetocyanine dyes on the color of fine Dan 14 200535300, and compare with commercial disperse dyes at supercritical. Carbon dioxide mechanism dyeing and cross-control with water / solvent dyeing using methyl propylene with a solubility parameter similar to that of polypropylene fiber, approximately 8.0 cal1 / 2 / cm3 / 2, toluene: 8.9ΐ) as solvent. In order to improve the understanding of the operation and principle of the present invention, the specific operation examples are described as follows: &lt; Synthetic dye part &gt; The azo dyes with long chain alkyl listed in the present invention are produced by the same process and process. Take the synthesis procedure of p-dodecyl aniline (H-dodecy 1 ani 1 ine) and # 工 基 4 奈 酸 (2-hydroxy-4-naphthanolic acid) as an example. First carry out the diazotization reaction. The first step is to add mole) of p-dodecylbenzylamine and 40 ml of distilled water in a 500 dagger beaker, and then add 20ral (35w / w%) hydrochloric acid. Stir and heat to obtain a fully mixed pink suspension solution, and then cool the temperature to ~ 5 by adding a small amount of ice cubes and an external ice bath. 〇, slowly add 38 grams (0.055 mole) of sodium nitrite aqueous solution 10ml to form a diazonium salt, the temperature is preferably to keep the solution below 5 ° C, and continue to stir, and the following items to check the weight The progress of nitriding. (a) Detecting the progress of gripping heavy gasification: Drop the 2-mercapto-4-naphthoic acid (2-15 200535300 hydroxy-4-naphthoic acid) solution and the reaction liquid on the filter paper. If the overlapping part is red The appearance of color indicates the presence of a diazonium salt. (b) Check whether the diazotization is complete. 4 -N, N-Diethylaminobenzaldehyde and the reaction liquid can be dropped on the filter paper. If the overlapping part produces yellow, it means the reaction is not Complete, the reaction should be continued or sodium sulfite added. If no yellow is produced, the diazotization reaction is complete. (c) Test for nitrite residue: use potassium iodide (π) test paper to check whether nitrite remains in the reaction solution. If there is any residue, add sulfamic acid or urea to eliminate it. In this way, a dark yellow clear diazonium liquid can be obtained. If the diazonium liquid contains solid impurities, it must be filtered off, and the amount of coupling agent should be reduced in the subsequent coupling reaction step to reduce the generation of impurities in reaction ten. Then, a coupling reaction is performed, and 9.40 g (0.05 mole) of 2-hydroxy-4-naphthoic acid is added to a mixed solution of 8 to 10 g of sodium hydroxide and 150 ml of distilled water. Medium, stir to completely dissolve, and then cool the mixture to VC-5t, stir at a constant temperature, and slowly drop the above diazo solution into the coupling mixture in a small container, and cover it with crushed ice Cover the beaker, make sure to keep the temperature below 51. After the dripping, the temperature 16 200535300 degrees must still be kept below 5 ° C. The P value is maintained at 1 q — 1 2 and fully paid for 2 small days. Adjust the pH value to 5-7. After filtering, washing, drying, and b7 sub-sweetening with Gan + Yi, net, and Huizhou 7 to 2G. 94 g (yield about 81%) of deep red dye. In the process of dye production, there may be impurities or by-products because of improper control of reaction conditions or incomplete reaction of intermediates. This will affect the results of organic spectrum in the future. Therefore, purification is required after dye synthesis. The purification steps are as follows : Add 2 grams of dye # 2 to an appropriate amount of ethanol, heat to dissolve it, and supplement it with a condensation device to prevent the ethanol from volatilizing. After dissolution, it will be allowed to recrystallize. Because the impurities are only a small amount, and the structure is similar, the mouth is rising. Therefore, the pure dye molecules will first form crystals and precipitate out. Take out the crystalline part, put it into the extraction device, put the dye crystals into the cylindrical filter paper, and continuously carry out 200ml reagent grade acetone. The dyes are circulated until no dyes are extracted. Acetone containing dyes will continue to be siphoned into the flask below the extractor, and the extract will be placed in a fume hood and dried at room temperature for several days. In order to obtain a relatively pure dye, the purity was tested by thin-layer colorimetric analysis (TLC), and the formula of the developer was toluene: ethyl acetate: acetic acid = 8: 2: 1. This step is continued until the pure dye is obtained. <Dyeing Operation Example> 17 200535300 Dyeing process operation Please cooperate with the first m and Tongkoudi Turing test as described below. The needle valve and the filter valve pass through the cooling system (0t: below). The supercritical non-recording steel temporary, or 4th element is Pujiabao, the pressurized fluid flows through the dyed The dye bottle dissolves part of the dye, ^ Muya, into the dyeing tank (D) to dye fine denim polypropylene knitted fabric. Bi Shengmu color t is equipped with a heating wire and insulation device.铉 钿 蜇 ^ Xiaoxiu Steel pump controls the temperature and pressure, using a temperature probe and a pressure gauge to measure the temperature and pressure in the dyeing system. In the experiment, carbon dioxide was injected at room temperature at the same time, and the temperature was increased and the rate of daylight increased. Slightly lower than the heating rate 'until the entire system reaches the dyeing conditions (dyeing pressure 4000 psi, dyeing temperature 11).) Turn on the Xunyuyi controller. The circulator controls the movement of the piston by magnetic force, the piston moves up and down, squeezes two :: Carbon fluid, allowing supercritical carbon dioxide fluid to flow, because during the dyeing process, the fluid flow can make the dyed fabric achieve a uniform dyeing effect, and the fabric has no tension state in the dyeing tank. Keep the temperature and pressure during the cycle and wait for the dyeing time , Shi Shishu release pressure in stages, gradually release pressure in five stages (each time release

Ps1 )，然 後完成染色。 〈檢驗與測試&gt; 73和 烯針織 利用DYEGAIN電腦測色系統，依astm Ε-313 ASTM D-1 925-70標準，將超臨界染色之細丹尼聚兩 物測試其表面反射率，經電腦換算求得其表觀濃户 200535300 U/s)。耐水洗染色 水洗染色堅牢戶於，人-係根據AATCC 6卜1989 &amp;牛度檢驗法為 j 為：加4‘準進行檢測，該檢驗法的操作 υ· 2 %之清省令丨 t ’置入10顆鋼珠，將色紗於50 本午下進行水洗4 5公4立^ ^ 洗30八Λ 刀4里，隨後再於30 t：之清水中清 分鐘後以烘心乾’再和未水洗的色布進行色相比 卜卜 龟驷測色系統測其表觀濃度（κ/s)值，再經電腦運 算後、隹/一Ps1), and then staining was completed. <Inspection and Test> 73 Heene Knitting uses the DYEGAIN computer color measurement system to test the surface reflectance of super denatured fine denim polymer in accordance with the standard astm Ε-313 ASTM D-1 925-70. Conversion to obtain the apparent thick household 200535300 U / s). Wash-resistant dyeing Wash-washing and dyeing strong households, according to AATCC 6 1989 &amp; cattle test method is j: add 4 'standard for testing, the operation of this test method · 2% of the provincial order 丨 t' set Into 10 steel balls, wash the colored yarn at 50 this afternoon 4 5 meters 4 ^ ^ wash 30 eight Λ knife 4 inside, and then clean in 30 t: clear water for 30 minutes, and then dry to dry. The washed color cloth is compared with the color measurement system of the turtle colorimeter to measure its apparent concentration (κ / s) value, and then calculated by the computer.

暹行變褪色堅牢度之級數判定。評定等級中以i 最差， 、馬I ’而5級為最佳，其結果如下表一。 其中’選定測試的三種染料分別為： 染料I之化學結構（η = 8 )Determining the fastness of fading in Siam. In the rating, i is the worst, and horse I ′ is the best. The results are shown in Table 1 below. Among them, the three dyes selected for testing are: Chemical structure of dye I (η = 8)

OHOH

C H 3(C Η])?·—. ·Ν —Ν 染料11之化學結構（η = 12 )C H 3 (C Η])? · —. · Ν—Ν chemical structure of dye 11 (η = 12)

染料III之化學結構（η = 12)Chemical structure of dye III (η = 12)

COOH CH3(CH2)n 200535300 表一：長鏈烷基偶氮染料在超臨界條件下對細丹尼聚丙烯纖維染色-耐水洗染色堅牢度 染料種 耐水洗堅 染料I 染料π 染料III 變褪色灰色標 3〜4 3-4 3 染污灰色標 棉 5 5 5 聚酯 5 5 5 由表一的耐水洗染色堅牢度試驗結果可知，經過水洗 L牛度’則试後後’耐水洗變视色灰色標染料I與染料11為 3〜4級，因染料π I具有羧基，增加染料的親水性，因此水 洗後變褪色灰色標約較另兩支染料低半級。但與導染劑/ 水染色之耐水洗褪色灰色標相比，以自行合成之長鏈烷基 分散性染料在超臨界流體中染色有較好的效果。而在染污 方面，白胚布並無受到染料移_，棉胚布及聚醋白胚布水 洗巧染灰色標皆為5級’這是因為長_基偶氮染料的分 子較大，在非適當的條件下异 f旰卜疋無法因外力而附著或進入纖 、准内部。結果顯示出倍用斤 用長鏈烷基偶氮染料具有良好的上 色率’且耐水洗染色堅牢度可達3-4級以上。 由上述的說明及實駱）圼Α ^ 驗侍知，本發明中所製備的長鏈烷 基偶氮型染料，確實具有 艮好的木色效果，其主要原因在 於染料結構因其具分子内氫 卞囬往艮好，再加上烷基 長鏈與聚烴基纖維高分 仃’可使染料分子與聚丙烯 20 200535300 纖維分子鏈間形成較大的 寸瓦爾力，增加染料與聚丙烯 分子間的結合力，同時利&amp; T〜用具有向滲透性的傳輪媒介之二 氧化碳超臨界流體進行染色，使大染料粒子得以進… 緻密性結晶之聚丙浠纖維㈣，讓染料的與聚丙烯分：： 結合更為均勻完整。 綜上所述，本發明由於藉由 使用長鏈烧基偶氮染料進 行對未改質聚丙婦纖維染备COOH CH3 (CH2) n 200535300 Table 1: Long-chain alkyl azo dyes dyeing fine denier polypropylene fibers under supercritical conditions-fastness to washing dyeing fastness dye type washing fast dye I dye π dye III becomes faded gray Standard 3 ~ 4 3-4 3 stained gray standard cotton 5 5 5 polyester 5 5 5 According to the fastness test results of washing and dyeing in Table 1, it can be seen that after washing, the degree of hardness will be changed after washing, Gray scale dye I and dye 11 are grades 3 to 4. Because dye π I has a carboxyl group, which increases the hydrophilicity of the dye, the faded gray scale is about half a grade lower than the other two dyes after washing. However, compared with the dye-resistant agent / water-stained fade-resistant gray scale, self-synthesized long-chain alkyl disperse dyes have better results in dyeing in supercritical fluids. In terms of staining, the white germs were not affected by the dye migration. The cotton germs and polyacetic white germs were washed and dyed with gray labels. The grade 5 was' This is because the molecules of the long-based azo dyes are large. Under improper conditions, foreigners cannot attach or enter the fiber and quasi-interior due to external forces. The results show that the long-chain alkyl azo dyes for double use have good coloring rate 'and the fastness to washing and dyeing can reach grades 3-4 and above. From the above description and practical knowledge), the long-chain alkyl azo dye prepared in the present invention does have a good wood-color effect, the main reason is that the dye structure Hydrogen hydration is good, plus the long alkyl chain and high hydrocarbon-based fiber 'can make the dye molecules and polypropylene 20 200535300 fiber molecular chain to form a relatively large wall force, increasing the dye and polypropylene molecules At the same time, Lee &amp; T ~ dyed with carbon dioxide supercritical fluid with osmotic transmission medium, so that large dye particles can enter ... Dense crystalline polypropylene fiber fiber, let the dye be separated from polypropylene ::: The combination is more uniform and complete. In summary, the present invention is based on the preparation of unmodified polypropylene fiber by using a long-chain alkyl azo dye.

那哉、、隹木色，確貫可以讓染料與聚丙烯分 子之間有效且強力έ士人，里一士 &amp; ^ 娌刀、、、〇 口，另方面，使用二氧化碳超臨界 流體作為傳輸媒介，讓染料的分散與滲透更為均勻，因 此，能有效地增加染料後的上色率與耐水洗染色堅牢度， 所以本發明具有相當的進步性、實用性及產業利用性，符 合發明專利申請要件，因此具文提出發明專利申請。 【圖式簡單說明】That 哉 ,, 隹 wood color, can surely make the dye and polypropylene molecules effective and powerful. 士 士 娌, 娌, 〇 口, on the other hand, use carbon dioxide supercritical fluid as transmission The medium makes the dispersion and penetration of the dye more uniform. Therefore, it can effectively increase the dyeing rate and fastness to washing and dyeing after dyeing. Therefore, the invention has considerable progress, practicality and industrial applicability, and is in line with the invention patent. The application requirements, so the document filed an invention patent application. [Schematic description]

(一）圖式部分 第一圖：係為超臨界流體染色設備配置圖。 (二）元件代表符號 (D)染色槽 （T)溫度探針 (P )壓力計 21(I) Schematic part The first figure: the configuration diagram of the supercritical fluid dyeing equipment. (2) Symbols of components (D) Dyeing tank (T) Temperature probe (P) Pressure gauge 21

Claims (1)

200535300 拾、申請專利範圍： 1 · 一種使用長鏈烧基偶氮 染色的方法，其主要在於使用 染料對未改質聚丙烯纖維 具有萘酚-烷笨基偶氮 (naphthol-alkylphenyl azos)化合物及其衍生物， 在一氧化 碳超臨界流體作為傳輸媒介的操作 ^ 、 ，對♦丙烯纖維進行 染色 2·如申請專利範圍第1項之方法 氮之結構式為： 其中萘酚-烷苯基偶 OH200535300 The scope of patent application: 1 · A method for dyeing with long-chain alkyl azo, which mainly consists of using naphthol-alkylphenyl azos compounds on unmodified polypropylene fibers with dyes and Its derivative is the operation of carbon monoxide supercritical fluid as the transmission medium, dyeing of propylene fibers. 2 · As the method of the scope of patent application No. 1, the structural formula of nitrogen is: where naphthol-alkylphenyl OH 其中，R 為—C4H9，—hi 3·如申請專利範圍第1 氮之結構式為： ’〜C12H25，或—c16H31。 項之方法，其中萘酚-烷苯基偶Among them, R is —C4H9, —hi 3 · If the nitrogen formula of the first patent application is: ′ ~ C12H25, or —c16H31. Item method, wherein naphthol-alkylphenyl couple R ，〜C!2H25，或—Ci6h3i。 項之* 、万法，其中萘酚-烷苯基偶 其中，R 為-C4H9，-c8H17 4·如申請專利範圍第i 氮衍生物之結構式為·· 22 200535300R, ~ C! 2H25, or -Ci6h3i. Item *, Wanfa, where naphthol-alkylphenyl couple, where R is -C4H9, -c8H17 4 · If the scope of the patent application, the structural formula of the nitrogen derivative is ... 22 200535300 其中 ’ R 為—CgHg ’ -CgHi? ’ _C12H25 ’ 或—匸16丑31。 5.如申請專利範圍第1項之方法，其中萘酚-烷苯基 偶氮之衍生物結構式為：Where ‘R is —CgHg’ -CgHi? ’_C12H25’ or — 匸 16ug31. 5. The method according to item 1 of the patent application scope, wherein the structural formula of the naphthol-alkylphenylazo derivative is: 其中 ’ R 為-CgHg ’ -CgHn ’ _C12H25 ’ 或—〇16只31。 6.如申請專利範圍第1項之方法，其中萘酚-烷苯基偶 氮衍生物之結構式為：Among them, 'R is -CgHg' -CgHn'_C12H25 'or -01616. 6. The method according to item 1 of the scope of patent application, wherein the structural formula of the naphthol-alkylphenylazo derivative is: 其中 ’ R為-CqHg’ -CgHu ’ _C12H25’ 或—C16H31。 7.如申請專利範圍第1項之方法，其中萘酚-烷苯基偶 氮衍生物之結構式為： 23 200535300Where 'R is -CqHg' -CgHu'_C12H25 'or -C16H31. 7. The method according to item 1 of the patent application scope, wherein the structural formula of the naphthol-alkylphenylazo derivative is: 23 200535300 其中，R為-C4H9，—c8h17，—c12h25，或—c16h31。 8。如申請專利範圍第1項之方法，其中二氧化碳超 臨界流體的最適操作條件為：壓力4000 psi ;溫度110 。。。 拾壹、圖式： 如次頁Among them, R is -C4H9, -c8h17, -c12h25, or -c16h31. 8. For example, the method of claim 1 in the patent scope, wherein the optimal operating conditions of the carbon dioxide supercritical fluid are: pressure 4000 psi; temperature 110. . . Pick up, schema: as the next page 24twenty four