201128007 六、發明說明： 【發明所屬之技術領域】 本發明之主題是供反射性衣物（例如在標準E N 4 7 1中 所述者）應用之具有螢光性質之再生纖維素纖維，其在製 造紗及織物的用途以及製造這些纖維之方法。 【先前技術】 EN 471專特地處理個人防護性裝置的警告效果，特別 是處理反射性衣物。原則上，防護性衣物包含螢光底材料 及逆反射性材料。爲本發明之目的，依照E N 4 7 1中之定義 ，發射較長之波長之輻射而非吸收該輻射的材料被稱爲螢 光材料；在其另外的內文中，高黏膠材料（High-Vis-M at eri al ) —詞用來稱呼此材料。本發明係關於該螢光材 料而非逆反射性材料。 迄今高黏膠織物主要是在合成纖維（特別是聚酯，然 而其顯露出與穿著舒適性及安全性相關之缺點）之基礎上 被製造。與此類似之紡織品的缺點特別是在於其令人討厭 的皮膚觸感，及在長時間穿戴後，因爲水分調節用材料的 性質不足使異味發生；以及在於典型與合成纖維有關之靜 電增加的危險。 複雜之紡織品結構提供一替代方式，該結構外側包含 高黏膠成分且其內側主要包含纖維素纖維以改良穿著舒適 性，例如在W02006/017709中所描述的。今日，最重要的 是，依本發明之黏膠方法及萊塞爾（Lyocell)方法之纖糸隹 201128007 已知是再生纖維素纖維。在世上這些係在紡織品及非紡織 物部門中製造成具有0.8至16 dtex的個別纖維纖度以供標 準應用。 再生纖維素纖維確實可以使用一般之浴染色方法以螢 光染料染色。然而，以此方式被染色之纖維不滿足光牢度 的要求（ISO 105-B02方法2>5)。在氙輻射之後，彼明顯 地褪色且其明暗度明顯改變。再者，色彩深淺度大幅地減 低，此例如可以用色品座標的移動所確認。 數十年來，已知：膠黏纖維可以藉由合併染料顏料以 永久的方式被染色。對應之纖維在市面上可獲得。然而直 到今日，不能獲得符合EN 47 1要求之經紡絲染色的再生纖 維素纖維。 任務之指派： 與此先前技藝相比，任務是要獲得一種纖維，其一方 面滿足防護性及反射性衣物之要求（例如在EN 47 1中所描 述的）且另一方面滿足此衣物的穿著舒適性及安全方面的 要求，並有合理經濟的費用。因這理由，應可能從類似此 之纖維，在不添加任何其他型式之纖維的狀況下製造該防 護性及反射性纖維。在此方面，特別重要的是：由這些纖 維製造之紡織品通過以下之依照EN 471對底材料之要求： •亮度係數（依照CIE公告15.2之標準値）及色品座 標 •在氙輻射後之色彩：依照iso 105-B02方法3進行樣 201128007 品之曝照 •乾及濕的摩擦牢度（iso 105-A02) 此外’該纖維之光牢度依照IS Ο 1 0 5 - B 0 2方法2測定。 另外’該任務是要使適合之製造方法可用於這些纖維 【發明內容】 令人驚訝地，可使用再生纖維素纖維解決此任務，該 纖維含有經合倂之染料顏料及藉由過度染色施加之螢光染 料。依本發明之這些纖維，除了因該基本纖維素結構而有 的改良的穿著舒適性及增加的安全性之外，還具有依照 ISO 105-B02方法2所測得之大於5的光牢度。這是不可能 利用迄今已知之纖維素纖維實現的。 該纖維在摩擦牢度、對汗水之牢度、對清洗之牢度、 乾洗牢度、次氯酸鹽漂白劑之牢度及熨燙牢度方面也滿足 在EN 471中要求之其他値。 經紡絲染色的再生纖維素纖維可以使用黏膠方法、改 良之黏膠方法（例如莫代爾（Modal )方法、使用硫酸鋁 之無鋅的黏膠方法等）以及利用有機溶劑（諸如熔化之含 水的胺氧化物類或也稱爲離子性液體）進行之溶劑方法。 該纖維可以對應地指明爲黏膠、莫代爾及/或萊塞爾。 再生纖維素纖維可以含有其他添加劑。在本發明之一 較佳具體實例中，再生纖維素纖維另外配備阻燃劑。 阻燃性纖維之一較佳具體實例係藉由合併顏料形狀之 201128007 阻燃劑製造。此外，可以考慮其他型式（ 合物）作爲顏料形狀之阻燃劑，對於黏膠 適且習知之2,2’-氧基雙[5,5-二甲基-1，3, dioxaphosphorinan) ]2,2’ 二硫化物，其 Sandoflam®之商業名取得。 在本發明之其他較佳具體實例中，再 配備抗菌劑。在此方面，可以使用專家已 可以利用適於纖維素材料之染料（例 直接染料、染缸染料等）進行隨後之高黏 可以在經紡絲染色之纖維束中、在含 之纖維的紗中或在含有該經紡絲染色之纖 過度染色，亦即浴染色。在此方面，基本 家已知之連續或不連續染色方法。 藉由合適地選擇顏料以供紡絲染色及 浴染色，可以獲得彩色明暗度，對此迄今 式。 本發明之主題也是依本發明之纖維在 爲要特徵化適合個別應用範圍之性質，依 了含有依本發明之纖維以外，也可以含有 ，例如（阻燃性）聚酯、Modacryl、對位 、聚醯胺醯亞胺（Kermel® )、（阻燃性 咪唑（PBI)、聚醯亞胺（P84®)、聚醯 聚醯胺、阻燃性丙烯酸系纖維、三聚氰胺 (PPS )、聚四氟乙烯（PTFE)、玻璃纖 特別是有機磷化 而言是例如極合 2-二氧雜磷烷（ :可以Exolit®或 生纖維素纖維也 知的物質。 如反應性染料、 膠浴染色。 有該經紡絲染色 維的織物中進行 上，可以使用專 高黏膠染料以供 尙無個別解決方 製造紗的用途。 本發明之紗，除 其他來源之纖維 :-及間位-芳醯胺 )羊毛、聚苯並 胺、（阻燃性） 纖維、聚苯硫醚 維、棉、絲、碳 201128007 纖維、經氧化之熱安定化的聚丙烯腈纖維（PAN OX® )及 導電性纖維，以及這些纖維之摻合物。在本發明之一具體 實例中，摻合用之配合物同樣地進行高黏膠後處理。 同樣地’依本發明之纖維在製造織物的用途是本發明 之主題。除了依本發明之纖維之外，此織物也可以含有其 他纖維’例如（阻燃性）聚酯、Modacryl、對位-及間位-芳醯胺、聚醯胺醯亞胺（Kermel® )、（阻燃性）羊毛、 聚苯並咪唑（PBI )、聚醯亞胺（P84® )、聚醯胺、（阻 燃性）聚醯胺、阻燃性丙烯酸系纖維、三聚氰胺纖維、聚 苯硫醚（PPS )、聚四氟乙烯（PTFE )、玻璃纖維、棉、 絲、碳纖維、經氧化之熱安定化的聚丙烯腈纖維（ PANOX®)及導電性纖維，以及這些纖維之摻合物。在本 發明之一較佳具體實例中，其他纖維也可有高黏膠後處理 的特徵。 織物較佳是紡織織物、翹曲織物或針織織物，但基本 上也可以是非紡織織物。在紡織或針織織物的事例中，藉 由以下方式可能有依本發明之纖維與其他纖維之摻合物： 藉由在紗製造前摻合（所謂之緊密摻合物），或藉由在編 織、捲曲或針織時在每一情況中聯合使用不同型式之纖維 的純紗。 同樣地，本發明之主題也是依本發明之纖維在製造衣 物之反射性物件或其他種類之反射性物件的用途’藉此一 般地，上述之紗及/或平面的紡織品結構顯現在紡織品生 產鏈的中間步驟中。爲本發明之目的，其他種類之反射性 -9 - 201128007 物件應被了解爲例如飄帶、旗幟、警告條及類似者，其顯 出特別高之可見度及/或吸引極多注意。依本發明之用途 因此不只是純粹的警告效果。若使用如上述之非紡織織物 作爲織物，例如在飄帶、旗幟、警告條及類似者之用途， 則當然該中間之紗是不適用的。衣物物件或此類之其他反 射性物件的不同具體實例對專業人士是習知的且因此不需 任何其他的描述。 同樣地，上述依本發明之螢光之再生纖維素纖維的製 造方法也是本發明的主題，其中染料顏料被倂入纖維中且 這些纖維在稍後之處理步驟中利用螢光染料過度染色。 一般藉由添加染料顏料至紡絲溶液進行此合倂。此類 之合倂方法對黏膠、莫代爾及溶劑紡絲方法二者的專家而 言基本上是已知的。然而，經紡絲染色之纖維素纖維一般 不在另一步驟中用另外染料過度染色，因爲該紡絲染色方 法一般已知是極有效之方法，利用此方法可以達成高牢度 値、以及摩擦及光牢度、對清洗及汗水之牢度。然而，本 發明（其爲包含在稍後階段之過度染色的組合方法）滿足 用於反射性衣物之纖維素纖維的特殊要求。 過度染色（亦即浴染色）是在含有經紡絲染色之纖維 的纖維束中或在含有經紡絲染色之纖維的紗或紡織品結構 上進行。在這方面，可以使用專家通常已知之連續或不連 續染色方法。 本發明現在將藉由實例說明。這些據了解是本發明之 可能的具體實例。本發明決不限於這些實例之範圍。 -10- 201128007 【實施方式】 實例1 : 經紡絲染色之阻燃性黏膠纖維含有，相關於纖維_ , 1.25重量％之黃顏料3 (例如Aquarine Yellow 10G)及22重; 量％之2,2’-氧基雙[5,5-二甲基-1，3,2-二氧雜磷烷]2,2，二硫 化物（Exolit 5060，Messrs. Clariant)。然後依照以下方· 法，利用 Remazol Leuchtgelb FL(Messrs. DyStar)依照 以下方法將此纖維過度染色： 該束置於染料浴中，該染料浴含有2%之Remaz()1201128007 VI. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD The subject of the present invention is a regenerated cellulose fiber having fluorescent properties for use in reflective clothing (for example as described in the standard EN 47 1 1), which is manufactured The use of yarns and fabrics and methods of making these fibers. [Prior Art] EN 471 specifically handles the warning effects of personal protective devices, especially reflective clothing. In principle, protective clothing consists of a fluorescent base material and a retroreflective material. For the purposes of the present invention, a material that emits longer wavelength radiation rather than absorbing the radiation is referred to as a fluorescent material as defined in EN 47 1; in its other context, a high viscosity material (High- Vis-M at eri al ) — The word is used to refer to this material. The present invention is directed to the fluorescent material rather than the retroreflective material. High-adhesive fabrics have hitherto been manufactured mainly on the basis of synthetic fibers (especially polyesters which, however, exhibit disadvantages associated with wearing comfort and safety). Disadvantages of textiles similar thereto are, in particular, their annoying skin feel, and after a long period of wear, the odor is caused by insufficient properties of the moisture-regulating material; and the danger of increased static electricity typically associated with synthetic fibers. . A complex textile structure provides an alternative, the outer side of the structure comprising a high viscose component and the inner side comprising predominantly cellulosic fibers to improve wearing comfort, such as described in WO2006/017709. Today, and most importantly, the viscose method according to the present invention and the fiber of the Lyocell method 201128007 are known as regenerated cellulose fibers. These lines are manufactured in the textile and non-textile sectors to have individual fiber deniers of 0.8 to 16 dtex for standard applications. Regenerated cellulose fibers can indeed be dyed with fluorescent dyes using conventional bath dyeing methods. However, the fiber dyed in this manner does not satisfy the light fastness requirement (ISO 105-B02 Method 2 > 5). After the xenon radiation, it apparently fades and its brightness changes significantly. Furthermore, the color depth is greatly reduced, which can be confirmed, for example, by the movement of the chromaticity coordinates. For decades, it has been known that adhesive fibers can be dyed in a permanent manner by combining dye pigments. Corresponding fibers are available on the market. However, until today, it is not possible to obtain a spun dyed regenerated cellulose fiber in accordance with EN 47 1. Assignment of tasks: Compared to this prior art, the task is to obtain a fiber that meets the requirements of protective and reflective clothing on the one hand (for example as described in EN 47 1) and on the other hand satisfies the wearing of this garment. Comfort and safety requirements, and reasonable and economical costs. For this reason, it is possible to manufacture the protective and reflective fibers from fibers similar to this without adding any other type of fibers. In this respect, it is particularly important that the textiles made from these fibers pass the following requirements for the base material in accordance with EN 471: • Brightness factor (according to CIE Bulletin 15.2) and chromaticity coordinates • Color after 氙 radiation : According to method 105 of ISO 105-B02, the exposure of the product 201128007 • Dry and wet rubbing fastness (iso 105-A02) In addition, the light fastness of the fiber is determined according to IS Ο 1 0 5 - B 0 2 method 2 . In addition, the task is to make suitable manufacturing methods available for these fibers. [Inventive content] Surprisingly, this task can be solved using regenerated cellulose fibers containing conjugated dye pigments and applied by excessive dyeing. Fluorescent dyes. These fibers according to the present invention have light fastness greater than 5 as measured in accordance with ISO 105-B02 Method 2, in addition to improved wearing comfort and increased safety due to the basic cellulosic structure. This is not possible with the cellulose fibers known to date. The fibers also meet other requirements in EN 471 for rubbing fastness, fastness to perspiration, fastness to cleaning, fastness to dry cleaning, fastness to hypochlorite bleach and ironing fastness. The spun-dyed regenerated cellulose fibers may be obtained by a viscose method, a modified viscose method (for example, a Modal method, a zinc-free adhesive method using aluminum sulfate, etc.), and an organic solvent (such as a molten aqueous solution). A solvent process carried out with amine oxides or also known as ionic liquids. The fibers can be correspondingly designated as viscose, modal and/or lysell. The regenerated cellulose fibers may contain other additives. In a preferred embodiment of the invention, the regenerated cellulose fibers are additionally provided with a flame retardant. A preferred embodiment of one of the flame-retardant fibers is produced by incorporating a pigment-shaped 201128007 flame retardant. In addition, other types of compounds can be considered as pigment-type flame retardants, and 2,2'-oxybis[5,5-dimethyl-1,3, dioxaphosphorinan] 2 is suitable for the viscose. , 2' disulfide, obtained under the trade name of Sandoflam®. In other preferred embodiments of the invention, an antimicrobial agent is further provided. In this respect, it is possible to use experts who have been able to use dyes suitable for cellulosic materials (eg direct dyes, dyeing dyes, etc.) for subsequent high viscosity in the spun dyed fiber bundles, in the yarns containing the fibers or Excessive staining, i.e., bath dyeing, of the fibers containing the spun dyeing. In this respect, continuous or discontinuous dyeing methods are known in the home. Color shading can be obtained by suitably selecting a pigment for spin dyeing and bath dyeing, which is heretofore determined. The subject matter of the invention is also that the fibers according to the invention, in order to characterize the properties suitable for the individual application, may also contain, for example, (flame retardant) polyester, Modacryl, para-position, in addition to the fibers according to the invention. Polyamide ylide (Kermel®), (flame retardant imidazole (PBI), polyimine (P84®), poly phthalamide, flame retardant acrylic, melamine (PPS), polytetrafluoroethylene Ethylene (PTFE), glass fiber, in particular, organic phosphating is, for example, a 2-dioxaphosphane (: a substance which can also be known as Exolit® or raw cellulose fibers. For example, reactive dyes, dye bath dyeing. In the spinning dyed fabric, the special high-viscosity dye can be used for the purpose of producing yarn without individual solution. The yarn of the invention, among other sources: - and meta-arylamine ) wool, polybenzoamide, (flame retardant) fiber, polyphenylene sulfide, cotton, silk, carbon 201128007 fiber, oxidized heat stabilized polyacrylonitrile fiber (PAN OX® ) and conductive fiber, And blends of these fibers. In the present invention In a specific example, the blending compound is similarly subjected to a high-viscosity post-treatment. Similarly, the use of the fiber according to the invention in the manufacture of a fabric is the subject of the present invention. In addition to the fibers according to the invention, the fabric may also Contains other fibers such as (flame retardant) polyester, Modacryl, para- and meta-arlenamide, polyvinylamine (Kermel®), (flame retardant) wool, polybenzimidazole (PBI) ), polyimine (P84® ), polyamine, (flame retardant) polyamide, flame retardant acrylic fiber, melamine fiber, polyphenylene sulfide (PPS), polytetrafluoroethylene (PTFE), Glass fiber, cotton, silk, carbon fiber, oxidized heat stabilized polyacrylonitrile fiber (PANOX®) and conductive fiber, and blends of these fibers. In a preferred embodiment of the invention, other fibers It may also have the characteristics of high-viscosity post-treatment. The fabric is preferably a woven fabric, a warped fabric or a knitted fabric, but may basically be a non-woven fabric. In the case of a woven or knitted fabric, there may be a basis in the following manner. The fiber of the invention Blends of other fibers: by blending before the yarn is produced (so-called intimate blend), or by using a combination of different types of fibers in each case when weaving, crimping or knitting. The subject of the invention is also the use of the fibres according to the invention for the production of reflective articles or other kinds of reflective articles of clothing 'by which, in general, the above-mentioned yarns and/or planar textile structures are manifested in the textile production chain. In the intermediate step, for the purposes of the present invention, other types of reflective -9 - 201128007 objects should be understood as, for example, streamers, flags, warning bars, and the like, which exhibit particularly high visibility and/or attractive attention. The use according to the invention is therefore not merely a pure warning effect. If a non-woven fabric as described above is used as the fabric, for example in the use of streamers, flags, warning strips and the like, the intermediate yarn is of course not applicable. Different specific examples of clothing items or other reflective items of this type are well known to those skilled in the art and therefore do not require any other description. Similarly, the above-described method of producing a regenerated cellulose fiber according to the present invention is also the subject of the present invention in which dye pigments are drawn into fibers and these fibers are over-stained with a fluorescent dye in a later processing step. This combination is generally carried out by adding a dye pigment to a spinning solution. The combined method of this type is basically known to experts in both viscose, modal and solvent spinning processes. However, the spun dyed cellulosic fiber is generally not over-dyed with another dye in another step because the spinning dyeing process is generally known to be an extremely effective method by which high fastness, and friction can be achieved. Light fastness, fastness to cleaning and sweat. However, the present invention, which is a combination method including excessive dyeing at a later stage, satisfies the special requirements of cellulose fibers for reflective clothing. Over-dyeing (i.e., bath dyeing) is carried out in a fiber bundle containing spun-dyed fibers or on a yarn or textile structure containing spun-dyed fibers. In this regard, continuous or discontinuous dyeing methods generally known to experts can be used. The invention will now be illustrated by way of example. These are understood to be possible specific examples of the invention. The invention is in no way limited to the scope of these examples. -10- 201128007 [Embodiment] Example 1: Spin-dyed flame-retardant viscose fiber contains, related to fiber _, 1.25 wt% of yellow pigment 3 (such as Aquarine Yellow 10G) and 22 weight; 2'-oxybis[5,5-dimethyl-1,3,2-dioxaphosphane] 2,2, disulfide (Exolit 5060, Messrs. Clariant). The fiber was then over-stained according to the following method using Remazol Leuchtgelb FL (Messrs. DyStar) according to the following method: The bundle was placed in a dye bath containing 2% Remaz() 1
Leuchtgelb FL( Messrs. DyStar)及具有 1: 10之液體比例 之100克/升的硫酸鈉及25 t之起初溫度及1 °C / min之加 熱速率至5(TC。在此溫度10分鐘之後，添加5克/升之蘇 打；且在另外之30分鐘後，添加1.2毫升/升之NaOH (含 5〇% )。在另外之4〇分鐘後，使該染色浴冷卻，然後在專 家已知之沖洗-浸漬-沖洗-浸漬步驟後接著進行後處理 〇 纖維然後被乾燥且由此纖維製造紡織織物。此產生在 表1中所含之測試結果。這些結果顯示依本發明所製造之 纖維、紗及紡織品在反射性衣物之用途上是優越的且不褪 色。 -11 - 201128007 表1 :測試結果（實例1) 開始 在曝露後(ISO 105-B02,方 亮度係數 0,7304 0,7282 色品座標 X座標 0,3830 0,3852 Y座標 0,4917 0,4915 摩擦牢度(濕及乾） 4 光牢度(ISO 105-B02方法2) 5-6 實例2 (比較用實例）： 使用與實例1中之相同方法，將商業上可得之黏膠纖 維（LENZING FR)過度染色，其也利用不合倂染料顔料 之E X ο 1 i t 5 0 6 0使之具有阻燃性。在此方面，使用6 %之 Remazol Leuchtgelb FL ( Messrs. D y S t a r )而非如實例1之 2%。該纖維展現表2中所含之測試結果。 表2 :測試結果（實例2) 開始 在曝露後(ISO 105-B02,方法3) 亮度係數 0,7666 0,7011 色品座標 X座標 0,3711 0,3920 Y座標 0,5184 0,5067 摩擦牢度(濕及乾） 4 光牢度(ISO 105-Β02方法2) 3-4 由於曝照，在實例2中之現有技藝之纖維色彩的明暗 度及深淺度比依本發明之實例1的纖維者改變甚爲強烈， 這也可以清楚地在色品座標之座標方面的強的移動上被確 認。同樣地，在非依本發明之纖維的亮度係數由於曝照所 致之變差遠大於依本發明之纖維者。然而，與依本發明之 實例1的纖維相比，在實例2中之纖維之光牢度甚差，此是 特別重大的。 -12-Leuchtgelb FL (Messrs. DyStar) and 100 g/l sodium sulfate with a liquid ratio of 1:10 and an initial temperature of 25 t and a heating rate of 1 ° C / min to 5 (TC. After 10 minutes at this temperature, Add 5 g / liter of soda; and after another 30 minutes, add 1.2 ml / liter of NaOH (containing 5 〇%). After another 4 〇 minutes, let the dye bath cool, and then rinsed by experts - Dip-rinse-impregnation step followed by post-treatment of the ruthenium fibers which are then dried and thereby fabricate the woven fabric. This produces the test results contained in Table 1. These results show the fibers, yarns and yarns produced according to the invention. Textiles are superior in the use of reflective clothing and do not fade. -11 - 201128007 Table 1: Test results (Example 1) Start after exposure (ISO 105-B02, square brightness coefficient 0,7304 0,7282 chromaticity coordinates) X coordinate 0,3830 0,3852 Y coordinate 0,4917 0,4915 Rubbing fastness (wet and dry) 4 Light fastness (ISO 105-B02 method 2) 5-6 Example 2 (comparative example): Use and examples In the same way as in 1, the commercially available viscose fiber (LENZING FR) is over-dyed. Color, which also makes it flame retardant using EX ο 1 it 5 0 60 without the dye pigment. In this respect, 6% Remazol Leuchtgelb FL (Messrs. D y S tar ) is used instead of Example 1 2%. The fiber exhibits the test results contained in Table 2. Table 2: Test results (Example 2) Start after exposure (ISO 105-B02, Method 3) Luminance coefficient 0,7666 0,7011 Chroma coordinates X coordinate 0,3711 0,3920 Y coordinate 0,5184 0,5067 Rubbing fastness (wet and dry) 4 Light fastness (ISO 105-Β02 method 2) 3-4 Fiber of the prior art in Example 2 due to exposure The brightness and depth of the color are much stronger than those of the fiber according to Example 1 of the present invention, which can also be clearly confirmed in the strong movement of the coordinates of the chromaticity coordinates. Similarly, in accordance with the present invention The brightness coefficient of the fiber is much worse than that of the fiber according to the present invention because of the exposure. However, the light fastness of the fiber in Example 2 is very poor as compared with the fiber according to Example 1 of the present invention. It is particularly significant. -12-