564268 A7 B7 五、發明説明（丨） 技術領域 本發明涉及可裝飾的夜光性繡線、或適宜衣料用的編織物 等各種用途的高輝度夜光性纖維及其製備方法，和使用該高輝 度夜光性纖維的編織物。 背景技術 以前，爲賦予各種纖維多種多樣的色彩效果，可用各種各 樣的材料進行著色處理，特別是近年來，使用各種功能性著色 材料作爲著色材料，試圖賦予纖維高度的附加價値，含有稱爲 蓄光顔料或夜光顔料的發光性著色材料的纖維就是其中之一。 經濟部智慧財產局員工消費合作社印製 作爲這種發光性著色材料，在特開昭49-47646號公報、特 公平3-70020號公報中公開了以硫化化合物作爲主體的用各 種金屬啓動的蓄光顔料的發光纖維織品。另外，特開平112414 號公報中公開了硫化鋅做主體的複合蓄光纖維，但是，在這些 公開的發登光的纖維中，發光輝度弱，發光時間也短到只有5 分鐘。一方面，如果在這種蓄光顔料中添加放射性物質，可以 提高發光功能，但是，在這種日常使用中的纖維材料用含放射 性物質的顔料，應當考慮避免對人體的影響。再者，在含氧化 總和/或氧化銘的金屬氧化物中，摻雜含銪和/或鏑的稀土元 素的夜光性顔料，儘管實質上不含放射性物質，可能長時間高 輝度發光，含有該夜光性顔料的纖維公開在特開平7—3〇〇722 號公報和特開2〇〇〇-%439號公報中。但是，近年來，消費者 對輝度性能的要求非常高，因而要求提高輝度性能。一 在上述的要求下，爲了提高輝度性能，特開平1〇_23148〇564268 A7 B7 V. Description of the Invention (Technical Field) The present invention relates to high-luminance noctilucent fibers for various purposes, such as decorative luminous embroidery threads or knitted fabrics suitable for clothing, and a method for preparing the same, and to use the high-luminance noctilucent Braid of sex fiber. BACKGROUND In the past, in order to impart various color effects to various fibers, a variety of materials can be used for coloring. In particular, in recent years, various functional coloring materials have been used as coloring materials in an attempt to add a high value to the fibers. The fiber of the luminescent coloring material of the luminous pigment or the luminous pigment is one of them. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs as such a luminous coloring material, JP 49-47646 and JP 3-70020 disclose light-storage activated by various metals, which is mainly composed of sulfur compounds. Pigmented luminescent fiber fabric. In addition, Japanese Unexamined Patent Publication No. 112414 discloses a composite light-storing fiber composed mainly of zinc sulfide. However, among these disclosed light-emitting fibers, the luminous brightness is weak and the luminous time is as short as 5 minutes. On the one hand, if radioactive substances are added to this light-storing pigment, the luminous function can be improved. However, in this daily use, pigments containing radioactive materials for fiber materials should be considered to avoid effects on the human body. Furthermore, in a metal oxide containing a total oxidation oxide and / or an oxidation oxide oxide, a noctilucent pigment doped with a rare earth element containing thorium and / or thorium may not emit radioactive substances and may emit light with high luminance for a long time. The fiber of the luminous pigment is disclosed in Japanese Patent Application Laid-Open No. 7-300022 and Japanese Patent Application Laid-Open No. 2000-% 439. However, in recent years, consumers have very high requirements for the luminance performance, and thus have been required to improve the luminance performance. 1. Under the above requirements, in order to improve the brightness performance, JP-A-Hei 10-23148.
564268 經濟部智慧財產局員工消費合作564268 Consumer Cooperation of Intellectual Property Bureau, Ministry of Economic Affairs
A7 B7 五、發明說明（>) 號 公 報 公 開 了 用 通 式 (M〇. 9995-0. 998EU0. 0005-0. 〇〇2)A12〇4 · (M〇. 9995-〇. 998EU〇. 0005-0. 0〇2) 〇A7 B7 V. Description of the Invention (>) Publication discloses that the general formula (M 0.9995-0. 998EU 0.005-0. 〇〇2) A12〇4 (M. 9995-〇. 998EU). 0005-0. 0〇2) 〇
BbQa) 2〇3[式中，M是選自由Sr、Ca、Mg和Ba組成組中的至少一 種元素，Q 是 La、Ce、pr、Nd、Sm、Gd、Tb、Dy、Ho、Er、Tm、 Yb、Y、Lu、Mn和Bi組成組中的至少一種元素。a爲 0· 0005-0· 002, b爲〇· 0〇1一〇· 35, n爲卜8的整數]表示的由燒 成體得到的夜光性顔料，此後，特開2000-136438號公報公開 了使用該夜光性顔料的聚烯烴纖維。但是，在這裏使用的聚烯 煙纖維’熔點爲160°C，在加工工程中因摩擦易熔解，另外， 該聚烯烴纖維的比重低於〇· 9,加工成細的纖維困難，在要求 手感柔軟的織物的衣料等的用途中不能夠使用，用途受到限 制。 發明內容 根據上述的問題’本發明的目的是提供可夜光性裝飾的刺 繡線，或者可在衣料用編織物等各種用途中使用的，而且對人 體沒有不良影響、得到長時間高輝度、發多色光的夜光纖維及 其製備方法和使用該夜光性纖維的編織織物。 本發明人爲達到上述目的反覆深入硏究的結果，開發成功 了含有特定的夜光性顔料的聚烯烴樹脂或聚酯樹脂作芯成 分，不含有夜光性顔料的聚酯樹脂爲殼成分，不存在上述問題 的高輝度夜光性纖維。 也就是說，本發明提供了下述1-8記載的高輝度夜光纖維; 和9-10記載的高輝度夜光性纖維的製備方法及11記載的用該 5 t適用中國國家標準（CNS)A4規格（210 X 297公釐） ---裝------—訂--------- (請先閱讀背面之注意事項再填寫本頁) 564268 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明（乃） 高輝度夜光性纖維的編織織物。 1 ·局輝度仪光纖維是含有通式（Mo. 9995_。· 998Eu〇. _5-o. G〇2) A12 · (M〇.9995-a998Eu。.。。·。⑻2)〇 · η(Α1 卜b-aBbQa)2〇^BbQa) 2 03 [where M is at least one element selected from the group consisting of Sr, Ca, Mg and Ba, and Q is La, Ce, pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Y, Lu, Mn, and Bi constitute at least one element in the group. a is 0. 0005-0. 002, b is 0. 0001-35, n is an integer of 8] is a luminous pigment obtained from a fired body, and thereafter, Japanese Patent Application Laid-Open No. 2000-136438 A polyolefin fiber using the luminous pigment is disclosed. However, the polyolefin smoke fiber used here has a melting point of 160 ° C and is easily melted due to friction during processing. In addition, the specific gravity of the polyolefin fiber is less than 0.9, and it is difficult to process into fine fibers. It cannot be used for applications such as clothing of soft fabrics, and its use is limited. SUMMARY OF THE INVENTION In view of the above-mentioned problem, an object of the present invention is to provide a luminous decorative embroidery thread, or to be used in various applications such as knitted fabrics for clothing, and has no adverse effects on the human body. Colored luminous fiber, preparation method thereof, and knitted fabric using the luminous fiber. In order to achieve the above-mentioned objective, the inventors repeatedly researched and developed a polyolefin resin or a polyester resin containing a specific luminous pigment as a core component, and a polyester resin containing no luminous pigment as a shell component, which did not exist. The high-luminance noctilucent fiber of the above problem. That is, the present invention provides the high-intensity noctilucent fiber described in the following 1-8; and the method for producing the high-intensity noctilucent fiber described in 9-10 and the 5t applicable Chinese National Standard (CNS) A4 described in 11-10 Specifications (210 X 297 mm) --- install -------- order --------- (Please read the precautions on the back before filling out this page) 564268 Employees ’Consumption of Intellectual Property Bureau, Ministry of Economic Affairs A7 printed by the cooperative V. Description of invention (is) Woven fabric of high-brightness luminous fiber. 1 · The optical fiber of the local luminance meter contains the general formula (Mo. 9995_. 998Eu〇. 5-o. G〇2) A12 · (M〇.9995-a998Eu ...... 2) η (Α1 B-aBbQa) 2〇 ^
Sr、Ca、Mg和Ba組成組中的至少一種元素，Q是La、Ce、 Pr、Nd、Sm、Gd、Tb、Dy、Ho、Er、Tm、Yb、Y、Lu、Μη 和 Bi 組成組中的至少一種元素。a爲0·0005-0.002，b爲 G· 001-〇· 35, η爲1-8的整數]表示的由燒成體得到的夜光性顔 料的聚酯樹脂或聚烯烴樹脂作芯成分的和不含有夜光性顔料 的聚酯樹脂作殼成分的芯殼型複合纖維，相對全部纖維，含有 夜光性顔料7-25重量%，從激發停止1分鐘後的殘光輝度爲 500mcd/m2以上，單根纖維的粗度爲40 μ m以下。 2·上述1記載的高輝度夜光纖維，在9(TC的熱水中處理 3〇分鐘後，激發停止1分鐘後，殘光輝度是400mcd/m2以上。 3·上述各項記載的高輝度夜光纖維，含有夜光性顔料的芯 成分和不含有夜光性顔料的殻成分的體積比爲1/5-2/1。 4.上述各項記載的高輝度夜光性纖維，在波長爲 515-525nm範圍發光色爲綠色，在波長485-495 nm範圍發光色 爲青色，在波長420-440 rim範圍發光色爲紫色，在波長 560-580 nm範圍發光色爲黃色。 5·上述各項記載的高輝度夜光性纖維，夜光性顔料的平均 粒徑爲1-10 μ m，而且，夜光性顔料用4⑻目的金屬網篩過濾時， 殘渣量爲lOOppm以下。 6·上述各項記載的高輝度夜光性纖維，芯成分的聚酯樹脂 6 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 564268 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（令） 是熔點爲200-27CTC的聚酯樹脂。 7.上述各項記載的局輝度夜光性纖維，芯成分的聚烯烴樹 脂是熔點爲80-18CTC、MFR 1-40克/10分鐘的的聚烯烴樹脂。 8·上述各項記載的局輝度夜光性纖維，殼成分的聚酯樹脂 是熔點爲2⑻-27CTC的聚酯樹脂。 9·上述各項記載的高輝度夜光性纖維的製備方法，其特徵 是製備含有 10-60 重量％的通式 (Μ〇· 9995-。· 998EU。· _5-。·。。2) A12〇4 · (M。· 9995-。. 998EUq. _5-。·。。2) 0 · Π (A 1 卜b-aBbQa )2〇3 [式中，Μ是選自由Sr、Ca、Mg和Ba組成組中的至少一種 兀素 ’ Q 是 La、Ce、Pr、Nd、Sm、Gd、Tb、Dy、Ho、Er、Tm、 Yb、Y、Lu、Mn和Bi組成組中的至少一種元素。a爲 0· 0005-0· 002, b爲0· 001-〇· 35, η爲1-8的整數]表示的由燒 成體得到的夜光性顔料的聚酯樹脂或聚烯烴樹脂配製的芯成 分，配製的不含有夜光性顔料的聚酯樹脂作殼成分，以全部纖 維中夜光性顔料爲7-20重量%的芯殼比率熔融複合紡絲後，在 拉伸率爲2-4倍，拉伸溫度爲70-KXTC，熱定形溫度爲100-220 °匚的條件下，進行拉伸。 10·上述各項記載的高輝度夜光性纖維的製備方法，其特 徵是在熔融複合紡絲後，在拉伸倍率爲2-4倍，在拉伸溫度爲 70-1⑻°C，熱定形溫度爲1⑻-220°C的條件下進行拉伸後，在 鬆驰率爲1-10%和鬆驰溫度爲100-220°C的條件下進行鬆驰熱 處理。 11·使用上述各項的任一項記載的高輝度夜光性纖維的編 7 冢紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱^ I ^-------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 564268 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明（< ) 織織物。 具體的實施方式 本發明的高輝度夜光性纖維的發光性能在激發停止1分鐘 後的殘光輝度必須在500mcd/m2以上。激發停止1分鐘後的殘 光輝度小於500mcd/m2，不能達到本發明的目的，即在可裝飾 的夜光性刺繡線或衣料用編織物等各用途中不宜使用。 而且，本發明的夜光性纖維，在90°C熱水中處理30分鐘 後’激發ί亨止1分鐘後的殘光輝度必須在400mcd/m2以上。聚 酯纖維的通常染色溫度爲120-130°C。但是要維持夜光性性能， 可能的染色條件是溫度儘可能低，時間儘可能的短，優選9CTC 溫度和30分鐘。在9CTC熱水中處理30分鐘後，激發停止1 分鐘後的殘光輝度小於400mcd/m2時，染色後的發光性能差。 爲了在90°C熱水中處理30分鐘後，激發停止1分鐘後的殘光 輝度在400mcd/m2以上，在處理前1分鐘後的殘光輝度必須在 500mcd/m2以上。不滿足這些條件時，達不到本發明的目的， 即夜光性刺繡線或衣料用編織物等不宜使用。 製備夜光性纖維，必須製備含有夜光性顔料的聚烯烴樹月旨 或聚酯樹脂的芯成分，製備不含有夜光性顔料的透明性高的聚 酯樹脂的殼成分，然後將兩者製成芯殼型複合結構。構成芯成 分的樹脂，染色工程爲必要時，優選聚烯烴樹脂。構成芯成分 的樹脂是聚酯樹脂時，在染色工程等熱水中處理時，芯部易被 水浸透，蓄光顔料與水接觸時，蓄光顔料變成水合物，容易降 低蓄光性能。 8 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---------------------------- (請先閱讀背面之注音？事項再填寫本頁) 564268 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（L ) 另外，構成殼成分的聚酯樹脂，爲了防止在製絲工程、力口 工工程等中夜光性顔料脫落，必須是不含有夜光性顔料的聚酯 測旨。而且，爲了提高夜光性顔料的激動效率和發光透過率， 必須是透明性高的聚酯樹脂。 纖維中夜光性顔料的含量，含量越高夜光性性能越好，但 是’必須在7-25重量%的範圍內。小於7重量％，不能確保充 足的夜光性性能。超過25重量％，製絲的穩定性差。 本發明的高輝度夜光性纖維的單纖纖維的粗度必須小於 40//m。纖維的粗度超過40//m，沒有柔軟織物的手感，達不 到本發明的目的，即難於在刺繡線或衣料等用途中使用。 在本發明中所使用的夜光性顔料，大粒徑的顔料夜光性性 能良好，但是，從製絲性、得到的夜光性纖維的纖維性的觀點 來看，平均粒徑必須在1-10 //m範圍內。使用的夜光性顔料的 平均粒徑超過10//m，製絲性降低，得到的夜光性纖維的纖維 強度降低，或者後加工工程的通過性也降低。另外，平均粒徑 小於1 /zm，幾乎沒有發光性能，難以製成夜光性纖維。 另外，夜光性顔料用400目的金屬網篩過濾時，殘留渣量必 須在lOOppm以下。該値是夜光性顔料中存在的粗大粒子含有 率的指標，按下述的方法測定。即在夜光性顔料的試樣中，攪 拌下加入六偏磷酸鈉水溶液，將塊打碎調製成分散液，求出在 4〇〇目的金屬篩網過濾通過時的濾過殘渣量。沒有通過400目 金屬篩網的試樣的殘渣是30 // m以上粗大粗子，這種粗大粒子 的含量超過100 ppm，在紡絲或拉伸工程中多發生斷線，在紡 9 ------------裝--------tr'--------- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 564268 A7 _________ B7 五、發明說明) 絲工程中因篩檢程式堵塞易引起壓力上升，産生噴嘴更換周期 短的問題。 本發明的高輝度夜光性纖維的芯殼比率，從製絲性、纖維 物性的觀點考慮，芯殼的體積比必須在1/5-2/1的範圍內. 芯殼比小於1/5,在構成纖維的芯部發生斷面斑，製絲性降低. 另外，芯殼比超過2/1，製絲性並不變差，但是，在編織工程機 織等後加工工程中的通過性差。 構成纖維的芯成分中的夜光性顔料的濃度必須在10-60重 量％。芯成分中的夜光性顔料的濃度小於10%時，得到的夜光 性纖維中的夜光性顔料的濃度在7重量％以上時，芯殼比率必 須超過2/1，發生製絲性穩定性差等的問題。芯成分中夜光 性顔料的濃度超過60重量％時，聚合物的流動性顯著惡化， 製絲困難。 在本發明中使用的夜光性顔料、是用前述通式表示的燒成 體，在室溫下200-450nm的紫外線照射和/或可見光照射，在 紫外線和/或可見光線遮斷後，以高輝度發出綠色、青色、紫色 或黃色的各種顔色。在上述的通式中，Μ、Eu的數値是表示該 元素含有比率的摩爾數。在該通式中，Eu是啓動成分，Eu的 含有比率必須在〇· 0005-0· 002摩爾範圍。Eu的含有比率超過 0· 002摩爾，引起濃度消光現象，沒有發光性。另外，小於 0· 0005摩爾，發光中心數不夠，發光性弱。 而且，在本發明中所使用的夜光性顔料是有高的發光輝 度，同時有長殘光性，而且發光峰値波長爲489 nm發青色光， 10 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱1 --------,§ (請先閱讀背面之注意事項再填寫本頁)Sr, Ca, Mg, and Ba are at least one element in the group, and Q is La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Y, Lu, Mn, and Bi. At least one of the elements. a is 0 · 0005-0.002, b is G · 001-〇 · 35, η is an integer of 1-8], and the sum of the core components of the polyester resin or polyolefin resin of the luminous pigment obtained from the fired body is expressed as Core-shell composite fibers containing no luminous pigments as the shell component, containing 7-25% by weight of luminous pigments relative to all fibers, and having a residual brightness of 500 mcd / m2 or more after 1 minute from the stop of excitation. The thickness of the root fiber is 40 μm or less. 2. The high-brightness luminous fiber according to 1 above, after 30 minutes of treatment in hot water at 9 ° C, and after 1 minute of excitation stop, the afterglow brightness is 400mcd / m2 or more. 3. The high-brightness luminous light according to the above items The volume ratio of the fiber, the core component containing the noctilucent pigment and the shell component not containing the noctilucent pigment is 1 / 5-2 / 1. 4. The high-brightness noctilucent fiber described in the above items, in the wavelength range of 515-525nm The light emission color is green, the light emission color is cyan in the wavelength range of 485-495 nm, the light emission color is purple in the wavelength range of 420-440 rim, and the light emission color is yellow in the wavelength range of 560-580 nm. 5. High brightness according to the above items Noctilucent fibers have an average particle size of 1-10 μm, and when the noctilucent pigments are filtered through a 4-mesh metal mesh sieve, the amount of residue is 100 ppm or less. 6. The high-brightness noctilucent fibers described in the above items. Polyester resin with core composition 6 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -------------------- Order- ------- line (please read the notes on the back before filling this page) 564268 A7 B7 printed by Fei cooperatives 5. Description of the invention (Order) is a polyester resin with a melting point of 200-27CTC. 7. The local-brightness luminous fiber described in the above items, and the polyolefin resin with a core component of 80-18CTC, Polyolefin resin with MFR 1-40 g / 10 minutes. 8. The polyester resin with local brightness and luminous fiber as described in the above items is a polyester resin with a melting point of 2⑻-27CTC. 9. The above items A method for preparing a high-brightness noctilucent fiber, which is characterized in that it contains 10-60% by weight of a general formula (M0 · 9995- ·· 998EU. · _5 -... 2) A12〇4 (M. · 9995- .. 998EUq. _5 -... 2) 0 · Π (A 1 b b-aBbQa) 2 0 [where M is at least one element selected from the group consisting of Sr, Ca, Mg, and Ba. The prime 'Q is at least one element in the group consisting of La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Y, Lu, Mn, and Bi. A is 0.00005-0 · 002, b is 0 · 001-〇 · 35, η is an integer of 1-8] The core component prepared from the polyester resin or polyolefin resin of the luminous pigment obtained from the fired body, which is formulated without luminous Sexual face Polyester resin as the shell component, after melt-spinning with a core-shell ratio of 7-20% by weight of the luminous pigment in all the fibers, the stretch ratio is 2-4 times, and the stretching temperature is 70-KXTC. Stretch at a setting temperature of 100-220 °-. 10. The method for preparing the high-brightness noctilucent fiber described in the above items, which is characterized in that after melt-composite spinning, the draw ratio is 2-4 times, the draw temperature is 70-1⑻ ° C, and the heat setting temperature is After stretching under the conditions of 1⑻-220 ° C, the relaxation heat treatment is performed under the conditions of a relaxation rate of 1-10% and a relaxation temperature of 100-220 ° C. 11. Use of high-luminance noctilucent fibers as described in any of the above items. 7 The paper size of the mound paper is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 public love ^ I ^ -------------) ---------- Order --------- line (please read the notes on the back before filling out this page) 564268 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 V. Invention Description (≪) Weaving fabric. Specific embodiments The afterglow luminance of the high-brightness noctilucent fiber of the present invention after the stop of excitation must be 500mcd / m2 or more. The afterglow after the stop of excitation for 1 minute is less than 500mcd / m2, cannot achieve the purpose of the present invention, that is, it is not suitable for use in various applications such as decorative luminous embroidery threads or knitted fabrics. Moreover, the luminous fiber of the present invention is treated in 90 ° C hot water for 30 minutes After 1 minute of post-excitation, the afterglow brightness must be above 400mcd / m2. The normal dyeing temperature of polyester fiber is 120-130 ° C. However, to maintain luminous properties, the possible dyeing condition is that the temperature is as low as possible , The time is as short as possible, preferably 9CTC temperature and 30 minutes. After 30 minutes of intermediate treatment, the residual luminosity after dyeing for 1 minute after stopping the excitation is less than 400mcd / m2. After treatment for 30 minutes in 90 ° C hot water, the residual brightness after 1 minute of stopping the excitation Above 400mcd / m2, the residual brightness after 1 minute before treatment must be above 500mcd / m2. When these conditions are not met, the purpose of the present invention is not achieved, that is, luminous embroidery threads or knitted fabrics for clothing are not suitable for use. To prepare noctilucent fibers, it is necessary to prepare the core component of a polyolefin tree containing a noctilucent pigment or a polyester resin, to prepare a shell component of a highly transparent polyester resin that does not contain a noctilucent pigment, and then make both Core-shell composite structure. The resin constituting the core component is preferably a polyolefin resin when the dyeing process is necessary. When the resin constituting the core component is a polyester resin, the core is easily penetrated by water when processed in hot water such as dyeing process. When the light-storing pigment is in contact with water, the light-storing pigment becomes a hydrate, which is likely to reduce the light-storage performance. 8 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ----------- --- -------------- (Please read the note on the back? Matters before filling out this page) 564268 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (L) In addition, The polyester resin constituting the shell component must be a polyester that does not contain a luminous pigment in order to prevent the luminous pigment from falling off during the silk-making process and the mouth-opening process. In addition, in order to improve the excitement efficiency of the luminous pigment and The luminous transmittance must be a polyester resin with high transparency. The higher the content of the luminous pigment in the fiber, the better the luminous performance, but it must be in the range of 7-25% by weight. Less than 7% by weight, sufficient luminous properties cannot be ensured. When it exceeds 25% by weight, the stability of the yarn production is poor. The single-fiber thickness of the high-brightness noctilucent fiber of the present invention must be less than 40 // m. The thickness of the fiber is more than 40 // m, there is no feel of a soft fabric, and the object of the present invention is not achieved, that is, it is difficult to use in embroidery threads or clothing. The luminous pigments used in the present invention have good luminous properties for pigments with large particle diameters. However, from the viewpoint of the silk-forming properties and the fiber properties of the luminous fibers obtained, the average particle diameter must be 1-10 / / m range. The average particle diameter of the luminous pigment used exceeds 10 // m, and the silk-making property is reduced. The fiber strength of the luminous fiber obtained is reduced, or the passability of the post-processing process is also decreased. In addition, the average particle diameter is less than 1 / zm, there is almost no light emitting performance, and it is difficult to make a luminous fiber. In addition, when the luminous pigment is filtered through a 400-mesh metal mesh sieve, the amount of residual slag must be 100 ppm or less. This gadolinium is an index of the content ratio of coarse particles present in a luminous pigment, and was measured by the following method. That is, in a sample of a luminous pigment, an aqueous solution of sodium hexametaphosphate was added with stirring, and the block was crushed to prepare a dispersion liquid, and the amount of filtration residue during filtration through a 400 mesh metal sieve was determined. The residue of the sample that did not pass through the 400 mesh metal sieve is 30 // m or more coarse particles. The content of such coarse particles exceeds 100 ppm. In the spinning or drawing process, thread breakage occurs. In spinning 9- ---------- Loading -------- tr '--------- (Please read the precautions on the back before filling in this page) The paper size applies to Chinese national standards (CNS) A4 specification (210 X 297 mm) 564268 A7 _________ B7 V. Description of the invention) In the silk project, the pressure rise due to the blockage of the screening program is prone to cause the problem of short nozzle replacement cycle. The core-shell ratio of the high-brightness noctilucent fiber of the present invention must be in the range of 1 / 5-2 / 1 from the viewpoint of silk-making property and fiber physical properties. The core-shell ratio is less than 1/5, A cross-section spot occurs at the core of the constituent fiber, and the silk-making property is reduced. In addition, the silk-making property is not inferior when the core-shell ratio exceeds 2/1. However, it has poor passability in post-processing processes such as weaving engineering and weaving. The concentration of the luminous pigment in the core component constituting the fiber must be 10 to 60% by weight. When the concentration of the noctilucent pigment in the core component is less than 10%, when the concentration of the noctilucent pigment in the obtained noctilucent fiber is more than 7% by weight, the core-shell ratio must exceed 2/1, resulting in poor silk stability and the like. problem. When the concentration of the luminous pigment in the core component exceeds 60% by weight, the fluidity of the polymer is significantly deteriorated, and it is difficult to produce silk. The luminous pigment used in the present invention is a fired body represented by the aforementioned general formula, and is irradiated with ultraviolet rays of 200-450 nm and / or visible light at room temperature. After being interrupted by ultraviolet rays and / or visible rays, it has a high luminance. Glow in green, cyan, purple or yellow. In the above general formula, the numbers of M and Eu are the number of moles indicating the content ratio of the element. In the general formula, Eu is a starting component, and the content ratio of Eu must be in the range of 0.0005-0.002 mol. The content ratio of Eu exceeds 0.002 mol, which causes a concentration extinction phenomenon and has no luminescence. In addition, if it is less than 0.005 mol, the number of light-emitting centers is insufficient and the light-emitting property is weak. In addition, the luminous pigment used in the present invention has high luminous brightness and long residual luminescence, and the luminescence peak has a wavelength of 489 nm and emits cyan light. 10 This paper size applies Chinese National Standard (CNS) A4 Specifications (210 X 297 Public Love 1 --------, § (Please read the precautions on the back before filling this page)
訂---------線I 經濟部智慧財產局員.工消費合作社印製 564268 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（g) 或在520nm附近發黃綠色光的新的燒成體。特別是優選用通式 中的Q表示的Dy、Nd、Bi和Μη組成組中選擇的至少一種元素 作附加啓動成分時，根據殘光性點特別優選Dy。另外，用Q 表示的Dy等元素的量，a=0· 0005-0· 002摩爾，a小於〇· 〇〇〇5 時，對結晶體的長殘光蓄光性能沒有什麽影響。另外，a大於 0. 002時，因爲進入結晶體空隙中的量一定，造成不經濟。 另外，夜光性顔料，具有啓動成分和附加啓動成分的協同 作用的長殘光的性能，得到了有高的輝度的物質。此時，發光 的峰値波長，因爲通過改變前g通式中Μ的種類或其用量而變 化，所以得到不同的發光色。 在夜光性顔料中硼的含量，b=0· 001-0· 35,優選這個範圍， b小於0· 001時，發現對結晶體的長殘光發光性能沒有什麽影 響。另外，硼的含量大於〇· 35時，在燒成體中，氧化硼類的 生成物多，由於減少了長殘光性物質，因而不好。 從上述的構成元素燒結的夜光性顔料，非常地堅固，具有 莫氏硬度爲6· 2-7. 5的硬度。 從前述通式表示的燒成體得到的夜光性顔料，在紫外線和 /或可見光線遮斷後，在515-525nm的波長範圍內，發綠色的 光，可列舉出用下式(1)表示爲PICARK：0(^々U a)CP-05(商 品名)。 (1) (Sr〇. 999δΕΐ1〇. 0005) AI2O4 # (Sr〇. 999δΕΐΙ〇. 000δ) 〇 # (Α1 卜〇.。卜〇. 〇〇〇5Β〇.〇iDy〇. 0005) 2〇3 485-495 nm 卞皮長車(內，發 青色光，用下式⑵表示PICARIC0 CP-10 (商品名）。 11 ·*·· ί II------看------- —訂--------- 華 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 564268 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（q ) (2) (Sr 〇. 9995EU0.0005) AI2O4 · (Sr〇. 9995E1I0.0005) Ο · 2 (Ali-a〇i-()._5BG.〇iDya_5) 2〇3 在 42〇_44〇 nm 波長範圍內，發紫色光 用下式(3)表示PICARICO CP-20 (商品名）。 (3) (Sr〇.9992Ca〇.89928Eu〇.〇〇〇8)Al2〇4 · (Sr〇.9992Ca〇.89928ElI〇.0〇〇8)〇· (A1 1-0. 01-0. ΟΟΙδΒο. 01 Dy〇._8Nd〇._8)2〇3 在 560-580 nm 波長範圍內 ρ 黃色光，用下式(4)表示PICARICO CP-30 (商品名）。 (4) (Sr〇. 7996Ca〇. 1999EU0· 0006) AI2O4 · (Sr〇. 7996Ca〇. 1999E1I0. 0005) Q , (A1 l-o. 02-0. 002 Bo. 02 Dy〇.〇()2)2〇3,追些都是凱密股份有限公司製，在市 場上可以上述商品名購得。 本發明的局輝度仪光性纖維的構成成分，芯成分或殼成分 都是用的聚醋纖維樹脂時’其溶點必須在2⑻-270°c範圍內， 而其他沒有必要加以特別限制，例如，聚對苯二甲酸乙二醇 酯、聚對苯二甲酸丁二醇酯等，或者它們的共聚合的聚酯。熔 點低於200°C，因摩擦熱易熔化，後加工工程的通過性降低。熔 點超過270°C，熔融紡絲時的纖維化困難。 另外，芯成分用的聚烯烴樹脂時，必須是熔點爲80-180 °C，MFR 1-40克/10分鐘的聚烯烴樹脂，但是，其他的特性沒有 必要加以特別限制。熔點低於80°C，在染色工程中，因熱水 的溫度使芯成分融解，芯成分易被水浸透，使夜光性能下降。 MPR値在1-40克/10分鐘外，聚酯在複合紡絲時的製絲穩定性 下降。 前述通式表示的燒成體的夜光性顔料，構成芯成分的聚酯 樹脂或聚烯烴樹脂都是直接添加，而且在彩色高濃度染色配料 12 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） •* 丨^----^---------------訂---------^^1 (請先閱讀背面之注意事項再填寫本頁) 564268 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明u〇) 時，添加彩色高濃度染色配料用樹脂。 構成本發明的高輝度夜光性纖維的芯成分，將聚烯烴樹脂 或聚酯樹脂熔融，按10-60重量%的範圍將平均粒徑爲1-10# m的前述通式表示的由燒成體得到的夜光性顔料混合分散在 其中，可形成混合分散體，假如夜光性顔料預先在聚烯烴樹脂 或聚酯樹脂中熔融分散成彩色高濃度染色配料的形態，可以提 高在芯成分用的樹脂中夜光性顔料的分散性。另外，含有夜光 性顔料的聚烯烴樹脂或聚酯樹脂作芯成分，不含夜光性顔料的 聚酯樹脂作殼成分，按芯成分與殼成分的體積比爲1/5-2/1 複合紡絲，紡絲方法沒有特別限制，可以使用本技術領域內公 知的複合紡絲裝置進行。 這樣得到的複合纖維，按拉伸倍率爲2-4倍，拉伸溫度爲 70 - 10Q°C的溫度，熱定形溫度爲100-200°C的條件進行拉伸， 可以得到高輝度夜光性纖維。此時的拉伸倍率小於2倍時，製 得的纖維強度降低，另外，拉伸倍率超過4倍，製絲的穩定性 下降。拉伸溫度低於7〇°C，不能進行均勻拉伸，其結果，在 纖維軸向方向發生粗的斑，局部地方纖維強度差，染色情況不 好。溫度超過l〇〇°C，不能進行均勻拉伸，發生與上述同樣的 問題。而且，熱定形溫度低於l〇〇°C，纖維的熱收縮率升高， 織品加工後的尺寸穩定性差。另外，熱定形溫度超過2〇〇°C ’ 製絲的穩定性下降。因此，優選的拉伸溫度爲75-90°C，熱定 形溫度爲100-18CTC。 再者，紡絲、拉伸用1次連續的方法（或者一次停製絲法) 13 本紙張尺度適用中國國家標準(CNS)A4規格（210 X 297公釐) 鱗 - -----------裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 564268 A7 B7 五、發明說明（丨I ) 進行，同樣可以得到高輝度夜光性纖維。 另外，拉伸的絲，可以按鬆驰率爲卜10%，鬆弛溫度爲 100-220°C的條件連續牽引，實施鬆驰熱處理，可提高尺寸的穩 定性。鬆弛率小於1 %和鬆驰溫度低於l〇〇°C，纖維的收縮率 不可能明顯降低，不能得到提高尺寸穩定性的效果。鬆弛率超 過10%，鬆驰時牽引輥(roll)易黏住絲，穩定性差。鬆驰溫 度超過220°C，熱使纖維易熔解，易發生斷絲。 另外，本發明的高輝度夜光性纖維的截面形狀，芯殼構造 呈圓形、三角形等異型截面，中空截面也行。另外，總纖度沒 有特別限制，可爲任意纖度。 使用本發明的高輝度夜光性纖維編織織物，對編織機、編 織組織沒有特別限制，使用至少一部是本發明的目的之一，在 可裝飾夜光性衣料用編織物等的各種用途中均可使用。 實施例 下面，列舉實施例更詳細地描述本發明，但是，只要不超 出本發明的旨意，本發明不受這些實施例的限制。 殘光輝度 1·將’械維均句地捲在塑膠卡片上(纖維層厚1毫米）。 2·捲取的樣品遮斷光5小時。 3. 將樣品水平置於27W臺式螢光燈下60鐘米處（1〇〇〇流 明），照射啓動30分鐘。 4. 照射停止後，用T0PC0N股份有限公司製的τ〇ρ⑶NBM_8 輝黯測定殘光輝度(T0PC0N BM-"軍度計的檢測鎌度最小 14 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁)Order --------- Line I Printed by the Intellectual Property Bureau of the Ministry of Economy. Printed by the Industrial and Consumer Cooperatives 564268 Printed by the Consumers Cooperative of the Intellectual Property Bureau of the Ministry of Economy A7 B7 V. Description of the invention (g) or yellow-green near 520nm New fired body of light. In particular, when at least one element selected from the group consisting of Dy, Nd, Bi, and Mη represented by Q in the general formula is preferably used as an additional activating component, Dy is particularly preferred depending on the afterglow point. In addition, when the amount of elements such as Dy represented by Q is a = 0.0005-0. 002 mol, and a is less than 0.005, there is no effect on the long residual light storage performance of the crystal. In addition, when a is greater than 0.002, it is uneconomical because a certain amount enters the crystal void. In addition, noctilucent pigments have the properties of long afterglow with the synergistic effect of the priming component and the additional priming component, resulting in a substance with high luminance. At this time, the peak chirp wavelength of the light emission is changed by changing the type of M in the previous g formula or the amount thereof, so that different emission colors are obtained. The content of boron in the luminous pigment is b = 0.001-0.35, which is a preferred range. When b is less than 0.001, it is found that there is no effect on the long-lasting light emission performance of the crystal. In addition, when the content of boron is more than 0.35, there are many boron oxide products in the sintered body, and it is not good because the long residual light-emitting substances are reduced. The luminous pigment sintered from the above-mentioned constituent elements is very strong and has a Mohs hardness of 6 · 2-7 · 5. The luminous pigment obtained from the fired body represented by the aforementioned general formula emits green light in the wavelength range of 515-525 nm after being cut off by ultraviolet and / or visible light. The following formula (1) is used as an example PICARK: 0 (^ 々 U a) CP-05 (trade name). (1) (Sr. 999δΕΐ10.0 0005) AI2O4 # (Sr. 999δEΐ1〇. 000δ) 〇 # (Α1 卜 .. 卜 〇. 〇〇〇〇〇〇〇〇〇〇Dy〇. 0005) 2〇3 485 -495 nm long leather car (inside, emits cyan light, and expresses PICARIC0 CP-10 (trade name) with the formula 。. 11 · * ·· ί II ------ Look ----------- Order --------- Hua (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 564268 Employees of Intellectual Property Bureau, Ministry of Economic Affairs Printed by the consumer cooperative A7 B7 V. Description of the invention (q) (2) (Sr 0.999995EU0.0005) AI2O4 · (Sr 0.99995E1I0.0005) 0 · 2 (Ali-a〇i-() ._ 5BG.〇 iDya_5) 2〇3 In the wavelength range of 42-440 nm, the purple light is expressed by the following formula (3) PICARICO CP-20 (trade name). (3) (Sr.9992Ca.89928Eu〇.〇〇 〇8) Al2〇4 (Sr.9992Ca.89928ElI0.0.00)) (A1 1-0. 01-0. 〇ΙδΒο. 01 Dy〇._8Nd〇._8) 203 at 560 Ρ yellow light in the wavelength range of -580 nm, and PICARCO CP-30 (trade name) is expressed by the following formula (4). (4) (Sr〇. 7996Ca〇. 1999EU0 · 0006) AI2 O4 · (Sr〇. 7996Ca〇. 1999E1I0. 0005) Q, (A1 lo. 02-0. 002 Bo. 02 Dy〇.〇 () 2) 2 03, these are all made by Kaimi Co., Ltd., It can be purchased in the market under the above trade names. When the constituent components, core components or shell components of the optical fiber of the local luminance meter of the present invention are all used in the polyester fiber resin, its melting point must be in the range of 2⑻-270 ° c. And others do not need to be particularly limited, for example, polyethylene terephthalate, polybutylene terephthalate, etc., or their copolymerized polyesters. Melting point is lower than 200 ° C due to friction It is easy to melt due to heat, and the passability of the post-processing process is reduced. The melting point exceeds 270 ° C, and fibrillation during melt spinning is difficult. In addition, the polyolefin resin used for the core component must have a melting point of 80-180 ° C, MFR 1 -40g / 10min polyolefin resin, but other characteristics do not need to be specially limited. Melting point is below 80 ° C. In dyeing process, the core component is melted due to the temperature of hot water, so the core component is easily saturated with water. To reduce luminous performance. When the MPR 値 is from 1 to 40 g / 10 minutes, the spinning stability of the polyester during composite spinning decreases. The luminous pigment of the fired body represented by the aforementioned general formula, the polyester resin or polyolefin resin constituting the core component are directly added, and the color high-concentration dyeing ingredients are used. 12 This paper size applies the Chinese National Standard (CNS) A4 specification ( 210 X 297 mm) • * 丨 ^ ---- ^ --------------- Order --------- ^^ 1 (Please read the note on the back first Please fill in this page again for details) 564268 Printed A7 B7 by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description u〇), add color high-concentration dyeing ingredients resin. The core component of the high-brightness noctilucent fiber of the present invention is a polyolefin resin or a polyester resin which is melted, and the average particle diameter is 1 to 10 # m in the range of 10 to 60% by weight. The luminous pigment obtained by mixing and dispersing the luminous pigment can form a mixed dispersion. If the luminous pigment is previously melt-dispersed in a polyolefin resin or polyester resin into a form of colored high-concentration dyeing ingredients, the resin for the core component can be improved. Dispersibility of medium luminous pigment. In addition, a polyolefin resin or polyester resin containing a luminous pigment is used as a core component, and a polyester resin containing no luminous pigment is used as a shell component. The volume ratio of the core component to the shell component is 1 / 5-2 / 1. The spinning method is not particularly limited, and can be performed using a composite spinning device known in the art. The composite fiber thus obtained can be drawn at a draw ratio of 2-4 times, a draw temperature of 70-10Q ° C, and a heat setting temperature of 100-200 ° C. High-glow luminous fibers can be obtained. . When the draw ratio at this time is less than 2 times, the strength of the obtained fiber decreases, and when the draw ratio exceeds 4 times, the stability of the yarn production decreases. The stretching temperature is lower than 70 ° C, and uniform stretching cannot be performed. As a result, coarse spots occur in the axial direction of the fiber, the fiber strength is poor in some places, and the dyeing is not good. If the temperature exceeds 100 ° C, uniform stretching cannot be performed, and the same problems as described above occur. Moreover, the heat-setting temperature is lower than 100 ° C, the thermal shrinkage of the fibers increases, and the dimensional stability of the fabric after processing is poor. In addition, when the heat-setting temperature exceeds 200 ° C, the stability of the yarn is reduced. Therefore, the preferred stretching temperature is 75-90 ° C and the heat-setting temperature is 100-18CTC. In addition, one continuous method (or one-stop spinning method) is used for spinning and drawing. 13 This paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm) scales ------- ----- Install -------- Order --------- (Please read the precautions on the back before filling this page) 564268 A7 B7 V. Description of the invention (丨 I) Similarly, high-brightness noctilucent fibers can be obtained. In addition, the stretched yarn can be continuously drawn at a relaxation rate of 10% and a relaxation temperature of 100-220 ° C. Relaxation heat treatment can be performed to improve dimensional stability. With a relaxation rate of less than 1% and a relaxation temperature of less than 100 ° C, the shrinkage of the fiber cannot be significantly reduced, and the effect of improving dimensional stability cannot be obtained. The relaxation rate exceeds 10%, and the traction roll is liable to stick to the wire when loosened, and the stability is poor. The relaxation temperature exceeds 220 ° C, and the fiber is easily melted by heat, and the filament is easily broken. In addition, the cross-sectional shape of the high-brightness noctilucent fiber of the present invention has a core-shell structure having a special-shaped cross section such as a circle or a triangle, and a hollow cross section is also acceptable. In addition, the total fineness is not particularly limited, and may be any fineness. The use of the high-brightness noctilucent fiber woven fabric of the present invention is not particularly limited to knitting machines and knitting structures. The use of at least a part of the present invention is one of the objects of the present invention, and can be used in various applications such as decorative knit fabrics use. EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited by these examples, as long as the purpose of the present invention is not exceeded. Afterglow brightness 1. The ‘machine’ is uniformly rolled onto a plastic card (fiber layer thickness is 1 mm). 2. The rolled sample was blocked for 5 hours. 3. Place the sample horizontally at 60 minutes (1000 lumens) under a 27W desktop fluorescent lamp, and start the irradiation for 30 minutes. 4. After the irradiation is stopped, use τ〇ρ⑶NBM_8 made by T0PC0N Co., Ltd. to measure the residual light brightness (T0PC0N BM- " the tester ’s detection sickness is at least 14 This paper standard is applicable to the Chinese National Standard (CNS) A4 specification ( 210 X 297 mm) (Please read the notes on the back before filling this page)
訂---------線I 經濟部智慧財產局員工消費合作社印製 564268 A7 B7 五、發明說明（θ ) 爲1400米/分。另外，這種纖維在拉伸溫度爲85°C、拉伸倍 率爲2. 6倍進行拉伸後，以鬆弛率爲5%，在155°C溫度下熱定形， 得到133dtex24絲(f)的佼光性纖維。 得到的纖維中夜光性顔料的含量爲10. 3重量%/線，從明的 場所轉移到暗的場所時，具有數小時發高輝度綠色光(波長 518-520nm)的功能。表1示出了纖維物性，表2示出了殘光輝 度試驗結果，表3币出了熱水處理後殘光輝度試驗結果。另 外，得到的夜光性纖維的單纖維的粗度爲22 μ m。 實施例2 除芯部的蓄光劑濃度爲30%外，其他與實施例1相同， 得到133dtex24絲(f)的夜光性纖維。 得到的纖維中夜光性顔料的含量爲13.7重量%/線，從明 的場所轉移到暗的場所時，具有數小時發高輝度綠色光(波長 518-520nm)的功能。表1示出了纖維物性，表2示出了殘光輝 度試驗結果，表3示出了熱水處理後殘光輝度試驗結果。另 外，得到的夜光性纖維的單纖維的粗度爲22 μ m。 實施例3 除芯成分樹脂是MFR値4克/10分、熔點=106°C的聚乙 烯樹脂外，其他與實施例1相同，得到133dtex24絲(f)的夜 光性纖維。 得到的纖維中夜光性顔料的含量爲10· 5重量%/線，從明 的場所轉移到暗的場所時，具有數小時發高輝度綠色光(波長 518-520nm)的功能。表1示出了纖維物性，表2示出了殘光輝 16 本紐尺度顧中關家#ί (CNS)A4規格（21G x 297公爱）"麵 " (請先閱讀背面之注意事項再填寫本頁) 訂--- 經濟部智慧財產局員工消費合作社印製 564268 A7 B7 五、發明說明（V4r) 度試驗結果，表3示出了熱水處理後殘光輝度試驗結果。另 外，得到的夜光性纖維的單纖維的粗度爲22 μ m。 實施例4 首先，使用80重量％的[77 ]=0· 71，熔點=255°C的聚對苯 二甲酸乙二醇酯樹脂和20重量%作爲夜光性顔料的平均粒徑 爲4 μ m的前述通式表示的由燒成體得到的夜光性顔料，商品 名PICARI⑶CP-05 (凱密股份有限公司株式會社製)熔融成形， 製備MB。將這種MB配製成芯成分，使用[π ]=〇· 71，熔點=255 °C的聚對苯二甲酸乙二醇酯樹脂作殻成分，芯殻比（體積 比)1/1，在285°C下熔融，用圓形截面芯殼型0· 30X24孔的複 合紡絲噴嘴成形，捲取的牽引速度爲1400米/分。另外，這種 纖維在拉伸溫度爲85°C、拉伸倍率爲2· 9倍進行拉伸後，以鬆 弛率爲5%，在160°C溫度下熱定形，得到133dtex24絲(f)的夜 光性纖維。得到的纖維中夜光性顔料的含量爲10. 5重量%/線， 從明的場所轉移到日首的場所時，具有數小時發局輝度綠色光 (波長518-520nm)的功能。表1示出了纖維物性，表2示出了 殘光輝度試驗結果，表3示出了熱水處理後殘光輝度試驗結 果。另外，得到的夜光性纖維的單纖維的粗度爲22 μ m。 實施例5 除將芯部的夜光性顔料濃度變更爲40%、芯殼比（體積 比）變更爲1/2.5之外，其他與實施例4相同，得到 133dtex24絲(f)的夜光性纖維。得到的纖維中夜性顔料的 含量爲14· 2重量%/線，從明的場所轉移到暗的場所時，具有數 17 表紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐1 """""" (請先閱讀背面之注意事項再填寫本頁) ,¾ 訂---------線{ 經濟部智慧財產局員工消費合作社印製 564268 A7 五、發明說明（< ) 小時發高輝度綠色光(波長518-520ηπι)的功能。表1示出了纖 維物性，表2示出了殘光輝度試驗結果，表3示出了熱水處理 後殘光輝度試驗結果。另外，得到的夜光性纖維的單纖維的粗 度爲22 μ m 〇 比較例1 除芯殼比(體積比)爲1/3外，其他與實施例4相同，得到 133dtex24絲(f)的夜光性纖維。得到的纖維中夜光性顔料的 含量爲5重量%/線，從明的場所轉移到暗的場所時，與實施例 1 -5比較，發高輝度綠色光(波長518-520nm)的功能差。表1 示出了纖維物性，表2示出了殘光輝度試驗結果。 比較例2 首先，用40重量％的MFR値爲5克/10分、熔點=165t 的聚丙烯樹脂和60重量%作爲夜光性顔料的平均粒徑爲4以^ 的前述通式表示的由燒成體得到的夜光性顔料，商品名 PICARICO CP-〇5 (凱密股份有限公司)熔融成形，製備MB。将遠 種MB配製成芯成分，使用[π ]=〇· 71，熔點=255°C的聚對笨〜 甲酸乙二醇酯樹脂作殼成分，芯殼比(體積比)1/1，在285°C$ 熔融，用圓形截面芯殼型〇· 3〇Χ 24孔的複合紡絲噴嘴成形，試 圖以引取速度爲1400米/分捲取，因斷絲不能製絲。 18 -------------------訂--------- (請先閱讀背面之注音？事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 564268 A7 Β7 經濟部智慧財產局員工消費合作社印製 五、發明說明) 表1 -I-+- 心 部 聚 合 物 -Η- 心 部 濃 度 殼部 聚合 物 芯/殼 蓄光 劑含 量 (%) 織度 (detx) 強度 (cN/ detx ) 伸度 (%) 實施 例1 pp*1 23 PET 1/1 10.3 133.4 2. 36 25.9 實施 例2 PP 30 PET 1/1 13.7 132.8 2. 28 22.8 實施 例3 PE*2 23 PET 1/1 10. 5 133.4 2. 30 25.4 實施 例4 PET*3 20 PET 1/1 10.5 135. 1 2.85 29. 1 實施 例5 PET 40 PET 1/2.5 14.2 134.4 2.71 28.9 比較 例1 PET 20 PET 1/3 5.0 133.3 3.28 28.5 比較 例2 PP 60 PET 1/1 不可製絲 . - --------訂---------線 (請先閱讀背面之注意事項再填寫本頁) *1 PP表示聚丙烯 *2 PE表示聚乙烯 *3 PET表示聚對苯二甲酸乙二醇酯 19 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 564268 A7 B7 五、發明說明（li ) 經濟部智慧財產局員工消費合作社印製 表2 激發停 止後的 經過時 間 殘光輝度(mcd/m2) 實施例 1 實施例 2 實施例 3 實施例 4 實施例 5 比較例 1 5秒 2900 3200 2850 2900 3200 1590 15秒 1810 2120 1760 1650 1940 880 30秒 1080 1340 1030 1040 1260 560 1分 600 840 550 610 740 320 2分 320 470 280 310 430 180 3分 210 320 200 200 290 120 4分 160 240 140 150 220 90 5分 130 200 120 120 190 70 6分 100 170 90 90 160 60 7分 90 140 80 90 140 50 8分 80 130 70 80 120 50 9分 70 120 60 70 110 40 10分 60 110 50 60 100 30 20分 30 50 30 30 50 20 30分 20 30 20 20 30 10 1小時 10 20 10 10 20 <10 判斷 〇 〇 〇 〇 〇 X 20 丨^-------------------訂--------- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 564268 A7 B7 五、發明說明) 經濟部智慧財產局員工消費合作社印製 表3 激發停 止後的 經過時 間 殘光輝度(mcd/m2) 實施例1 實施例2 實施例3 實施例4 實施例5 5秒 2610 2900 2570 2270 2500 15秒 1630 1900 1580 990 1170 30秒 970 1210 930 590 720 1分 540 760 500 380 470 2分 290 420 250 190 260 3分 190 290 180 100 150 4分 140 220 130 80 110 5分 120 200 110 60 100 6分 100 150 80 50 80 7分 80 130 70 50 70 8分 70 120 60 40 60 9分 60 110 50 40 60 10分 50 100 40 30 50 20分 30 50 30 20 30 30分 20 30 20 10 20 1小時 10 20 10 10 10 判斷 〇 〇 〇 Δ 〇 21 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -JI!------f--------訂---------線# (請先閱讀背面之注意事項再填寫本頁) 564268 A7 _B7 五、發明說明（丨3) 發明效果 以上詳細地說明，本發明的高輝度夜光性纖維是含有特定 的夜光性顔料，以聚烯烴樹脂或聚酯樹脂作芯成分，不含有夜 光性顔料的聚酯樹脂作殼成分構成的夜光性纖維，該夜光性纖 維實質上不含有放射性物質，具有長時間高輝度發光性質，而 且具有柔軟的手感，可在可裝飾的夜光性刺繡線，或衣料用編 織物等用途中使用，作爲纖維材料是極其有用的材料。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 2 2 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）Order --------- Line I Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 564268 A7 B7 5. The description of the invention (θ) is 1400 m / min. In addition, this fiber was drawn at a drawing temperature of 85 ° C and a draw ratio of 2.6 times, and then was heat-set at a temperature of 155 ° C at a relaxation rate of 5% to obtain 133dtex24 filament (f). Outstanding optical fiber. The content of the luminous pigment in the obtained fiber was 10.3% by weight / line, and when transferred from a light place to a dark place, it had a function of emitting high-brightness green light (wavelength 518-520 nm) for several hours. Table 1 shows the fiber properties, Table 2 shows the results of the afterglow test, and Table 3 shows the results of the afterglow test after hot water treatment. The thickness of the single fiber of the obtained luminous fiber was 22 m. Example 2 A luminous fiber of 133 dtex 24 filaments (f) was obtained in the same manner as in Example 1 except that the concentration of the light storage agent in the core portion was 30%. The content of the luminous pigment in the obtained fiber was 13.7% by weight / line, and when transferred from a light place to a dark place, it had the function of emitting high-brightness green light (wavelength 518-520 nm) for several hours. Table 1 shows the fiber properties, Table 2 shows the results of the afterglow test, and Table 3 shows the results of the afterglow test after hot water treatment. The thickness of the single fiber of the obtained luminous fiber was 22 m. Example 3 A luminous fiber of 133 dtex 24 filaments (f) was obtained in the same manner as in Example 1 except that the core component resin was a polyethylene resin having a MFR of 4 g / 10 minutes and a melting point = 106 ° C. The content of the luminous pigment in the obtained fiber was 10.5 wt% / line, and when transferred from a light place to a dark place, it had the function of emitting high-brightness green light (wavelength 518-520 nm) for several hours. Table 1 shows the physical properties of the fiber, and Table 2 shows the afterglow of the 16-year-old Guzhongguanjia # ί (CNS) A4 specification (21G x 297 public love) " face " (Please read the precautions on the back first Fill out this page again) Order --- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 564268 A7 B7 V. Description of the invention (V4r) Degree test results, Table 3 shows the afterglow brightness test results. The thickness of the single fiber of the obtained luminous fiber was 22 m. Example 4 First, 80% by weight of [77] = 0.71 and a melting point = 255 ° C of a polyethylene terephthalate resin and 20% by weight as a luminous pigment have an average particle diameter of 4 μm. The luminous pigment obtained from the fired body represented by the aforementioned general formula has a trade name of PICARICDCP-05 (manufactured by Kaimi Co., Ltd.) and is melt-molded to prepare MB. This MB is formulated into a core component, and a polyethylene terephthalate resin with [π] = 0.71 and a melting point = 255 ° C is used as a shell component, and the core-shell ratio (volume ratio) is 1/1, It was melted at 285 ° C and formed with a composite spinning nozzle with a circular cross-section core-shell type 0. 30X24 hole. The take-up speed was 1400 m / min. In addition, this fiber was drawn at a drawing temperature of 85 ° C and a draw ratio of 2.9 times, and then was heat-set at 160 ° C at a relaxation rate of 5% to obtain 133 dtex24 filament (f). Luminous fiber. The content of the luminous pigment in the obtained fiber was 10.5% by weight / line, and when it was transferred from a bright place to a day place, it had the function of emitting local green light (wavelength 518-520nm) for several hours. Table 1 shows the fiber physical properties, Table 2 shows the results of the afterglow test, and Table 3 shows the results of the afterglow test after hot water treatment. The single fiber thickness of the obtained luminous fiber was 22 μm. Example 5 A luminous fiber of 133 dtex 24 filaments (f) was obtained in the same manner as in Example 4 except that the concentration of the luminous pigment in the core portion was changed to 40% and the core-shell ratio (volume ratio) was changed to 1 / 2.5. The content of the nocturnal pigment in the obtained fiber was 14.2% by weight / line, and when transferred from a light place to a dark place, it had a number of 17 sheets. The paper size was applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 1 " " " " " " (Please read the notes on the back before filling out this page), ¾ Order --------- line {Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 564268 A7 V. Description of the invention (<) Function of emitting high-brightness green light (wavelength 518-520ηι) in one hour. Table 1 shows the physical properties of the fiber, Table 2 shows the results of the afterglow luminance test, and Table 3 shows the heat Test results of residual brightness after water treatment. The single fiber thickness of the obtained luminous fiber was 22 μm. Comparative Example 1 The same as Example 4 except that the core-shell ratio (volume ratio) was 1/3. 133 dtex 24 silk (f) luminous fiber was obtained. The content of the luminous pigment in the obtained fiber was 5 wt% / thread, and when it was transferred from a bright place to a dark place, compared with Examples 1-5, high luminosity was obtained. Green light (wavelength 518-520nm) has poor function. Table 1 shows the fiber properties, and Table 2 shows the residual brightness. Comparative Example 2 First, a 40% by weight polypropylene resin having an MFR 値 of 5 g / 10min, a melting point = 165t, and 60% by weight as a luminous pigment having an average particle diameter of 4 is represented by the aforementioned general formula of ^ The luminous pigment obtained from the fired body, the product name PICARICO CP-〇5 (Kaimi Co., Ltd.) was melt-molded to prepare MB. A distant MB was formulated into a core component, using [π] = 0.71, Polyparaben with a melting point of 255 ° C ~ Formic acid ester resin as the shell component, core-shell ratio (volume ratio) 1/1, melted at 285 ° C $, core-shell type with circular cross section 0.3 The 24-hole composite spinning nozzle is formed, and it is attempted to take up at a take-up speed of 1400 meters per minute, and it cannot be made because of broken yarn. 18 ------------------- Order- -------- (Please read the note on the back? Matters before filling out this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 564268 A7 Β7 Employees of Intellectual Property Bureau, Ministry of Economic Affairs Printed by Consumer Cooperatives 5. Description of the invention) Table 1 -I-+-Heart polymer-Η- Heart concentration Shell polymer core / shell light storage agent content (%) Weaving degree (detx) Strength (cN / detx ) Elongation (%) Example 1 pp * 1 23 PET 1/1 10.3 133.4 2. 36 25.9 Example 2 PP 30 PET 1/1 13.7 132.8 2. 28 22.8 Example 3 PE * 2 23 PET 1/1 10 5 133.4 2. 30 25.4 Example 4 PET * 3 20 PET 1/1 10.5 135.1 1 2.85 29. 1 Example 5 PET 40 PET 1 / 2.5 14.2 134.4 2.71 28.9 Comparative Example 1 PET 20 PET 1/3 5.0 133.3 3.28 28.5 Comparative Example 2 PP 60 PET 1/1 No silk can be made.--------- Order --------- Thread (Please read the precautions on the back before filling this page) * 1 PP means polypropylene * 2 PE means polyethylene * 3 PET means polyethylene terephthalate 19 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 564268 A7 B7 V. Description of the invention (Li) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 2 Elapsed time after excitation stop (mcd / m2) Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 5 seconds 2900 3200 2850 2900 3200 1590 15 seconds 1810 2120 1760 1650 1940 880 30 seconds 1080 1340 1030 1040 1260 560 1 minute 600 840 550 610 740 320 2 minutes 320 470 280 310 430 180 3 minutes 210 320 200 200 290 120 4 points 160 240 140 150 220 90 5 points 130 200 120 120 190 70 6 points 100 170 90 90 160 60 7 points 90 140 80 90 140 50 8 points 80 130 70 80 120 50 9 points 70 120 60 70 110 40 10 minutes 60 110 50 60 100 30 20 minutes 30 50 30 30 50 20 30 minutes 20 30 20 20 30 10 1 hour 10 20 10 10 20 < 10 Judgment 〇〇〇〇〇X 20 丨 ^- ----------------- Order --------- (Please read the precautions on the back before filling this page) This paper size applies to Chinese National Standards (CNS) A4 specifications (210 X 297 mm) 564268 A7 B7 V. Description of the invention) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Table 3 Elapsed time after the stop of excitation (mcd / m2) Example 1 Example 2 Implementation Example 3 Example 4 Example 5 5 seconds 2610 2900 2570 2270 2500 15 seconds 1630 1900 1580 990 1170 30 seconds 970 1210 930 590 720 1 minute 540 760 500 380 470 2 minutes 290 420 250 190 260 3 minutes 190 290 180 100 150 4 points 140 220 130 80 110 5 points 120 200 110 60 100 6 points 100 150 80 50 80 7 points 80 130 70 50 70 8 points 70 120 60 40 60 9 points 60 110 50 40 6 0 10 minutes 50 100 40 30 50 20 minutes 30 50 30 20 30 30 minutes 20 30 20 10 20 1 hour 10 20 10 10 10 Judgment 〇〇〇Δ 〇21 This paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 mm) -JI! ------ f -------- Order --------- Line # (Please read the notes on the back before filling this page) 564268 A7 _B7 V. Description of the invention (丨 3) The effects of the invention are explained in detail above. The high-brightness noctilucent fiber of the present invention contains a specific noctilucent pigment with polyolefin resin or polyester resin as the core component and no Luminous fiber composed of polyester resin as a shell component. The luminous fiber does not substantially contain radioactive substances, has long-term high-brightness luminous properties, and has a soft feel. It can be used in decorative luminous embroidery threads or clothing. It is used for applications such as knitted fabrics and is extremely useful as a fiber material. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 2 2 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)