TWI717578B - Dyed polypropylene fiber structure and clothing materials using it - Google Patents

Dyed polypropylene fiber structure and clothing materials using it Download PDF

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TWI717578B
TWI717578B TW106145570A TW106145570A TWI717578B TW I717578 B TWI717578 B TW I717578B TW 106145570 A TW106145570 A TW 106145570A TW 106145570 A TW106145570 A TW 106145570A TW I717578 B TWI717578 B TW I717578B
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polypropylene fiber
dyed
fiber structure
dye
polypropylene
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TW201823366A (en
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宮崎慶輔
古賀孝一
堀照夫
廣垣和正
田畑功
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學校法人金澤工業大學
國立大學法人福井大學
日商有本化學工業股份有限公司
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/16—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dispersed, e.g. acetate, dyestuffs
    • D06P1/20—Anthraquinone dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/94—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in solvents which are in the supercritical state
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/79—Polyolefins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/79—Polyolefins
    • D06P3/794—Polyolefins using dispersed dyes
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/14—Dyeability
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2509/00—Medical; Hygiene

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Dispersion Chemistry (AREA)
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Abstract

本發明提供一種染色之聚丙烯纖維構造物，其特徵係以下述通式(1)所表示之紅色染料染色：

Figure 106145570-A0305-02-0001-1
式中，R1係分別獨立選自碳數4~8的支鏈烷基、及碳數9~19的芳基烷基所成群中的1種，n為1~3。前述支鏈烷基係包含四級碳原子，前述芳基烷基之烷基部分係包含四級碳原子。 The present invention provides a dyed polypropylene fiber structure characterized by being dyed with a red dye represented by the following general formula (1):
Figure 106145570-A0305-02-0001-1
 In the formula, R 1 is one independently selected from the group of branched alkyl groups having 4 to 8 carbons and arylalkyl groups having 9 to 19 carbons, and n is 1 to 3. The aforementioned branched alkyl group contains quaternary carbon atoms, and the alkyl portion of the aforementioned arylalkyl group contains quaternary carbon atoms.

Description

染色之聚丙烯纖維構造物及使用其之衣料品 Dyed polypropylene fiber structure and clothing materials using it

本發明係關於染色之聚丙烯纖維構造物及使用其之衣料品。 The present invention relates to dyed polypropylene fiber structures and clothing materials using the same.

聚丙烯樹脂，係將丙烯加成聚合的結晶性之熱可塑性樹脂。此聚丙烯樹脂，係以石油煉製時之廢氣之丙烯做為原料因此係廉價；為近於可浮於水之低密度(0.90~0.92g/cm3)因此係輕量；幾乎無吸水.吸濕性(公定含水率0.0%)因此有速乾性。進一步地，聚丙烯樹脂係具有耐藥品性、耐磨性、耐彎曲性、防靜電性等非常多的優異特徵．特性(參照非專利文獻1、2)。 Polypropylene resin is a crystalline thermoplastic resin obtained by addition polymerization of propylene. This polypropylene resin uses propylene, which is the waste gas of petroleum refining, as a raw material, so it is cheap; it has a low density (0.90~0.92g/cm 3 ) that can float in water and is therefore lightweight; almost no water absorption. Hygroscopicity (0.0% of nominal moisture content) therefore has quick-drying properties. Furthermore, polypropylene resins have many excellent features such as chemical resistance, abrasion resistance, bending resistance, and antistatic properties. Characteristics (refer to Non-Patent Documents 1 and 2).

聚丙烯為單純支鏈烴之高分子，儘管具有為支基之甲基，卻無對與染料之化學反應有效的官能基。此外，聚丙烯的結晶相對緻密，且疏水性極高，幾乎不因水膨脹。由於此等理由，使用傳統之染色技法的聚丙烯之著色係極為困難。 Polypropylene is a polymer of simple branched chain hydrocarbons. Although it has a branched methyl group, it has no functional groups effective for chemical reactions with dyes. In addition, the crystals of polypropylene are relatively dense and highly hydrophobic, and hardly swell due to water. For these reasons, it is extremely difficult to color polypropylene using traditional dyeing techniques.

現在市面上的有色之聚丙烯纖維構造物，幾乎都是藉由於聚合物切粒之製造階段添加顏料的原液著色法(原著法)所成之原著線。 原著法係必須於纖維製品之製造中最初期的階段，亦即，有必須在熔融紡 線時便決定顏色之不便處，不能適時地選色。此外，由於原著線係添加了為異物之顏料，因此與未著色之常規線相比製線性較差，無法穩定地生產單線纖度為1dtex以下的細線。進一步地，變更製造之線之色時，必須以下一色的樹脂將熔融紡線裝置內的前色之樹脂推出而置換，因此需要捨棄大量樹脂及許多時間。若考量獲利性及市場價格，原著線勢必要以1個顏色生產一定量以上，色數自然就受限制。 Almost all of the colored polypropylene fiber structures on the market are original lines created by the dope coloring method (original method) in which pigments are added during the manufacturing stage of polymer cutting. The original method must be in the initial stage of the manufacture of fiber products, that is, it must be The inconvenience of the color is determined when the thread is threaded, and the color cannot be selected in time. In addition, because the original thread is added with foreign matter pigments, the linearity of the original thread is poorer than that of the uncolored conventional thread, and it is impossible to stably produce thin threads with a single thread fineness of 1 dtex or less. Furthermore, when changing the color of the thread to be manufactured, the resin of the next color must be pushed out and replaced by the resin of the previous color in the melt spinning device. Therefore, it is necessary to discard a large amount of resin and a lot of time. If profitability and market price are considered, the original line must be produced in a certain amount with one color, and the number of colors is naturally limited.

聚丙烯作為合成樹脂係與聚乙烯、聚氯乙烯、聚苯乙烯被並列舉為四大汎用合成樹脂中的一種，以廉價的原料費及優異特性為背景被應用於非常廣泛的領域(非專利文獻3)。與此對照地，聚丙烯作為合成纖維的用途相當受到限制(非專利文獻4)。此主要係由於聚丙烯常規線無法染色導致的色數稀少，及唯一有效之著色方法之原著法使單線纖度不得不變大等主要理由。 Polypropylene is listed as a synthetic resin series with polyethylene, polyvinyl chloride, and polystyrene as one of the four general-purpose synthetic resins. It is used in a very wide range of fields under the background of cheap raw materials and excellent characteristics (non-patented Literature 3). In contrast, the use of polypropylene as a synthetic fiber is considerably restricted (Non-Patent Document 4). This is mainly due to the scarcity of color numbers due to the inability of conventional polypropylene threads to be dyed, and the original method, which is the only effective coloring method, which makes the single thread size larger.

若將聚丙烯纖維自由染色的方法實用化，則無色數之限制，可將單線纖度小(細)之廉價常規線著色。如此一來，所追求的設計性變高，在目前尚未能適用聚丙烯纖維的領域，例如，車輛內裝材領域或衣料品領域中，將可期待活用此特性而開發的新用途。 If the method of free dyeing of polypropylene fibers is put into practical use, there is no restriction on the number of colors, and cheap conventional yarns with small (fine) single yarn denier can be colored. As a result, the desired design becomes higher, and in fields where polypropylene fiber is not currently applicable, for example, in the field of vehicle interior materials or clothing materials, new applications developed by utilizing this feature can be expected.

於1960年代，曾嘗試藉由變更染料的分子構造而水性染色聚丙烯纖維，專利文獻1~5、非專利文獻5中列舉了幾種用於聚丙烯染色的染料。進一步地，根據非專利文獻6~11中所記載的聚丙烯纖維之水性染色研究，用於如聚丙烯般疏水性非常高之纖維的染料，必須具有遠高於慣用之聚酯纖維用染料的疏水性。然而，能以水性染色完成且使所染色之聚丙烯纖維之耐光、洗滌、摩擦、昇華等之各種堅牢度皆良好的染料，係 尚未被發現。 In the 1960s, attempts were made to dye polypropylene fibers water-based by changing the molecular structure of dyes. Patent Documents 1 to 5 and Non-Patent Document 5 listed several dyes for dyeing polypropylene. Furthermore, according to the water-based dyeing studies of polypropylene fibers described in Non-Patent Documents 6 to 11, the dye used for fibers with very high hydrophobicity such as polypropylene must have a much higher performance than conventional dyes for polyester fibers. Hydrophobicity. However, dyes that can be dyed with water and make the dyed polypropylene fibers have good fastness to light, washing, rubbing, and sublimation. Has not been discovered yet.

代替水性染色的聚丙烯纖維之染色方法，已知被稱為超臨界(流體)染色，將超臨界二氧化碳(scCO2)作為染色媒介使用之方法。例如，專利文獻6中，係揭示了使用scCO2，可將聚酯纖維、聚丙烯纖維等疏水性纖維材料以各種染料染色。非專利文獻12~17中，係記載了以超臨界染色，可將聚丙烯纖維以現在市面所流通之聚酯用染料染色。 The dyeing method of polypropylene fiber instead of water-based dyeing is known as supercritical (fluid) dyeing, which uses supercritical carbon dioxide (scCO 2 ) as a dyeing medium. For example, Patent Document 6 discloses that by using scCO 2 , hydrophobic fiber materials such as polyester fibers and polypropylene fibers can be dyed with various dyes. Non-Patent Documents 12 to 17 describe that by supercritical dyeing, polypropylene fibers can be dyed with polyester dyes currently circulating in the market.

此外，非專利文獻18、19中，係揭示了可將聚丙烯布以scCO2染色的特定之藍色及黃色之染料，藉由以此等之染料染色，可提供具有優異染色堅牢度的染色聚丙烯纖維。 In addition, Non-Patent Documents 18 and 19 disclose specific blue and yellow dyes that can dye polypropylene cloth with scCO 2. By dyeing with such dyes, dyeing with excellent dye fastness can be provided. Polypropylene fibers.

【先前技術文獻】 【Prior Technical Literature】 【專利文獻】 【Patent Literature】

【專利文獻1】日本專利特公昭38-10741號公報 [Patent Document 1] Japanese Patent Publication No. 38-10741

【專利文獻2】日本專利特公昭40-1277號公報 [Patent Document 2] Japanese Patent Publication No. 40-1277

【專利文獻3】日本專利特公昭41-3515號公報 [Patent Document 3] Japanese Patent Publication No. 41-3515

【專利文獻4】英國專利第872,882號說明書 [Patent Document 4] Specification of British Patent No. 872,882

【專利文獻5】美國專利第3,536,735號說明書 [Patent Document 5] Specification of US Patent No. 3,536,735

【專利文獻6】日本專利第3253649號公報 [Patent Document 6] Japanese Patent No. 3253649

【非專利文獻】 【Non-Patent Literature】

【非專利文獻1】M Ahmed, Polypropylene fibers, science and technology (Amsterdam; New York: Elsevier Scientific Pub.Co.,1982). [Non-Patent Document 1] M Ahmed, Polypropylene fibers, science and technology (Amsterdam; New York: Elsevier Scientific Pub.Co., 1982).

【非專利文獻2】J Akrman and J Prikryl,J.Appl.Polym.Sci.,62 (1996) 235. [Non-Patent Document 2] J Akrman and J Prikryl, J. Appl. Polym. Sci., 62 (1996) 235.

【非專利文獻3】P.Galli, S.Danesi and T.Simonazzi, Polym. Eng.Sci,24 (1984) ,544. [Non-Patent Document 3] P. Galli, S. Danesi and T. Simonazzi, Polym. Eng. Sci, 24 (1984), 544.

【非專利文獻4】山本洋，纖維學會誌，61 (2005) ,319-321. [Non-Patent Document 4] Yamamoto Hiro, Journal of the Fiber Society, 61 (2005), 319-321.

【非專利文獻5】永井芳男，松尾昌季，有機合成化學協會誌，23 (1) (1965) ,2-11. [Non-Patent Document 5] Nagai Yoshio, Matsuo Masaki, Journal of the Synthetic Organic Chemistry Association, 23 (1) (1965), 2-11.

【非專利文獻6】Z H Cui, S F Zhang and J Z Yang,Chin.Chem.Lett.,18 (2007) 1145. [Non-Patent Document 6] Z H Cui, SF Zhang and J Z Yang, Chin. Chem. Lett., 18 (2007) 1145.

【非專利文獻7】T Kim, J Jung, K Jang, S Yoon and M Kim, Fibers Polym.,10 (2009) 148. [Non-Patent Document 7] T Kim, J Jung, K Jang, S Yoon and M Kim, Fibers Polym., 10 (2009) 148.

【非專利文獻8】T Kim, J Jung, S Son, S Yoon, M Kim and J S Bae, Fibers Polym.,9 (2008) 538. [Non-Patent Document 8] T Kim, J Jung, S Son, S Yoon, M Kim and J S Bae, Fibers Polym., 9 (2008) 538.

【非專利文獻9】T Kim, J Jung, S Yoon, M Kim and Y-A Son, J. Korean Soc.Dye.Finish.,19 (2007) 28. [Non-Patent Document 9] T Kim, J Jung, S Yoon, M Kim and Y-A Son, J. Korean Soc. Dye. Finish., 19 (2007) 28.

【非專利文獻10】T Kim, S Yoon, J Hong, H Kim and J Bae, J. Korean Soc.Dye.Finish.,18 (2006) 30. [Non-Patent Document 10] T Kim, S Yoon, J Hong, H Kim and J Bae, J. Korean Soc. Dye. Finish., 18 (2006) 30.

【非專利文獻11】S J Mangan, J Crouse and F Calogero,Text.Chem.Color.,21 (1989) 38. [Non-Patent Document 11] S J Mangan, J Crouse and F Calogero, Text.Chem.Color., 21 (1989) 38.

【非專利文獻12】W Oppermann, H Herlinger, D Fiebig and O Staudenmayer, Melliand Textilberichte-Int.Text.Rep.,77 (1996) 588. [Non-Patent Document 12] W Oppermann, H Herlinger, D Fiebig and O Staudenmayer, Melliand Textilberichte-Int.Text.Rep., 77 (1996) 588.

【非專利文獻13】E Bach, E Cleve and E Schollmeyer, J.Text.Inst. Part 1 Fiber Sci.Text.Tecnol.,89 (1998) 647. [Non-Patent Document 13] E Bach, E Cleve and E Schollmeyer, J. Text. Inst. Part 1 Fiber Sci. Text. Tecnol., 89 (1998) 647.

【非專利文獻14】E Bach, E Cleve and E Schollmeyer, J.Text.Inst.Part 1 Fiber Sci.Text.Tecnol.,89 (1998) 657. [Non-Patent Document 14] E Bach, E Cleve and E Schollmeyer, J.Text.Inst.Part 1 Fiber Sci.Text.Tecnol., 89 (1998) 657.

【非專利文獻15】D Knittel, W Saus and E Schollmeyer,Tech.Text.,38 (1995) 184. [Non-Patent Document 15] D Knittel, W Saus and E Schollmeyer, Tech.Text., 38 (1995) 184.

【非專利文獻16】S-K Liao, P-S Chang and Y-C Lin,J.Text.Eng.,46 (2000) 123. [Non-Patent Literature 16] S-K Liao, P-S Chang and Y-C Lin, J.Text.Eng., 46 (2000) 123.

【非專利文獻17】S-K Liao, P-S Chang and Y-C Lin,J.Polym.Res.,7 (2000) 155. [Non-Patent Document 17] S-K Liao, P-S Chang and Y-C Lin, J. Polym. Res., 7 (2000) 155.

【非專利文獻18】K.Miyazaki et al., Color.Technol.,128 (2012) ,51-59. [Non-Patent Document 18] K. Miyazaki et al., Color. Technol., 128 (2012), 51-59.

【非專利文獻19】K.Miyazaki et al., Color.Technol.,128 (2012) ,60-67. [Non-Patent Document 19] K. Miyazaki et al., Color. Technol., 128 (2012), 60-67.

如上所述，用於提供具有優異染色堅牢度之染色聚丙烯纖維構造物的染料，已找到藍色及黃色之染料(參照非專利文獻18、19)。然而，為了可自由獲得色彩，必須有與減法混色三原色(黃、洋紅、青)相近色相(黃、紅、藍)之染料至少各1種。而構成此三原色之紅色的染料尚未被發現。因此，在聚丙烯纖維構造物，尚未能實現藉由染料配合之自由的色調之染色。 As described above, blue and yellow dyes have been found for dyes used to provide dyed polypropylene fiber structures with excellent dye fastness (see Non-Patent Documents 18 and 19). However, in order to be able to obtain colors freely, there must be at least one dye each with a hue (yellow, red, blue) similar to the three primary colors of subtractive color mixing (yellow, magenta, and cyan). The dye that constitutes the red of the three primary colors has not yet been discovered. Therefore, in the polypropylene fiber structure, the dyeing of the free hue by the dye combination has not yet been realized.

進一步地，在專利文獻6，揭示了包括分散染料或油溶性 染料等之中性的色素，但作為染色之對象的疏水性合成纖維僅被概括列舉。實際上，即使使用專利文獻6所記載之染料將聚丙烯纖維構造物染色，染料幾乎無法染著，即使染著，所染色之聚丙烯纖維構造物的染色堅牢度也顯著低劣。 Further, in Patent Document 6, it is disclosed that a disperse dye or oil-soluble Neutral pigments such as dyes, but hydrophobic synthetic fibers that are dyed objects are only listed in general. In fact, even if the polypropylene fiber structure is dyed with the dye described in Patent Document 6, the dye can hardly be dyed, and even if it is dyed, the dye fastness of the dyed polypropylene fiber structure is significantly poor.

本發明，係鑒於此等課題而成者，其目的在於提供一種染色之聚丙烯纖維構造物，其係以具有優異的染色堅牢度，並得以表現出構成減法混色三原色之紅色的染料所染色。 The present invention was made in view of these problems, and its object is to provide a dyed polypropylene fiber structure which is dyed with a dye that has excellent dye fastness and can exhibit red, which constitutes the three primary colors of subtractive mixed colors.

本發明於一態樣中，提供一種染色之聚丙烯纖維構造物，其特徵係以下述通式(1)所表示之紅色染料染色：

Figure 106145570-A0305-02-0007-2
式中，R1係分別獨立選自碳數4~8的支鏈烷基、及碳數9~19的芳基烷基所成群中的1種，n為1~3之整數。前述支鏈烷基係包含四級碳原子，前述芳基烷基之烷基部分係包含四級碳原子)。 In one aspect, the present invention provides a dyed polypropylene fiber structure, which is characterized by being dyed with a red dye represented by the following general formula (1):
Figure 106145570-A0305-02-0007-2
 In the formula, R1 is one independently selected from the group of branched alkyl groups having 4 to 8 carbons and arylalkyl groups having 9 to 19 carbons, and n is an integer of 1 to 3. The aforementioned branched alkyl group contains quaternary carbon atoms, and the alkyl portion of the aforementioned arylalkyl group contains quaternary carbon atoms).

在此，本說明書使用「四級碳原子」時，係指與4個其他碳原子結合的碳原子。 Here, when "quaternary carbon atom" is used in this specification, it refers to a carbon atom bonded to 4 other carbon atoms.

上述通式(1)中，n可為2。 In the above general formula (1), n may be 2.

上述通式(1)中，亦可為：n為2，且R1基分別獨立為前 述支鏈烷基。此外，上述通式(1)中，亦可為：n為1，且R1基為前述支鏈烷基。 In the above general formula (1), it may also be that n is 2, and the R 1 groups are each independently the aforementioned branched alkyl group. In addition, in the above general formula (1), n is 1 and the R 1 group is the aforementioned branched alkyl group.

此外，上述染色之聚丙烯纖維構造物，亦可為布。 In addition, the above-mentioned dyed polypropylene fiber structure may also be cloth.

本發明於另一態樣中，提供一種衣料品，其特徵係其使用上述染色之聚丙烯纖維構造物。 In another aspect, the present invention provides a clothing product characterized by using the above-mentioned dyed polypropylene fiber structure.

藉由本發明，可提供一種得以表現出減法混色三原色之紅色的染色之聚丙烯纖維構造物，其係以具有優異染色堅牢度及染色性的紅色染料所染色。 According to the present invention, it is possible to provide a dyed polypropylene fiber structure capable of expressing the red of the subtractive mixed color three primary colors, which is dyed with a red dye having excellent dye fastness and dyeability.

100:染色性試驗所使用裝置 100: Device used for dyeability test

101:液體CO2氣缸 101: Liquid CO 2 cylinder

102:停止閥 102: Stop valve

103:針閥 103: Needle valve

104:冷卻器 104: cooler

105:高壓幫浦 105: high pressure pump

106:送液幫浦 106: Liquid delivery pump

107:停止閥 107: Stop valve

108:安全閥 108: safety valve

109:壓力計 109: Pressure gauge

110:停止閥 110: Stop valve

111:預熱器 111: preheater

112:染色槽 112: Dyeing tank

116:過濾器 116: filter

117:磁力攪拌器 117: Magnetic stirrer

118:恆溫空浴槽 118: Constant temperature empty bath

119:磁力攪拌恆溫空浴槽 119: Magnetic stirring constant temperature empty bath

120:溫度計 120: Thermometer

121:停止閥 121: Stop valve

122:背壓控制閥 122: Back pressure control valve

123:加熱器 123: heater

124:半自動背壓控制閥 124: Semi-automatic back pressure control valve

200:超臨界流體染色裝置 200: Supercritical fluid dyeing device

201:液體CO2氣缸 201: Liquid CO 2 cylinder

202:過濾器 202: filter

203:冷卻套 203: Cooling jacket

204:高壓幫浦 204: high pressure pump

205:預熱器 205: preheater

206、207、208:壓力計 206, 207, 208: pressure gauge

209:磁力驅動部 209: Magnetic Drive

210:DC馬達 210: DC motor

211、212:安全閥 211, 212: safety valve

213:冷卻器 213: cooler

214、215、216、217、218:停止閥 214, 215, 216, 217, 218: stop valve

219:針閥 219: Needle Valve

220:加熱器 220: heater

221:滾筒 221: roller

222:高壓不鏽鋼槽 222: high pressure stainless steel tank

223:擦拭紙所包覆之染料 223: Dyes covered by wipes

224:葉輪 224: Impeller

【圖1】表示實施例中染色性試驗所使用之裝置的概略圖。 [Fig. 1] A schematic diagram showing the apparatus used in the dyeability test in the examples.

【圖2】表示實施例中用於超臨界流體染色之裝置的概略圖。 [Fig. 2] A schematic diagram showing the apparatus used for supercritical fluid dyeing in the embodiment.

實施型態中染色之聚丙烯纖維(PP)構造物，其特徵係其以下述通式(1)所表示之紅色染料染色：

Figure 106145570-A0305-02-0008-3
式中，R1係分別獨立選自碳數4~8的支鏈烷基、及碳數9~19的芳基烷基 所成群中的1種，n為1~3之整數。前述支鏈烷基係包含四級碳原子，前述芳基烷基之烷基部分係包含四級碳原子。 The polypropylene fiber (PP) structure dyed in the embodiment is characterized in that it is dyed with a red dye represented by the following general formula (1):
Figure 106145570-A0305-02-0008-3
 In the formula, R 1 is one independently selected from the group of branched alkyl groups having 4 to 8 carbons and arylalkyl groups having 9 to 19 carbons, and n is an integer of 1 to 3. The aforementioned branched alkyl group contains quaternary carbon atoms, and the alkyl portion of the aforementioned arylalkyl group contains quaternary carbon atoms.

以上述染料染色之聚丙烯纖維構造物，可表現出減法混色三原色之紅色。進一步地，該染色之聚丙烯纖維構造物，係洗滌堅牢度、耐光堅牢度、昇華堅牢度中任一者皆優異。 The polypropylene fiber structure dyed with the above-mentioned dyes can show the red of the three primary colors of subtractive mixed color. Furthermore, the dyed polypropylene fiber structure is excellent in any of washing fastness, light fastness, and sublimation fastness.

(染料) (dye)

構成本發明之染色聚丙烯纖維構造物的紅色染料，為上述通式(1)所表示之化合物。為了使聚丙烯纖維構造物可良好染上構成減法混色三原色之紅色，且使其為洗滌堅牢度、耐光堅牢度、昇華堅牢度中任一者皆良好者，必要係：上述通式(1)中之R1分別獨立選自碳數4~8的支鏈烷基、及碳數9~19的芳基烷基所成群中的1種；n為1~3之整數；前述支鏈烷基包含四級碳原子；前述芳基烷基之烷基部分包含四級碳原子。 The red dye constituting the dyed polypropylene fiber structure of the present invention is a compound represented by the above general formula (1). In order for the polypropylene fiber structure to be well dyed with the red color constituting the three primary colors of subtractive color mixing, and to make it have good washing fastness, light fastness, and sublimation fastness, it is necessary to be: the above general formula (1) Where R 1 is independently selected from the group of branched alkyl groups with 4 to 8 carbons and aryl alkyl groups with 9 to 19 carbons; n is an integer of 1 to 3; the aforementioned branched alkanes The group contains quaternary carbon atoms; the alkyl portion of the aforementioned arylalkyl group contains quaternary carbon atoms.

使R1之上述烷基及上述芳基烷基中之烷基部分為支鏈狀且包含四級碳原子，可獲得染色堅牢度較優異之染料。進一步地，由於上述通式(1)所表示之染料為固體，因此容易操作，且可微調整染色之程度(色之濃淡)，有利於工業生產 The above-described alkyl group of the R 1 alkyl group and the aryl moiety is branched alkyl of four carbon atoms and includes, than can be obtained excellent fastness of dyeing dye. Furthermore, since the dye represented by the above general formula (1) is a solid, it is easy to handle, and the degree of dyeing (color intensity) can be adjusted slightly, which is beneficial to industrial production

含有四級碳原子之上述烷基，可列舉例如：2-甲基丙烷-2-基(tert-丁基)基、2-甲基丁烷-2-基(tert-胺)基、2，4，4-三甲基戊烷-2-基(tert-辛)基、2-甲基庚烷-2-基。此等之中，基於染色時殘留染料較少、染色堅牢度較優異，以2-甲基丙烷-2-基、2-甲基丁烷-2-基、2，4，4-三甲基戊烷-2-基為較佳。 The above-mentioned alkyl groups containing quaternary carbon atoms include, for example, 2-methylpropan-2-yl (tert-butyl) group, 2-methylbutan-2-yl (tert-amine) group, 2, 4,4-Trimethylpentan-2-yl (tert-octyl), 2-methylheptan-2-yl. Among these, based on the fact that there are fewer residual dyes during dyeing and excellent dyeing fastness, 2-methylpropane-2-yl, 2-methylbutane-2-yl, 2,4,4-trimethyl Pentan-2-yl is preferred.

含有四級碳原子之上述芳香基烷基，可列舉例如：2-苯基 丙烷-2-基(枯基)基、2-苯基丁烷-2-基、2-(鄰-甲苯醯基)丙烷-2-基、1，1-二苯基丙基、1，1，1-三苯基甲基(三苯基甲基)。 又，上述芳香基烷基之碳數以9或10為佳。 The above-mentioned arylalkyl groups containing quaternary carbon atoms include, for example, 2-phenyl Propan-2-yl (cumyl) group, 2-phenylbutan-2-yl, 2-(o-tolyl)propan-2-yl, 1,1-diphenylpropyl, 1,1 , 1-Triphenylmethyl (triphenylmethyl). In addition, the carbon number of the arylalkyl group is preferably 9 or 10.

n=2或3之情形下，其2個或3個R1可各別為同一者，亦可為不同者。 In the case of n=2 or 3, the 2 or 3 R 1 may be the same or different.

以上述通式(1)所表示之化合物，亦可為下述通式(2)所表示之化合物。 The compound represented by the above general formula (1) may be a compound represented by the following general formula (2).

Figure 106145570-A0305-02-0010-4
式中，R2~R4分別獨立選自氫原子、碳數4~8的支鏈烷基、及碳數9~19的芳基烷基所成群中的1種。前述支鏈烷基包含四級碳原子，前述芳基烷基之烷基部分包含四級碳原子，R2~R4中至少1個為前述支鏈烷基或前述芳基烷基。
Figure 106145570-A0305-02-0010-4
 In the formula, R 2 to R 4 are each independently selected from a hydrogen atom, a branched alkyl group having 4 to 8 carbons, and an arylalkyl group having 9 to 19 carbons. The aforementioned branched alkyl group contains quaternary carbon atoms, the alkyl portion of the aforementioned arylalkyl group contains quaternary carbon atoms, and at least one of R 2 to R 4 is the aforementioned branched alkyl group or the aforementioned aryl alkyl group.

可進一步提升染色堅牢度，苯氧基上的取代基之數以兩個為佳，亦即，上述通式(1)中，n為2較佳。此外，基於同樣的理由，上述通式(2)中，較佳係R2~R4中有2個分別獨立為前述支鏈烷基或前述芳基烷基，剩餘1個為氫原子。 The color fastness can be further improved, and the number of substituents on the phenoxy group is preferably two. That is, in the above general formula (1), n is 2 preferably. In addition, for the same reason, in the above general formula (2), it is preferable that two of R 2 to R 4 are each independently the aforementioned branched alkyl group or the aforementioned aryl alkyl group, and the remaining one is a hydrogen atom.

基於可使染色時之殘留染料較少，且可良好調整染色之程度的再現性，較佳係R1為前述支鏈烷基，且n為1或2。此外，基於同樣的理由，上述通式(2)中，較佳係R2~R4分別獨立為氫原子或前述支鏈 烷基，且R2~R4中有1個或2個為前述支鏈烷基。特別係，基於可成為染色堅牢度較優異者，使染色時之殘留染料較少，上述通式(1)中，進一步較佳係R1為前述支鏈烷基，n為2。基於同樣的理由，上述通式(2)中，進一步較佳係R2~R4中有2個分別獨立為前述支鏈烷基，剩餘1個為氫原子。 Since the residual dye during dyeing can be reduced and the reproducibility of the degree of dyeing can be adjusted well, it is preferable that R 1 is the aforementioned branched alkyl group, and n is 1 or 2. In addition, for the same reason, in the above general formula (2), it is preferable that R 2 to R 4 are each independently a hydrogen atom or the aforementioned branched alkyl group, and one or two of R 2 to R 4 are the aforementioned Branched alkyl. In particular, it is more preferable that R 1 is the aforementioned branched alkyl group, and n is 2 in the above general formula (1), based on the fact that the dyeing fastness is better and the residual dye is less. For the same reason, in the above general formula (2), it is more preferable that two of R 2 to R 4 are each independently the aforementioned branched alkyl group, and the remaining one is a hydrogen atom.

本發明之特佳的實施型態中，上述染料係：上述通式(1)之R1為2，4，4-三甲基戊烷-2-基，n為1，苯氧基之4位有R1存在的化合物；或上述通式(1)之R1為2-甲基丙烷-2-基或2-甲基丁烷-2-基，n為2，苯氧基之2位及4位有R1存在的化合物。此等之化合物，具有優異染色堅牢度及染色性，在染色時特別不殘留染料，可再現性良好地控制染色之顏色。 In a particularly preferred embodiment of the present invention, the above-mentioned dye system: R 1 of the above general formula (1) is 2,4,4-trimethylpentan-2-yl, n is 1, 4 of phenoxy R 1 bit present in the compound; or R in the general formula (1) of 2-methyl-2-1-yl or 2-methyl-butan-2 group, n is 2, the two phenoxy And compounds with R 1 at position 4. These compounds have excellent fastness to dyeing and dyeability, especially no dye remains during dyeing, and the color of dyeing can be controlled with good reproducibility.

上述通式(1)所表示之紅色染料，藉由與可染聚丙烯纖維構造物之藍色染料及黃色染料，特別係，藉由與非專利文獻3、4中分別記載的藍色染料及黃色染料共同使用，可在聚丙烯纖維構造物上染色自由之色調。 The red dye represented by the above-mentioned general formula (1) is combined with the blue dye and the yellow dye that can dye polypropylene fiber structures, and in particular, is combined with the blue dye and the blue dye described in Non-Patent Documents 3 and 4, respectively. Yellow dyes can be used together to dye free hues on polypropylene fiber structures.

上述通式(1)所表示之染料為公知，可以該領域具通常知識者習知之方法製造。例如，可藉由在如Dyes and Pigments,95,2012,201-205所記載之公知之條件下，使市售的1-胺基-2-溴基-4-羥蒽-9，10-二酮與市售的經支鏈烷基或芳香烷基取代之酚反應而製造。 The dye represented by the above general formula (1) is publicly known and can be produced by a method known to those with ordinary knowledge in the field. For example, the commercially available 1-amino-2-bromo-4-hydroxyanthracene-9,10-bis can be made under known conditions as described in Dyes and Pigments, 95, 2012, 201-205 Ketones are produced by reacting commercially available phenols substituted with branched or aryl alkyl groups.

(聚丙烯纖維構造物) (Polypropylene fiber structure)

本發明之聚丙烯纖維構造物係包含聚丙烯纖維。在此，聚丙烯纖維只要包含聚丙烯樹脂，則無特別限定。可使用由聚丙烯樹脂單獨構成之纖維 形成聚丙烯纖維構造物，亦可使用聚丙烯纖維中配合及/或接合其他聚合物成分而配置的纖維，形成聚丙烯纖維構造物。 The polypropylene fiber structure of the present invention contains polypropylene fibers. Here, the polypropylene fiber is not particularly limited as long as it contains a polypropylene resin. Can use fiber made of polypropylene resin alone In order to form a polypropylene fiber structure, it is also possible to use polypropylene fiber blended and/or joined with other polymer components to form a polypropylene fiber structure.

可基於上述聚丙烯纖維，根據該領域習知之方法，製造各種形態的聚丙烯纖維構造物。聚丙烯纖維構造物之型態，可列舉例如線狀構造物(長纖線、短纖線、切割(slit)線、撕裂(split)線等)、綿(棉)狀構造物、紐狀構造物、布狀構造物(紡織品、編織品、不織布、氈、毛絨束織品等)及此等之組合，但並不限定於此等。此外，亦可使用市售之聚丙烯纖維構造物。又，亦可將聚酯等其他纖維混紡及/或混纖於聚丙烯纖維而製造纖維構造物。 Based on the above-mentioned polypropylene fibers, various forms of polypropylene fiber structures can be manufactured according to methods known in the field. The types of polypropylene fiber structures include, for example, linear structures (long fiber thread, short fiber thread, slit thread, split thread, etc.), cotton (cotton)-like structure, and button-like structure. Structures, cloth-like structures (textiles, knitted products, non-woven fabrics, felts, pile fabrics, etc.) and combinations thereof, but are not limited to these. In addition, commercially available polypropylene fiber structures can also be used. In addition, other fibers such as polyester may be blended and/or blended with polypropylene fibers to produce a fiber structure.

(染色之聚丙烯纖維構造物之製造方法) (Method of manufacturing dyed polypropylene fiber structure)

本發明之染色之聚丙烯纖維構造物，可使用超臨界二氧化碳流體，以上述通式(1)所表示之染料將上述聚丙烯纖維構造物染色而製造。以超臨界二氧化碳流體為媒介將聚丙烯纖維構造物染色之方法，為該領域具通常知識者所習知。例如，可根據非專利文獻3、4所記載之超臨界二氧化碳流體染色法，進行聚丙烯纖維構造物之染色。 The dyed polypropylene fiber structure of the present invention can be produced by dyeing the polypropylene fiber structure with the dye represented by the general formula (1) using supercritical carbon dioxide fluid. The method of dyeing polypropylene fiber structures with supercritical carbon dioxide fluid as a medium is well known to those with ordinary knowledge in this field. For example, the polypropylene fiber structure can be dyed according to the supercritical carbon dioxide fluid dyeing method described in Non-Patent Documents 3 and 4.

經上述通式(1)所表示之染料染色之聚丙烯纖維可呈現出減法混色三原色之紅色。又，「減法混色三原色之紅色」的範圍為該領域所習知，係指色彩之三屬性(色相、明度、彩度)之中所有色相(H值)被視為紅色範圍者。即色知覺之屬性之中，將色相量表化後的色相H(JIS Z8721：1993)以10RP為中心，由10P至10R之範圍。此外，上述通式(1)所表示之染料，亦可與例如非專利文獻3、4中分別記載的藍色染料及黃色染料組合，將聚丙烯纖維構造物染色而製造染色之聚丙烯纖維構造 物。此情形下，可將聚丙烯纖維構造物染色為自由之色調。 The polypropylene fiber dyed with the dye represented by the above general formula (1) can show the red of the three primary colors of subtractive mixed color. In addition, the range of "red of the three primary colors of subtractive mixed color" is well-known in this field, and refers to those whose hue (H value) among the three attributes of color (hue, lightness, chroma) is regarded as the red range. That is, among the attributes of color perception, the hue H (JIS Z8721: 1993) after the hue quantity is represented is centered at 10RP and ranges from 10P to 10R. In addition, the dye represented by the above general formula (1) may be combined with the blue dye and yellow dye described in Non-Patent Documents 3 and 4, respectively, to dye a polypropylene fiber structure to produce a dyed polypropylene fiber structure Things. In this case, the polypropylene fiber structure can be dyed in free colors.

(染色聚丙烯纖維構造物之用途) (Use of dyed polypropylene fiber structure)

本發明之染色聚丙烯纖維構造物之用途雖無特別限定，可列舉例如衣服、內衣、帽子、襪子、手套、運動用衣料等之衣料品、座椅片材等之車輛內裝材、地毯、窗簾、地蓆、沙發罩、抱枕套等之室內用品等。本發明之染色纖維構造物，由於可表現自由色調，因此可適合用於衣料品。 Although the use of the dyed polypropylene fiber structure of the present invention is not particularly limited, examples include clothing, underwear, hats, socks, gloves, sports clothing and other clothing materials, seat sheets and other vehicle interior materials, carpets, Curtains, floor mats, sofa covers, pillowcases and other indoor products. Since the dyed fiber structure of the present invention can express free colors, it can be suitably used for clothing.

以下揭示實施例，而詳細說明本發明，惟本發明係並非限定於此等之實施例者。 Examples are disclosed below to describe the present invention in detail, but the present invention is not limited to these examples.

【實施例】 [Example]

(材料) (material)

試驗所使用之染料1~26之化學構造如下表表1所示。此外，關於染料1~23、25、26，下表係一併表示對應此等的專利文獻6中所記載之構造式與取代基。 The chemical structures of the dyes 1~26 used in the experiment are shown in Table 1 below. Regarding dyes 1 to 23, 25, and 26, the following table shows the structural formulas and substituents described in Patent Document 6 corresponding to these.

Figure 106145570-A0305-02-0014-5
Figure 106145570-A0305-02-0014-5

Figure 106145570-A0305-02-0015-6
Figure 106145570-A0305-02-0015-6

Figure 106145570-A0305-02-0016-7
Figure 106145570-A0305-02-0016-7

Figure 106145570-A0305-02-0017-8
Figure 106145570-A0305-02-0017-8

Figure 106145570-A0305-02-0017-9
Figure 106145570-A0305-02-0017-9

Figure 106145570-A0305-02-0018-10
Figure 106145570-A0305-02-0018-10

染料1~5、7、8、12、14、15、24、25、26，係由有本化學工業股份有限公司所取得之試作合成品。以下此等係由紀和化學工業股份有限公司所取得：染料9之製品名為KP Plast Blue G；染料21之製品名為KP Plast Yellow HR；染料22之製品名為KP Plast Yellow 2HR；染料23之製品名為KP Plast Brilliant Red MG。以下此等係由日本化藥股份有限公司所取得：染料6之製品名為Kayaset Red B；染料10之製品名為Kayaset Blue FR；染料11之製品名為Kayaset Red 168。染料13、染料16、及染料20係分別從日本亨斯邁(Huntsman Japan)股份有限公司製的Teratop Pink 3G、Terasil Pink 2GLA、Terasil Blue BGE萃取分離所得。染料17，係從日本化藥股份有限公司製的Kayalon Polyester Blue EBL-E所萃取。染料18、染料19，係分別從日本德斯達(DyStar Japan)製Dianix Blue GL-FS、Dianix Blue AM-77萃取分離所得。 Dyestuffs 1~5, 7, 8, 12, 14, 15, 24, 25, 26 are prototype synthetic products obtained by Arimoto Chemical Industry Co., Ltd. The following are obtained by Jihe Chemical Industry Co., Ltd.: The product of dye 9 is called KP Plast Blue G; the product of dye 21 is called KP Plast Yellow HR; the product of dye 22 is called KP Plast Yellow 2HR; The product name is KP Plast Brilliant Red MG. The following are obtained by Nippon Kayaku Co., Ltd.: The product of dye 6 is named Kayaset Red B; the product of dye 10 is named Kayaset Blue FR; the product of dye 11 is named Kayaset Red 168. Dye 13, Dye 16, and Dye 20 were extracted and separated from Teratop Pink 3G, Terasil Pink 2GLA, and Terasil Blue BGE manufactured by Huntsman Japan Co., Ltd., respectively. Dye 17 is extracted from Kayalon Polyester Blue EBL-E manufactured by Nippon Kayaku Co., Ltd. Dye 18 and Dye 19 were obtained by extraction and separation from Dianix Blue GL-FS and Dianix Blue AM-77 manufactured by DyStar Japan.

2種聚丙烯布，係從三菱麗陽股份有限公司(三菱Rayon)所取得。其中一種，為110dtex/36 filaments之聚丙烯纖維線所成，圓編試驗機所編織者(聚丙烯布No.1)。此織物之紗圈密度粗(經圈 20/2.54cm；緯圈32/2.54cm)，因此，可以磁力攪拌器之弱攪拌力容易地均染。剩下的另一種，為用於測定染色堅牢度的二段針織(聚丙烯布No.2；250g/m2；190dtex/48 filaments之線；經圈2×33/2.54cm：緯圈2×34/2.54em)者。此兩段針織，係使用蘇打灰(工業用等級，2g/dm3)、1g/dm3界面活性劑(Daisurf MOL-315；第一工業製藥股份有限公司)、0.5g/dm3螫合劑(Sizol FX-20；第一工業製藥股份有限公司)，於液流染色機以水系在80℃下精煉。其後，離心脫水聚丙烯布No.2，作為前處理將切開者以130℃熱固。 Two types of polypropylene fabrics are obtained from Mitsubishi Rayon Co., Ltd. (Mitsubishi Rayon). One of them is made of 110dtex/36 filaments polypropylene fiber thread, which is woven by a circular knitting machine (polypropylene cloth No.1). The yarn loop density of this fabric is thick (warp loop 20/2.54cm; weft loop 32/2.54cm), so it can be easily even dyed with the weak stirring power of a magnetic stirrer. The other one remaining is the two-stage knitting (polypropylene cloth No.2; 250g/m 2 ; 190dtex/48 filaments; warp loop 2×33/2.54cm: weft loop 2× 34/2.54em). The two-stage knitting uses soda ash (industrial grade, 2g/dm 3 ), 1g/dm 3 surfactant (Daisurf MOL-315; First Industrial Pharmaceutical Co., Ltd.), 0.5g/dm 3 chelating agent ( Sizol FX-20; First Industrial Pharmaceutical Co., Ltd.), refined in a liquid dyeing machine with water system at 80°C. Thereafter, the polypropylene cloth No. 2 was dewatered by centrifugation, and the cut pieces were heat-set at 130°C as a pretreatment.

木綿線(30/綿紗支數)，係從可樂牌股份有限公司(Clover Mfg Co.,Ltd.)所購入。染色程序中，使用3種綿布包覆聚丙烯布，使超臨界流體擴散。第1種具有線網構造(綿布No.1：縱線30條/2.54cm，橫線30條/2.54cm)，第2種具有單面法蘭絨構造(綿布No.2)。此等布係從蓓福藤本股份有限公司(Pip Fujimoto)購入。第3種具有平織構造(綿布No.3：縱線45條/2.54cm，橫線45條/2.54cm；製品名「山東晒」)，從長谷川綿行股份有限公司購入。 Wood wool thread (30/ cotton yarn count), from the Cola Brand Co., Ltd. (Clover Mfg Co., Ltd.). In the dyeing process, three kinds of cotton cloth are used to cover the polypropylene cloth to diffuse the supercritical fluid. The first type has a wire mesh structure (cotton cloth No. 1: 30 vertical lines/2.54 cm, and 30 horizontal lines/2.54 cm), and the second type has a single-sided flannel structure (cotton cloth No. 2). These cloths were purchased from Pip Fujimoto Co., Ltd. (Pip Fujimoto). The third type has a plain weave structure (cotton cloth No. 3: vertical threads 45/2.54cm, horizontal threads 45/2.54cm; product name "Shandong Sun"), purchased from Hasegawa Cotton Co., Ltd.

液體二氧化碳(>99.5%)，由宇野氧氣股份有限公司取得。試驗藥等級的丙酮，從納卡萊提斯克股份有限公司(Nacalai Tesque,INC.)購入。 Liquid carbon dioxide (>99.5%), obtained by Uno Oxygen Co., Ltd. Test drug grade acetone was purchased from Nacalai Tesque, INC..

使用上述染料1~26，依照下述方法進行聚丙烯布之染色試驗。 Using the above dyes 1~26, perform the dyeing test of polypropylene cloth according to the following method.

(染色性試驗) (Dyeability test)

染色性試驗所使用的裝置如圖1所示。染色性試驗裝置100，係由液 體CO2氣缸101、停止閥102、107、110、121、針閥103、送液幫浦106(由冷卻器104及高壓幫浦105所構成)、安全閥108、壓力計109、磁力攪拌恆溫空浴槽119(由預熱器111、染色槽112、過濾器116、磁力攪拌器117、恆溫空氣浴槽118所構成)、溫度計120、半自動背壓控制閥124(由背壓控制閥123、加熱器123所構成)所構成。磁力攪拌恆溫空浴槽119，係沿用日本分光股份有限公司製的溫度控制爐內的50cm3不鏽鋼槽之套組(SCF-Sro型)。送液幫浦106，係使用日本分光股份有限公司製的二氧化碳送液幫浦(SCF-Sro型)。半自動背壓控制閥124，係使用日本分光股份有限公司製的半自動背壓控制閥(SCF-Bpg/M型)。 The device used in the dyeability test is shown in Figure 1. The dyeability test device 100 consists of a liquid CO 2 cylinder 101, stop valves 102, 107, 110, 121, a needle valve 103, a liquid delivery pump 106 (consisting of a cooler 104 and a high pressure pump 105), and a safety valve 108 , Pressure gauge 109, magnetic stirring thermostatic air bath 119 (consisting of preheater 111, dyeing tank 112, filter 116, magnetic stirrer 117, constant temperature air bath 118), thermometer 120, semi-automatic back pressure control valve 124 (by Back pressure control valve 123 and heater 123). The magnetic stirring constant temperature air bath 119 is a set (SCF-Sro type) of a 50cm 3 stainless steel tank in a temperature controlled furnace manufactured by JASCO Corporation. The liquid feeding pump 106 is a carbon dioxide liquid feeding pump (SCF-Sro type) manufactured by JASCO Corporation. The semi-automatic back pressure control valve 124 is a semi-automatic back pressure control valve (SCF-Bpg/M type) manufactured by JASCO Corporation.

使用玻璃纖維濾紙(2×2cm；ADVANTEC GA-55；艾德凡提克東洋股份有限公司(ADVANTEC東洋)製)，使各染料(約3mg)保持如下：首先將一張濾紙浸漬於丙酮，接著，將染料置於剩餘的濾紙上，以經浸漬的濾紙覆蓋之。丙酮，係為了使兩張濾紙容易積層而使用。接著，將此等於室溫乾燥，使丙酮除去。將攪拌子115、聚丙烯布No.1(約10g)114、夾於兩張濾紙間之染料113，依序置入染色槽112內，再將染色槽112密封。在大氣壓力下將染色槽112內之空氣換置成二氧化碳。 Using glass fiber filter paper (2×2cm; ADVANTEC GA-55; manufactured by ADVANTEC Toyo Co., Ltd.), the dyes (approximately 3 mg) are maintained as follows: First, a filter paper is immersed in acetone, and then , Place the dye on the remaining filter paper and cover it with the impregnated filter paper. Acetone is used to make it easy to stack two filter papers. Next, this was dried at room temperature to remove acetone. Put the stir bar 115, the polypropylene cloth No. 1 (about 10g) 114, and the dye 113 sandwiched between two filter papers into the dyeing tank 112 in order, and then seal the dyeing tank 112. The air in the dyeing tank 112 is replaced with carbon dioxide under atmospheric pressure.

待恆溫空浴槽118內之溫度到達所定之溫度(120℃)後，藉由二氧化碳送液幫浦106，將染色槽112加壓至二氧化碳壓力25MPa，再加熱至染色溫度(120℃)。藉由背壓控制閥122，將染色性試驗裝置系統內之二氧化碳之壓力控制於25MPa，以磁力攪拌器攪拌染浴。60分鐘後，一邊維持攪拌，一邊藉由背壓控制閥122，將染色槽112漸漸減壓至大氣壓力。 After the temperature in the constant-temperature empty bath 118 reaches a predetermined temperature (120°C), the dyeing tank 112 is pressurized to a carbon dioxide pressure of 25 MPa by the carbon dioxide delivery pump 106, and then heated to the dyeing temperature (120°C). By the back pressure control valve 122, the pressure of carbon dioxide in the dyeability test device system is controlled to 25 MPa, and the dye bath is stirred with a magnetic stirrer. After 60 minutes, while maintaining stirring, the dyeing tank 112 is gradually decompressed to atmospheric pressure by the back pressure control valve 122.

將處理後的聚丙烯纖維布從染色槽112取出。接著，若為染料未於纖維內部擴散而於纖維表面析出之情形，使染色布浸漬於室溫之丙酮30秒，去除染色布之表面上所析出的染料。取出浸漬之布，在室溫下乾燥去除丙酮。關於染色能，係將結果分類如下。 The treated polypropylene fiber cloth is taken out from the dyeing tank 112. Next, if the dye does not diffuse inside the fiber and precipitates on the surface of the fiber, the dyed cloth is immersed in acetone at room temperature for 30 seconds to remove the dye deposited on the surface of the dyed cloth. Take out the impregnated cloth and dry it at room temperature to remove acetone. Regarding dyeing energy, the department classified the results as follows.

○：染色良好 ○: Good dyeing

△：染色淡 △: light dyeing

×：全未染色或僅有少許汙染。 ×: No staining at all or little contamination.

進一步地，確認兩張濾紙之間有無殘存之染料。此外，亦確認於染色槽112之內壁有無析出之染料。於濾紙殘留者及內壁所析出者合計為槽內殘留染料，將結果分類如下。 Further, confirm whether there is residual dye between the two filter papers. In addition, it is also confirmed whether there is any dye deposited on the inner wall of the dyeing tank 112. The residues on the filter paper and those deposited on the inner wall are the total dye remaining in the tank, and the results are classified as follows.

◎：無殘留 ◎: No residue

○：微量殘留(目視下可確認到粉末) ○: Trace residue (powder can be confirmed under visual inspection)

△：殘留多 △: much residue

×：幾乎全量殘留 ×: Almost all remains

(超臨界流體染色程序) (Supercritical fluid dyeing procedure)

對於染色性優異(亦即，染色能良好且槽內殘留染料少)的染料，將其製成評價染色堅牢度用之染色布。將聚丙烯布No.2裁切為20×150cm，秤量重量(約75g)。綿布No.1、2及3，分別裁切為20×100cm、20×75cm、20×35cm。首先，將綿布No.1及2依序捲繞於有打孔(直徑3mm、孔數/面積1.87/cm2、有效寬度190mm)的不鏽鋼滾筒(寬度220mm；外徑30mm、內徑26mm)。為了避免打孔對聚丙烯布No.2之染色的直接影響，將此等布做為底布使用。底布，係避免流體從打孔直線通 過，從而可均一流動於被染物。接著，將聚丙烯布No.2及綿布No.3依據捲繞。綿布No.3，係防止來自槽之放射熱導致聚丙烯布收縮。捲繞好之卷以綿線寬鬆地綁住先端而固定。 For dyes that are excellent in dyeability (that is, dyeability is good and there is little residual dye in the tank), they are made into dyed cloth for evaluating dye fastness. Cut polypropylene cloth No. 2 to 20×150 cm, and measure the weight (about 75 g). Cotton cloth No. 1, 2 and 3 are cut into 20×100cm, 20×75cm, 20×35cm, respectively. First, the cotton cloth Nos. 1 and 2 were wound in sequence on a stainless steel drum (width 220 mm; outer diameter 30 mm, inner diameter 26 mm) with perforations (diameter 3 mm, number of holes/area 1.87/cm 2 , effective width 190 mm). In order to avoid the direct impact of perforation on the dyeing of polypropylene cloth No.2, use this cloth as a base cloth. The base fabric prevents the fluid from passing straight through the perforations, so that it can flow uniformly on the dyed object. Next, polypropylene cloth No. 2 and cotton cloth No. 3 are wound according to the requirements. Cotton cloth No.3 prevents the shrinkage of the polypropylene cloth caused by the radiant heat from the groove. The wound roll is loosely tied to the tip with cotton thread and fixed.

用於超臨界流體染色之裝置係如圖2所示。超臨界流體染色裝置200，係由液體CO2氣缸201、過濾器202、冷卻套203、高壓幫浦204、預熱器205、壓力計206~208、磁力驅動部209、DC馬達210、安全閥211、212、冷卻器213、停止閥214~218、針閥219、加熱器220所構成。將捲繞有布試料之滾筒221置入高壓不鏽鋼槽222(容積2230cm3)。 將以擦拭紙(KimWipes S-200，日本製紙庫瑞西亞(Crecia)股份有限公司製)包覆之染料223(聚丙烯被染物之質量之0.3%；即0.3% omf)，置於槽222內之滾筒221之上的流體通路。 The device used for supercritical fluid dyeing is shown in Figure 2. The supercritical fluid dyeing device 200 consists of a liquid CO 2 cylinder 201, a filter 202, a cooling jacket 203, a high-pressure pump 204, a preheater 205, a pressure gauge 206~208, a magnetic drive unit 209, a DC motor 210, and a safety valve 211, 212, cooler 213, stop valves 214 to 218, needle valve 219, heater 220. The drum 221 wound with the cloth sample is placed in a high-pressure stainless steel tank 222 (volume 2230 cm 3 ). Dye 223 (0.3% of the weight of the polypropylene dyed object; that is, 0.3% omf) covered with wiping paper (KimWipes S-200, manufactured by Crecia Co., Ltd.) is placed in the tank 222 The fluid path above the roller 221.

關閉槽222之閥，120℃加熱。到達染色溫度後，以幫浦204，將液體二氧化碳(1.3kg)通過冷卻套203流動於槽222。二氧化碳流體，以槽222之底部所安裝的不鏽鋼葉輪224及磁力驅動部209使其循環。磁力驅動布209之轉速為750rpm。流體之流動方向，為從滾筒221之內側至外側。 Close the valve of tank 222 and heat at 120°C. After reaching the dyeing temperature, liquid carbon dioxide (1.3 kg) is flowed into the tank 222 through the cooling jacket 203 with the pump 204. The carbon dioxide fluid is circulated by the stainless steel impeller 224 and the magnetic drive part 209 installed at the bottom of the tank 222. The rotational speed of the magnetic drive cloth 209 is 750 rpm. The flow direction of the fluid is from the inside to the outside of the drum 221.

溫度、壓力循環速度到達一定值(即120℃、25MPa、750rpm)後，在此等條件下維持60分鐘，將聚丙烯布染色。控制放出速度，使壓力在15分鐘內從25MPa降低至大氣壓。循環係持續，直至槽內壓幾乎降低到臨界壓(8.0~7.4MPa)。其後，將染色之聚丙烯布從槽222取出。使用聚丙烯布No.2之情形下的染色能及槽內殘留染料，與使用聚丙烯布No.1之染色性試驗之結果為同等。 After the temperature and pressure cycle speed reaches a certain value (ie, 120°C, 25MPa, 750rpm), the polypropylene cloth is dyed by maintaining it under these conditions for 60 minutes. Control the release speed to reduce the pressure from 25MPa to atmospheric pressure within 15 minutes. The circulation system continues until the internal pressure of the tank is almost reduced to the critical pressure (8.0~7.4MPa). After that, the dyed polypropylene cloth is taken out from the tank 222. The dyeing performance and residual dye in the tank when using polypropylene cloth No. 2 are equivalent to the results of the dyeability test using polypropylene cloth No. 1.

藉由持續循環下慢慢釋壓之操作將聚丙烯布之表面上所析出的染料除去。因此，只要不是會導致大過剩之染料濃度，應不需要後續之洗淨程序。染料從表面析出時傾向表現異常低之性能的摩擦堅牢度(JIS L0849、II型、添付白布：綿)，係藉由此放壓操作使其為正常。本發明之實施例中，乾摩擦、濕摩擦皆表現為4-5級至5級。使用聚丙烯布No.2之情形下的染色能與槽內殘留染料，與使用聚丙烯布No.1之染色性試驗之結果為同等。 The dye deposited on the surface of the polypropylene cloth is removed by the operation of slowly releasing pressure under continuous circulation. Therefore, as long as it is not a dye concentration that will cause a large surplus, subsequent cleaning procedures should not be required. The rubbing fastness (JIS L0849, Type II, white cloth: cotton), which tends to exhibit abnormally low performance when the dye precipitates from the surface, is made normal by this depressurization operation. In the embodiment of the present invention, both dry friction and wet friction have a performance of 4-5 to 5. The dyeing performance in the case of using polypropylene cloth No. 2 and the residual dye in the tank is equivalent to the results of the dyeability test using polypropylene cloth No. 1.

(洗滌堅牢度) (Washing fastness)

洗滌堅牢度試驗，使用多纖交織布(交織1號：JIS L0803：2005；綿、尼龍、醋酸纖維、毛線、嫘縈、丙烯腈纖維、絹及聚酯所紡織之布)，以JIS L0844：2005 A-2法(基於ISO 105-C02：1989試驗2)實施。多纖交織布之汙染，係表示最被汙染之部分的評價。此外，不僅布之汙染，亦參照ISO 105-D01：1994，評價試驗液之汙染。試驗液之汙染之評價中，使容器內殘存之試驗液通過濾紙。使用汙染評價用之灰階之透過光，將經過濾之試驗液之汙染之著色，在置於白色卡之前的玻璃製試驗管(直徑25mm)內，與未使用過之試驗液者比較。 Washing fastness test, using multi-fiber interwoven fabric (Interwoven No. 1: JIS L0803: 2005; cotton, nylon, acetate fiber, wool, rayon, acrylonitrile fiber, silk and polyester cloth woven), according to JIS L0844: 2005 A-2 method (based on ISO 105-C02: 1989 Test 2) was implemented. The contamination of multi-fiber interwoven fabrics is an evaluation that represents the most contaminated part. In addition, not only the pollution of the cloth, but also the evaluation of the pollution of the test liquid with reference to ISO 105-D01:1994. In the evaluation of the contamination of the test liquid, the test liquid remaining in the container is passed through the filter paper. Use the transmitted light of the gray scale for pollution evaluation to color the pollution of the filtered test liquid in the glass test tube (diameter 25mm) before the white card, and compare it with the unused test liquid.

(耐光堅牢度) (Light fastness)

染色之聚丙烯纖維布之耐光堅牢度，以JIS L0842(第3曝光法)為基準而評價。耐光堅牢度試驗，係使用紫外線碳弧燈光，以3級及/或4級實施第3曝光法。 The light fastness of the dyed polypropylene fiber cloth was evaluated based on JIS L0842 (third exposure method). The light fastness test uses ultraviolet carbon arc lamp to implement the third exposure method at level 3 and/or level 4.

(昇華堅牢度) (Sublimation fastness)

染色聚丙烯布之昇華堅牢度，以JIS L0854為基準，於添付白布使用 尼龍(單一纖維布(I)7號：JIS L0803：2005)而評價。 The sublimation fastness of dyed polypropylene cloth is based on JIS L0854, and it is used for adding white cloth Nylon (single fiber cloth (I) No. 7: JIS L0803: 2005) was evaluated.

(測色) (Color measurement)

染色之聚丙烯布之測色，使用分光測色計(CM-600d：日本柯尼卡美能達股份有限公司製)。分光反射率之測定條件為：將4張試料重疊於無螢光白色紙，測定徑φ8mm，觀察條件2°視野，觀察光源D65，測定波長範圍400~700nm，測定波長間隔10nm，除去正反射光(SCE：Specular Component Exclude)。基於分光反射率，以CIE1976L*a*b*為基準求L*、a*、b*之值。進一步地，以JIS Z8721：1993為基準，求D65光源中色相H。 The color measurement of the dyed polypropylene cloth is performed with a spectrophotometer (CM-600d: manufactured by Konica Minolta Co., Ltd.). The spectroscopic reflectance measurement conditions are: superimpose 4 samples on non-fluorescent white paper, measure diameter φ8mm, observe condition 2° field of view, observe light source D65, measure wavelength range 400~700nm, measure wavelength interval 10nm, remove regular reflection light (SCE: Specular Component Exclude). Based on the spectral reflectance, the values of L*, a*, and b* are calculated based on CIE1976L*a*b*. Furthermore, based on JIS Z8721: 1993, the hue H in the D65 light source is determined.

(實施例1~6、比較例1~20) (Examples 1 to 6, Comparative Examples 1 to 20)

使用染料1~26之實施例1~6、比較例1~20之個別試驗結果係示於表2。確認聚丙烯布之染色良好的實施例1~6、比較例1~3、比較例6、7、19、20，亦進行染色堅牢度之評價。又，比較例3，由於染色所使用之染料5為焦油狀，秤量困難，因此並未評價洗滌堅牢度、昇華堅牢度。此外，進行實施例1~6、比較例1、2、20之染色聚丙烯布之測色。其結果係示於表3。 The individual test results of Examples 1 to 6 and Comparative Examples 1 to 20 using dyes 1 to 26 are shown in Table 2. Examples 1 to 6, Comparative Examples 1 to 3, and Comparative Examples 6, 7, 19, and 20 in which it was confirmed that the polypropylene cloth dyed well were also evaluated for dye fastness. In addition, in Comparative Example 3, since the dye 5 used for dyeing was tar-like and weighing was difficult, the washing fastness and the sublimation fastness were not evaluated. In addition, the color measurement of the dyed polypropylene fabrics of Examples 1 to 6, Comparative Examples 1, 2, and 20 was performed. The results are shown in Table 3.

Figure 106145570-A0305-02-0025-11
Figure 106145570-A0305-02-0025-11

Figure 106145570-A0305-02-0025-12
Figure 106145570-A0305-02-0025-12

如表2所示，實施例1~6之染色聚丙烯布，係同時表現優異染色性及優異染色堅牢度。相對於此，比較例1、2、20，染色能雖良好但槽內殘留染料多，洗滌堅牢度及昇華堅牢度之汙染惡劣；比較例4、5、8~18，聚丙烯布未被染料良好染色。比較例6、7、19雖表現良好染色 性，但比較例6中洗滌堅牢度及耐光堅牢度之兩者為不良，比較例7中洗滌堅牢度為不良，比較例19中耐光堅牢度為不良。 As shown in Table 2, the dyed polypropylene fabrics of Examples 1 to 6 showed both excellent dyeability and excellent fastness to dyeing. In contrast, in Comparative Examples 1, 2, and 20, although the dyeing performance is good, there are many residual dyes in the tank, and the pollution of washing fastness and sublimation fastness is bad; Comparative Examples 4, 5, 8~18, the polypropylene cloth is not dyed Good dyeing. Comparative examples 6, 7, and 19 showed good staining However, in Comparative Example 6, both washing fastness and light fastness were bad, the washing fastness in Comparative Example 7 was bad, and the light fastness in Comparative Example 19 was bad.

基於上述染色試驗之結果，相當於專利文獻6所記載之代表性染料的染料1~23中，可將聚丙烯布良好染色者，僅有染料1~8、11、12、25(實施例1~5、比較例1~3、6、7、實施例6)，可理解有許多染料即使藉由超臨界二氧化碳仍無法將聚丙烯布染色。另一方面，相當於非專利文獻19所記載之代表性染料(1，4-雙(辛基胺)-蒽醌)之位置異構物的染料24(比較例19)，雖染色性良好，但耐光堅牢度差。可理解僅以改變取代位置獲得目標色相之染料，係無法為染色性、染色堅牢度皆良好者。此外，根據實施例1~6與比較例1~3、6、7、8~11、19、20之比較所示，為了獲得染色性(染色能、槽內殘留染料)、染色堅牢度(洗滌堅牢度、耐光堅牢度、昇華堅牢度)皆良好者，染料之化學構造，如上述通式(1)所示，需要為：蒽醌環之1位之取代基為胺基；2位之取代基為苯氧基，且經包含四級碳原子之支鏈烷基或芳香基烷基取代；4位之取代基為羥基。 Based on the results of the above dyeing test, among the dyes 1 to 23 corresponding to the representative dyes described in Patent Document 6, only dyes 1 to 8, 11, 12, and 25 can dye polypropylene cloth well (Example 1 ~5. Comparative Examples 1~3, 6, 7, and Example 6), it can be understood that many dyes cannot dye polypropylene cloth even with supercritical carbon dioxide. On the other hand, dye 24 (Comparative Example 19) corresponding to the positional isomer of the representative dye (1,4-bis(octylamine)-anthraquinone) described in Non-Patent Document 19 (Comparative Example 19) has good dyeability, But the light fastness is poor. It can be understood that dyes that only obtain the target hue by changing the substitution position cannot be those with good dyeability and fastness. In addition, according to the comparison between Examples 1 to 6 and Comparative Examples 1 to 3, 6, 7, 8 to 11, 19, and 20, in order to obtain dyeability (dying energy, residual dye in the tank), dye fastness (washing If the fastness, light fastness, and sublimation fastness are all good, the chemical structure of the dye, as shown in the above general formula (1), needs to be: the substituent at position 1 of the anthraquinone ring is an amino group; the substituent at position 2 The group is a phenoxy group and is substituted by a branched alkyl or arylalkyl group containing four-stage carbon atoms; the substituent at the 4-position is a hydroxyl group.

此外，相對於實施例1~6所使用染料皆為固體，染料8相當於上述通式(1)中R2為碳數9之直鏈烷基者且為焦油狀，無法控制染色之程度(色之濃淡)，不適合工業生產。 Further, as used in Example 1 to 6 are all with respect to the solid dye, a dye corresponding to the general formula 8 (1), R 2 is a linear alkyl group having a carbon number of 9 persons and tar-like, can not control the degree of staining ( The shade of color), not suitable for industrial production.

如表3所示，實施例1~6之染色聚丙烯布皆表現減法混色三原色之赤色。實施例1、2、4、6使用上述通式(1)中之苯氧基上之取代基為支鏈烷基的染料1、2、4、20，其等係槽內殘留染料較少。特別係，實施例4使用染料4，其係上述通式(1)之R1為2-甲基丁烷-2- 基，n=2，於苯氧基之2位及4位存在有R1；實施例6使用染料25，其係上述通式(1)之R1為2-甲基丙烷-2-基，n=2，於苯氧基之2位及4位存在有R1，此兩者在染色時僅有痕跡量的染料作為擦拭紙上染漬殘留於槽內，此即代表，所使用的染料幾乎全被纖維所吸收。在此之上，實施例4、6，係洗滌堅牢度、耐光堅牢度、昇華堅牢度皆優異。 As shown in Table 3, the dyed polypropylene fabrics of Examples 1 to 6 all exhibit the red color of the three primary colors of subtractive mixed color. Examples 1, 2, 4, and 6 use dyes 1, 2, 4, and 20 in which the substituent on the phenoxy group in the general formula (1) is a branched alkyl group, and the remaining dyes in the tank are less. In particular, dye 4 is used in Example 4, which is that R 1 of the above general formula (1) is 2-methylbutan-2-yl, n=2, and R is present at the 2-position and 4-position of the phenoxy group. 1 ; Example 6 uses dye 25, which is that R 1 of the general formula (1) is 2-methylpropan-2-yl, n=2, and R 1 exists in the 2-position and 4-position of the phenoxy group, During dyeing, only traces of dye remain in the groove as stains on the wiping paper, which means that almost all the dye used is absorbed by the fiber. In addition, Examples 4 and 6 are excellent in washing fastness, light fastness, and sublimation fastness.

以上，雖參照上述之實施型態說明本發明，惟本發明並非限定於上述之實施型態，將實施型態之構成適宜組合或置換者亦屬於本發明所含括者。此外，亦可基於該領域具通常知識者之知識，對於實施型態加以在實施型態中組合或步驟之順序適宜組合更換，或變更各種設計等之變形，如此加以變形之實施型態，亦包含於本發明之範圍。 Above, although the present invention has been described with reference to the above-mentioned embodiments, the present invention is not limited to the above-mentioned embodiments, and suitable combinations or substitutions of the constitutions of the embodiments are also included in the present invention. In addition, based on the knowledge of a person with ordinary knowledge in the field, the implementation pattern can be combined in the implementation pattern or the order of the steps is appropriately combined, or various designs are changed. Such a modified implementation pattern is also It is included in the scope of the present invention.

【產業利用性】 【Industrial Utilization】

本發明，係可利用於衣服、內衣、帽子、襪子、手套、運動用衣料等之衣料品、座椅片材等之車輛內裝材、地毯、窗簾、地蓆、沙發罩、抱枕套等之室內用品等。 The present invention can be used in clothing, underwear, hats, socks, gloves, sports clothing and other clothing materials, seat sheets and other vehicle interior materials, carpets, curtains, floor mats, sofa covers, pillowcases, etc. Indoor supplies, etc.

Claims (9)

一種染色之聚丙烯纖維構造物，其特徵係其使用超臨界二氧化碳流體作為染色媒介，以下述通式(1)所表示之紅色染料染色：
Figure 106145570-A0305-02-0030-13
 前述通式(1)中，R1係分別獨立選自碳數4~8的支鏈烷基、及碳數9~19的芳基烷基所成群中的1種，n為1~3，前述支鏈烷基係包含四級碳原子，前述芳基烷基之烷基部分係包含四級碳原子。 A dyed polypropylene fiber structure, characterized in that it uses supercritical carbon dioxide fluid as the dyeing medium and is dyed with a red dye represented by the following general formula (1):
Figure 106145570-A0305-02-0030-13
 In the aforementioned general formula (1), R 1 is each independently selected from the group of branched alkyl groups having 4 to 8 carbons and aryl alkyl groups having 9 to 19 carbons, and n is 1 to 3. The aforementioned branched alkyl group contains quaternary carbon atoms, and the alkyl portion of the aforementioned arylalkyl group contains quaternary carbon atoms. 如申請專利範圍第1項所記載之染色之聚丙烯纖維構造物，其中，n為2。 Such as the dyed polypropylene fiber structure described in item 1 of the scope of patent application, where n is 2. 如申請專利範圍第2項所記載之染色之聚丙烯纖維構造物，其中，n為2，且R1基為前述支鏈烷基。 The dyed polypropylene fiber structure described in item 2 of the scope of patent application, wherein n is 2, and the R 1 group is the aforementioned branched alkyl group. 如申請專利範圍第1項所記載之染色之聚丙烯纖維構造物，其中，n為1，且R1基為前述支鏈烷基。 The dyed polypropylene fiber structure described in item 1 of the scope of patent application, wherein n is 1, and the R 1 group is the aforementioned branched alkyl group. 如申請專利範圍第1項所記載之染色之聚丙烯纖維構造物，其中，前述紅色染料為1-胺基-4-羥基-2-〔2，4-雙(2-甲基丙烷-2-基)苯氧基〕蒽-9，10-二酮。 As the dyed polypropylene fiber structure described in item 1 of the scope of patent application, the red dye is 1-amino-4-hydroxy-2-[2,4-bis(2-methylpropane-2- Yl)phenoxy]anthracene-9,10-dione. 如申請專利範圍第1項所記載之染色之聚丙烯纖維構造物，其中，前述紅色染料為1-胺基-4-羥基-2-〔4-(2，4，4-三甲基戊烷-2-基)苯氧基〕蒽-9，10-二酮。 The dyed polypropylene fiber structure described in item 1 of the scope of patent application, wherein the red dye is 1-amino-4-hydroxy-2-[4-(2,4,4-trimethylpentane) -2-yl)phenoxy]anthracene-9,10-dione. 如申請專利範圍第1至6項中任一項所記載之染色之聚丙烯纖維構造物，其中，前述染色之聚丙烯纖維構造物根據JIS L0849測定的摩擦堅牢度為4-5級以上。 The dyed polypropylene fiber structure described in any one of items 1 to 6 in the scope of the patent application, wherein the aforesaid dyed polypropylene fiber structure has a rubbing fastness measured in accordance with JIS L0849 of 4-5 or higher. 如申請專利範圍第1至6項中任一項所記載之染色之聚丙烯纖維構造物，且其係為布。 The dyed polypropylene fiber structure described in any one of items 1 to 6 of the scope of the patent application is cloth. 一種衣料品，其係使用申請專利範圍第1至8項中任一項所記載之染色之聚丙烯纖維構造物。 A clothing product using the dyed polypropylene fiber structure described in any one of items 1 to 8 in the scope of patent application.
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