WO2016184390A1 - 一种无染阻燃粘胶纤维有色长丝和短丝的纺丝成形方法 - Google Patents

一种无染阻燃粘胶纤维有色长丝和短丝的纺丝成形方法 Download PDF

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WO2016184390A1
WO2016184390A1 PCT/CN2016/082486 CN2016082486W WO2016184390A1 WO 2016184390 A1 WO2016184390 A1 WO 2016184390A1 CN 2016082486 W CN2016082486 W CN 2016082486W WO 2016184390 A1 WO2016184390 A1 WO 2016184390A1
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Prior art keywords
spinning
fiber
filaments
flame retardant
colored
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PCT/CN2016/082486
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English (en)
French (fr)
Inventor
刘承修
毕慎平
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北京赛欧兰阻燃纤维有限公司
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Priority claimed from CN201510259426.3A external-priority patent/CN104846452B/zh
Priority claimed from CN201510258077.3A external-priority patent/CN104831386B/zh
Application filed by 北京赛欧兰阻燃纤维有限公司 filed Critical 北京赛欧兰阻燃纤维有限公司
Publication of WO2016184390A1 publication Critical patent/WO2016184390A1/zh

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/02—Preparation of spinning solutions
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/08—Composition of the spinning solution or the bath
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/08—Composition of the spinning solution or the bath
    • D01F2/16—Addition of dyes to the spinning solution

Definitions

  • It relates to a spinning forming process, in particular to a wet spinning forming process.
  • fire-retardant fiber can solve these problems, especially the flame retardant viscose fiber produced by adding flame retardant to viscose fiber can improve fiber easily.
  • the color paste and the flame retardant coexist in the spinning mixture, various effects (such as weak coloration, poor curing effect of the flame retardant, and poor coagulability of the acid bath) may occur, and the flame retardant fibers currently produced and sold are Colorless (primary) base fiber, after dyeing into a cloth, dye (dye) color as needed. In this case, printing and dyeing wastewater and printing and dyeing products will inevitably pollute the environment and cause harm to human health.
  • Patent application CN200910186551.0 discloses a spinning forming process of colored flame retardant viscose fiber colored filaments and short filaments, however, it does not limit the particle diameter of the color paste, flame retardant liquid and color fiber and viscose. The weight ratio is small, resulting in poor flame retardancy and poor coloring.
  • the weight ratio of the fiber containing the fiber is 36-45%, and the weight ratio of the fiber contained in the color paste to the nail fiber is 0.7-2%;
  • the spinning mixture is defoamed, filtered, and sent to a spinning acid bath through a metering pump and a spinneret for solidification molding and spinning drawing to obtain colored continuous filaments and wound on a spinning disc, wherein the spinning
  • the acid bath temperature is 38-48 ° C
  • the spinning speed is 75-80 m / min
  • the spinneret drafting amount is 10-15%
  • the spinning disc drafting amount is 20-25%
  • the subsequent drafting amount is 5 -10%;
  • the colored continuous filaments are washed with water and centrifuged to form a filament-like filament;
  • the filament-shaped filaments are sent to a curing treatment liquid for curing treatment, wherein the temperature of the curing treatment liquid is 75-90 ° C; and the filaments after the curing treatment are separately washed with water, dried and packaged.
  • the spinning mixture viscosity (falling ball method) is preferably 19-36 seconds, and the ripening degree is preferably 9-16 mL (10% NH 4 Cl solution).
  • the above viscosity and ripeness calibration units are well known in the art.
  • the spinneret draft is set to 13%, the spinning draft is 25%, and the subsequent draw is 5%.
  • the above draft amounts is well known and customary to those skilled in the art.
  • the color paste is preferably prepared by grinding a natural pigment or a synthetic pigment to a particle size of ⁇ 0.4 ⁇ m; providing polyvinylpyrrolidone as a suspension dispersing agent; and adding the above-mentioned ground pigment to suspension dispersion And water to form an aqueous suspension paste, wherein the pigment has a specific gravity of 35-50%, polyvinylpyrrolidone has a specific gravity of 3-8%, and the balance is water.
  • the "methyl fiber" (by weight) content is preferably from 8 to 10%.
  • the curing treatment liquid used in the present invention can be preferably prepared by using 802 # curing agent produced and sold by Beijing Sauerland Flame Retardant Fiber Co., Ltd., and the concentration (curing agent weight content) is preferably 30-60%, more preferably 32%-35. %, most preferably 33%.
  • the silicon-nitrogen flame retardant used in the present invention may be an organosilane hydrolyzed dispersion having a chemical formula of [Me 2 O ⁇ nSiO 2 ]+[--CONH], wherein Me represents a metal ion and the SiO 2 content is 9.23-53%.
  • the amide [--CONH] content is 4.3-27%.
  • the silicon-nitrogen flame retardant reference is made to the applicant's prior patent application CN104032401A and CN103789858A, the entire contents of which are incorporated herein by reference.
  • the silicon-nitrogen flame retardant is a 801 # silicon-nitrogen flame retardant produced and sold by Beijing Sauerland Flame Retardant Fiber Co., Ltd.
  • the filament specifications prepared according to the process of the present invention can be in the very wide range of 70D-500D (representing the tow weight per unit length) and 15-60F (representing the number of monofilaments forming each bundle of filaments).
  • the spinning dope may also include a base and a dispersing agent.
  • the base may be sodium hydroxide or potassium hydroxide in a concentration of 7-8% in the spinning mixture.
  • 803 # dispersing agent produced and sold by Beijing Sauerland Flame Retardant Fiber Co., Ltd. can be preferably used.
  • the water temperature of each water wash treatment may be from 60 to 80 °C.
  • the oiling treatment may also be included after the curing treatment (spinning oil concentration preferably 0.8-1.5 g/L).
  • conventional barrel processing may also be included between the drying and packaging processes.
  • the weight ratio of the flame retardant to the nail fiber contained in the nail fiber viscose is 36-45%, and the weight ratio of the nail fiber contained in the color paste to the nail fiber viscose is 0.7-2%;
  • the spinning mixture is defoamed, filtered, and sent to a spinning acid bath through a metering pump and a spinneret for solidification molding and spinning drawing to obtain a colored continuous yarn, wherein the spinning acid bath temperature is 38-48 ° C. , the spinning speed is 35-40m/min, and the amount of drawing is 45-50%;
  • the colored continuous yarn is cut into short filaments of 38-120 mm and sent to a curing treatment liquid for curing treatment, wherein the curing treatment liquid temperature is 75-90 ° C;
  • the solidified treated short yarns are separately subjected to dehydration, drying and packaging treatment to obtain finished colored filaments.
  • the spinning mixture viscosity (falling ball method) is preferably 19-36 seconds, and the ripening degree is preferably 9-16 mL (10% NH 4 Cl solution).
  • the above viscosity and ripeness calibration units are well known in the art.
  • the paste is preferably prepared as follows:
  • the above milled pigment is added to a suspension dispersant and water to form an aqueous suspension paste in which the pigment has a specific gravity of 35-50%, the polyvinylpyrrolidone has a specific gravity of 3-8%, and the balance is water.
  • the "methyl fiber" (by weight) content is preferably from 8 to 10%.
  • the curing treatment liquid used in the present invention can be preferably prepared by using 802 # curing agent produced and sold by Beijing Sauerland Flame Retardant Fiber Co., Ltd., and the concentration (curing agent weight content) is preferably 30-60%, more preferably 32%-35. %, most preferably 33%.
  • the silicon-nitrogen flame retardant used in the present invention may be an organosilane hydrolyzed dispersion having a chemical formula of [Me 2 O ⁇ nSiO 2 ]+[--CONH], wherein Me represents a metal ion and the SiO 2 content is 9.23-53%.
  • the amide [--CONH] content is 4.3-27%.
  • the silicon-nitrogen flame retardant reference is made to the applicant's prior patent application CN104032401A and CN103789858A, the entire contents of which are incorporated herein by reference.
  • the silicon-nitrogen flame retardant is a 801 # silicon-nitrogen flame retardant produced and sold by Beijing Sauerland Flame Retardant Fiber Co., Ltd.
  • the staple gauges prepared according to the method of the present invention may be within a wide range from 1.0D to 6.0D (representing the weight per unit length).
  • the spinning dope may also include a base and a dispersing agent.
  • the base may be sodium hydroxide or potassium hydroxide in a concentration of 7-8% in the spinning mixture.
  • 803 # dispersing agent produced and sold by Beijing Sauerland Flame Retardant Fiber Co., Ltd. can be preferably used.
  • the water washing treatment (water temperature preferably 60-80 ° C) may be included before the curing treatment, and the oiling treatment may also be included after the curing treatment (the spinning oil concentration is preferably 0.8-1.5 g/L).
  • a fine opening treatment may be included between the drying and packaging processes to increase the bulkiness.
  • the spinning process of the filaments and the short yarns according to the present invention is achieved by using a unique spinning mixture, a selected spinning acid bath and/or a curing treatment liquid, and well-designed process conditions.
  • the industrial production of colored filaments/short filaments has the advantages of strong coloration, curing effect of flame retardant and good solidification effect of acid bath.
  • the present invention has the following advantages:
  • the fiber Due to the use of nitrogen-silicon series environmentally-friendly flame retardant, the fiber has green environmental protection performance, in line with the national energy conservation and environmental protection policy; and the process of producing flame-retardant colored filaments and short filaments by effectively mixing the color paste into the flame-retardant adhesive. Not only the downstream dyeing process is omitted, but also the environmental pollution of the textile printing and dyeing wastewater and the harm of the dyed product to the human body can be minimized or avoided.
  • the addition amount of the flame retardant liquid and the colorant to the nail fiber in the viscose is 36-45% and 0.7-2% by weight, respectively. After the addition, the mixture was vigorously stirred to make a homogeneous mixed colloid; then defoaming and filtration were carried out. The spinning mixture had a viscosity of 19-36 seconds and a ripening degree of 16-19 mL (10% NH 4 Cl solution).
  • the flame retardant uses a nitrogen-silicon environmentally friendly flame retardant.
  • the color paste is a suspension pigment paste with a diameter of ⁇ 0.4 ⁇ m, which is made of polyvinylpyrrolidone as a suspension dispersant, and is colloidally ground and dispersed for 2-4 hours to prepare a 35-50% aqueous suspension color paste.
  • a spinning acid bath was prepared using pure water, wherein 85-115 g/L of sulfuric acid, 9-12 g/L of zinc sulfate, and 222-268 g/L of sodium sulfate. Maintain the acid bath temperature 38-48 ° C.
  • the spinning mixture is reacted with the acid bath in the acid bath of the spinning machine through the metering pump and the spinneret, and solidified, the spinning speed is 75-80 m/min, the drafting amount of the spinning head is 10-15%, and the spinning disc The drafting amount is 20-25%, and the subsequent drafting amount is 5-10%.
  • the flame-retardant viscose fiber colored filaments are washed with water and centrifuged, and then passed into a rinsing or pressing process in the form of a cake and cured therein.
  • the curing treatment liquid has a temperature of 75-90 ° C and a curing agent concentration of 30-60%.
  • the curing agent is a complex solution containing a cation such as Ti 4+ or Ca 2+ .
  • the resulting colored filaments are available in sizes 70D-500D and 15-60F.
  • the addition amount of the flame retardant liquid and the colorant to the nail fiber in the viscose is 36-45% and 0.7-2% by weight, respectively. After the addition, the mixture was vigorously stirred to make a homogeneous mixed colloid; then defoaming and filtration were carried out. The spinning mixture had a viscosity of 19-36 seconds and a ripeness of 9-16 mL (10% NH 4 Cl solution).
  • the flame retardant uses a nitrogen-silicon environmentally friendly flame retardant.
  • the color paste is a suspension pigment paste with a diameter of ⁇ 0.4 ⁇ m, which is made of polyvinylpyrrolidone as a suspension dispersant, and is colloidally ground and dispersed for 2-4 hours to prepare a 35-50% aqueous suspension color paste.
  • a spinning acid bath was prepared using pure water, wherein 85-115 g/L of sulfuric acid, 9-12 g/L of zinc sulfate, and 222-232 g/L of sodium sulfate. Maintain the acid bath temperature 38-48 ° C.
  • the spinning mixture is reacted with an acid bath through a metering pump and a spinneret in an acid bath of a spinning machine to form a spinning speed of 35-40 m/min, and a drafting amount is 45-50%.
  • the colored flame-retardant viscose fiber colored yarn is cut into a refiner for curing.
  • the curing treatment liquid has a temperature of 75-90 ° C and a curing agent concentration of 30-60%.
  • the curing agent is a complex solution containing a cation such as Ti 4+ or Ca 2+ .
  • the resulting colored short filaments are available in sizes from 1.0D to 6.0D and from 38 to 120 mm.
  • Example 1 Non-dyed flame retardant viscose fiber red short wire 2D/38mm
  • Red pigment was taken and ultra-finely ground to a particle size of ⁇ 0.4 ⁇ m. 30% of the pigment after the above treatment, 6% polyvinylpyrrolidone and 64% pure water were added to a colloid mill for 3 hours, and cooled for use.
  • Flame retardant liquid, red color paste and viscose are contacted and mixed according to a certain weight ratio; ratio of compounding: IIF glue (including 8.2% of fiber; also available from Beijing Sauerland Flame Retardant Fiber Co., Ltd.) 16000L; silicon nitrogen resistance Fuel agent 801#2360L; 10% sodium hydroxide solution 1200L; dispersant 803#200L; red color paste 300kg. The order of addition is: II F glue---dispersant 803#---(alkali--flame retardant 801#)---color paste.
  • the spinning speed is 35m/min, a draft is stretched by 45%, and then cut, and then refined into the refining machine - washing, solidifying and oiling, drying and drying after dehydration , packaging is the finished product.
  • the washing temperature is 70 ° C
  • the curing liquid temperature is 75-90 ° C
  • the curing agent 802# concentration is 33%
  • the oil concentration is 1 g g/L.
  • Example 2 Non-dyed flame retardant viscose fiber blue short wire 2D/85mm
  • Blue pigment was taken and ultra-finely ground to a particle size of ⁇ 0.4 ⁇ m. 35% of the pigment after the above treatment, 4% polyvinylpyrrolidone and 61% pure water were added to a colloid mill for 3 hours, and cooled for use.
  • Flame retardant liquid, blue color paste and viscose are contacted and mixed according to a certain weight ratio; compounding ratio: IIF glue 16000L; silicon nitrogen flame retardant 801#2000L; 10% potassium hydroxide solution 1000L; dispersing agent 803#160L; Blue color paste 100kg.
  • the order of addition is: II F glue---dispersant 803#---(alkali--flame retardant 801#)---color paste.
  • it is mechanically mixed to make it a homogeneous mixed colloid; it is defoamed and filtered, and sent to the spinning through a pipeline under power (pump or compressed air), and solidified in an acid bath.
  • the spinning speed is 40m/min, a draft is 50%, and then cut, and then into the refining machine for refining - washing, solidifying and oiling, drying and drying after dehydration , packaging is the finished product.
  • the washing temperature is 70 ° C
  • the curing liquid temperature is 75-90 ° C
  • the curing agent 802# concentration is 33%
  • the oil concentration is 1 g g/L.
  • Example 3 Non-dyed flame retardant viscose fiber red filament 250D/60F
  • Red pigment was taken and ultra-finely ground to a particle size of ⁇ 0.4 ⁇ m. 30% of the pigment after the above treatment, 6% polyvinylpyrrolidone and 64% pure water were added to a colloid mill for 3 hours, and cooled for use.
  • Flame retardant liquid, red color paste and viscose are contacted and mixed according to a certain weight ratio; ratio of compounding: IIF glue (including 8.2% of fiber; also available from Beijing Sauerland Flame Retardant Fiber Co., Ltd.) 16000L; silicon nitrogen resistance Fuel agent 801#2360L; 10% sodium hydroxide solution 1200L; dispersant 803#200L; red color paste 300kg. The order of addition is: IIF glue---dispersant 803#---(alkali--flame retardant 801#)---color paste.
  • the spinning speed is 80m/min
  • the drafting amount of the spinning head is 10%
  • the drafting amount of the spinning disc is 25%
  • the downstream drawing amount is 5%, after which it is washed with water and centrifuged.
  • Silk cake, solidification, pressure washing / rinsing and oiling, etc., dewatering, drying and forming into a tube, packaging is the finished product.
  • the washing temperature is 70 ° C
  • the curing liquid temperature is 75-90 ° C
  • the curing agent 802# concentration is 33%
  • the oil concentration is 1 g g/L.
  • Example 4 Non-dyed flame retardant viscose fiber blue filament 75D/32F
  • Blue pigment was taken and ultra-finely ground to a particle size of ⁇ 0.4 ⁇ m. 35% of the pigment after the above treatment, 4% polyvinylpyrrolidone and 61% pure water were added to a colloid mill for 3 hours, and cooled for use.
  • Flame retardant liquid, blue color paste and viscose are contacted and mixed according to a certain weight ratio; compounding ratio: IIF glue 16000L; silicon nitrogen flame retardant 801#2000L; 10% potassium hydroxide solution 1000L; dispersing agent 803#160L; Blue color paste 100kg.
  • the order of addition is: II F glue---dispersant 803#---(alkali--flame retardant 801#)---color paste.
  • it is mechanically mixed to make it a homogeneous mixed colloid; it is defoamed and filtered, and sent to the spinning through a pipeline under power (pump or compressed air), and solidified in an acid bath.
  • the spinning speed is 80m/min
  • the drafting amount of the spinning head is 15%
  • the drafting amount of the spinning disc is 20%
  • the drafting amount is 10%
  • Silk cake, solidification, pressure washing / rinsing and oiling, etc., dewatering, drying and forming into a tube, packaging is the finished product.
  • the washing temperature is 70 ° C
  • the curing liquid temperature is 75-90 ° C
  • the curing agent 802# concentration is 33%
  • the oil concentration is 1 g g/L.

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  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
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  • General Chemical & Material Sciences (AREA)
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Abstract

一种无染阻燃粘胶纤维有色长丝或短丝的纺丝成形方法，包括：提供由硅氮阻燃剂、色浆与甲纤粘胶混合制备的纺丝混合液；提供由硫酸、硫酸锌与硫酸钠混合制备的纺丝酸浴；将纺丝混合液脱泡、过滤后通过计量泵和喷丝头送入纺丝酸浴中进行凝固成型和纺丝牵伸以得到有色连续长丝；提供含Ti4+、Ca2+阳离子络合溶液的固化处理液；将有色连续长丝进行固化处理，或将有色连续丝条切断成38-120mm的短丝后送入固化处理液进行固化处理；以及对固化处理后的长丝或短丝分别再进行水洗、烘干和包装处理以得到成品有色长丝或短丝。本发明省略了下游的染色工序，最大幅度减少或避免了纺织印染废水对环境的污染及染色产品对人体的危害。

Description

一种无染阻燃粘胶纤维有色长丝和短丝的纺丝成形方法 技术领域
涉及一种纺丝成形工艺，特别是一种湿法纺丝成形工艺。
背景技术
无论合成纤维、粘胶纤维或是天然棉纤维均易燃烧着火引起火灾，而阻燃纤维可以解决这些问题，尤其在粘胶纤维中加入阻燃剂生产的阻燃粘胶纤维，可以改善纤维容易着火的特性，避免火灾，减少财产和生命伤害，还保持了粘胶纤维本来的穿着舒适之独特性能。
由于色浆和阻燃剂共存于纺丝混合液中时会产生种种影响(例如着色不牢固、阻燃剂固化效果不佳以及酸浴凝固性差等问题)，目前生产销售的阻燃纤维均是无色(原色)基础纤维，纺织成布后根据需要再进行染料着(染)色。这种情况下印染废水及印染产品不可避免对环境造成污染且对人体健康产生危害。
专利申请CN200910186551.0公开了一种环保阻燃粘胶纤维有色长丝和短丝的纺丝成形工艺，然而其没有限定色浆的颗粒直径，阻燃剂液体与色浆和粘胶中甲纤的重量比例较小，导致其阻燃效果不佳，上色的效果也不佳。
发明内容
本发明的目的是提供一种无染阻燃粘胶纤维有色长丝和短丝的纺丝成形工艺或方法，其适合工业化并且有利环保。
实现一种无染阻燃粘胶纤维有色长丝的纺丝成形工艺或方法而采取的技术方案包括：
提供由硅氮阻燃剂、色浆与甲纤粘胶混合制备的纺丝混合液，其中色浆为直径≤0.4μm的悬浮颜料色浆，并且硅氮阻燃剂与甲纤粘胶中所含甲纤之重量比为36-45％，色浆与甲纤粘胶中所含甲纤之重量比为0.7-2％；
提供由硫酸、硫酸锌与硫酸钠混合制备的纺丝酸浴，其中硫酸浓度为85-115g/L、硫酸锌浓度为9-12g/L、硫酸钠浓度为222-268g/L；
将纺丝混合液脱泡、过滤后通过计量泵和喷丝头送入纺丝酸浴中进行凝固成型和纺丝牵伸以得到有色连续长丝并将其缠绕在纺盘上，其中纺丝酸浴温度为38-48℃，纺丝速度为75-80m/min，并且喷丝头牵伸量为10-15％、纺盘牵伸量为20-25％、后道牵伸量为5-10％；
提供含Ti4+、Ca2+阳离子络合溶液的固化处理液；
将有色连续长丝经过水洗和离心处理以形成丝饼状长丝；
将丝饼状长丝送入固化处理液进行固化处理，其中固化处理液温度为75-90℃；以及对固化处理后的长丝分别再进行水洗、烘干和包装处理。
在本发明的一个具体实施例中，纺丝混合液粘度(落球法)优选为19-36秒，熟成度优选为9-16mL(10％NH4Cl溶液)。上述粘度和熟成度标定单位均为本领域所熟知。
在本发明的优选实施例中，喷丝头牵伸量设为13％、纺盘牵伸量为25％、后道牵伸量为5％。上述各个牵伸量均为本领域技术人员所熟知并惯用。
在本发明的一个具体实施例中，色浆优选如下制备：将天然颜料或人工合成颜料研磨为粒径≤0.4μm；提供聚乙烯吡咯烷酮作为悬浮分散剂；以及将上述研磨后的颜料加入悬浮分散剂和水中以形成水性悬浮色浆，其中颜料比重为35-50％，聚乙烯吡咯烷酮比重为3-8％，余量为水。
在该实施例中，还可以使用胶体磨对制备的水性悬浮色浆或胶体色浆进一步 研磨分散2-4小时以提高胶体分散均匀度。
在本发明中使用的甲纤粘胶中，“甲纤”(重量)含量优选为8-10％。
本发明中使用的固化处理液可以优选采用北京赛欧兰阻燃纤维有限公司生产并销售的802#固化剂制备，浓度(固化剂重量含量)优选为30-60％，更优选为32％-35％，最优选为33％。
本发明中使用的硅氮阻燃剂可以采用有机硅烷水解分散液，其化学式为[Me2O·nSiO2]+[--CONH]，其中Me代表金属离子，SiO2含量为9.23-53％；酰胺[--CONH]含量为4.3-27％。关于硅氮阻燃剂，可以参见申请人之前的专利申请CN104032401A以及CN103789858A，在此分别以参见方式引入这两个申请的全部内容。在本发明的一个优选实施例中，硅氮阻燃剂采用北京赛欧兰阻燃纤维有限公司生产并销售的801#硅氮阻燃剂。
根据本发明的方法制备的长丝规格可以在70D-500D(表示单位长度之丝束重量)以及15-60F(表示形成每束长丝的单丝数量)的极宽范围之内。
在本发明的一个优选实施例中，纺丝混合液还可以包括碱和分散剂。碱可以是氢氧化钠或氢氧化钾，在纺丝混合液中的浓度为7-8％。分散剂则可以优选使用北京赛欧兰阻燃纤维有限公司生产并销售的803#分散剂。
在本发明的优选实施例中，各水洗处理的水温可以为60-80℃。
在本发明的其它实施例中，固化处理之后还可以包括上油处理(纺丝油剂浓度优选0.8-1.5g/L)。另外，在烘干和包装处理之间还可以包括常规成筒处理。
实现一种无染阻燃粘胶纤维有色短丝的纺丝成形工艺或方法而采取的技术方案包括：
提供由硅氮阻燃剂、色浆与甲纤粘胶混合制备的纺丝混合液(或可称为“纺胶”)，其中色浆为直径≤0.4μm的悬浮颜料色浆，并且硅氮阻燃剂与甲纤粘胶中所含甲纤之重量比为36-45％，色浆与甲纤粘胶中所含甲纤之重量比为0.7-2％；
提供由硫酸、硫酸锌与硫酸钠混合制备的纺丝酸浴，其中硫酸浓度为85-115g/L、硫酸锌浓度为9-12g/L、硫酸钠浓度为222-232g/L；
将纺丝混合液脱泡、过滤后通过计量泵和喷丝头送入纺丝酸浴中进行凝固成型和纺丝牵伸以得到有色连续丝条，其中纺丝酸浴温度为38-48℃，纺丝速度为35-40m/min，并且一道牵伸量为45-50％；
提供含Ti4+、Ca2+阳离子络合溶液的固化处理液；
将有色连续丝条切断成38-120mm的短丝后送入固化处理液进行固化处理，其中固化处理液温度为75-90℃；以及
对固化处理后的短丝分别再进行脱水、烘干和包装处理以得到成品有色短丝。
在本发明的一个具体实施例中，纺丝混合液粘度(落球法)优选为19-36秒，熟成度优选为9-16mL(10％NH4Cl溶液)。上述粘度和熟成度标定单位均为本领域所熟知。
在本发明的一个具体实施例中，色浆优选如下制备：
将天然颜料或人工合成颜料研磨为粒径≤0.4μm；
提供聚乙烯吡咯烷酮作为悬浮分散剂；以及
将上述研磨后的颜料加入悬浮分散剂和水中以形成水性悬浮色浆，其中颜料比重为35-50％，聚乙烯吡咯烷酮比重为3-8％，余量为水。
在该实施例中，还可以使用胶体磨对制备的水性悬浮色浆或胶体色浆进一步 研磨分散2-4小时以提高胶体分散均匀度。
在本发明中使用的甲纤粘胶中，“甲纤”(重量)含量优选为8-10％。
本发明中使用的固化处理液可以优选采用北京赛欧兰阻燃纤维有限公司生产并销售的802#固化剂制备，浓度(固化剂重量含量)优选为30-60％，更优选为32％-35％，最优选为33％。
本发明中使用的硅氮阻燃剂可以采用有机硅烷水解分散液，其化学式为[Me2O·nSiO2]+[--CONH]，其中Me代表金属离子，SiO2含量为9.23-53％；酰胺[--CONH]含量为4.3-27％。关于硅氮阻燃剂，可以参见申请人之前的专利申请CN104032401A以及CN103789858A，在此分别以参见方式引入这两个申请的全部内容。在本发明的一个优选实施例中，硅氮阻燃剂采用北京赛欧兰阻燃纤维有限公司生产并销售的801#硅氮阻燃剂。
根据本发明的方法制备的短丝规格可以在1.0D-6.0D(表示单位长度之重量)的宽范围之内。
在本发明的一个优选实施例中，纺丝混合液还可以包括碱和分散剂。碱可以是氢氧化钠或氢氧化钾，在纺丝混合液中的浓度为7-8％。分散剂则可以优选使用北京赛欧兰阻燃纤维有限公司生产并销售的803#分散剂。
在本发明的其它实施例中，固化处理之前还可以包括水洗处理(水温优选60-80℃)，固化处理之后还可以包括上油处理(纺丝油剂浓度优选0.8-1.5g/L)。另外，在烘干和包装处理之间还可以包括精开松处理以增加蓬松度。
根据本发明的长丝和短丝的纺丝成形工艺，由于采用了独特的纺丝混合液，配合选定的纺丝酸浴和/或固化处理液，以及精心设计的工艺条件，从而实现了工业化生产有色长丝/短丝并且具有着色牢固、阻燃剂固化效果以及酸浴凝固效果良好的优点。
此外，本发明还具有以下优点：
由于采用了氮硅系列环保阻燃剂，因而纤维具有绿色环保性能，符合国家节能环保政策；以及由于采用了把色浆有效混入阻燃粘胶中生产出阻燃有色长丝和短丝的工艺，不仅省略了下游的染色工序，而且可以最大幅度减少或避免纺织印染废水对环境的污染及染色产品对人体的危害。
具体实施方式
一种无染阻燃粘胶纤维有色长丝的纺丝成形方法，
(1)由阻燃剂和色浆与甲纤粘胶混合制备纺丝混合液
阻燃剂液体、色浆对粘胶中的甲纤添加量按照重量比分别为36-45％、0.7-2％。添加后，强烈搅拌使之成为均相一致的混合胶体；然后进行脱泡和过滤。纺丝混合液粘度为19-36秒，熟成度为16-19mL(10％NH4Cl溶液)。阻燃剂采用氮硅系环保阻燃剂。色浆为直径≤0.4μm的悬浮颜料色浆，由聚乙烯吡咯烷酮作悬浮分散剂，胶体磨研磨分散2-4小时而制成35-50％水性悬浮色浆。
(2)纺丝酸浴的制备
使用纯水配制纺丝酸浴，其中硫酸85-115g/L、硫酸锌9-12g/L、硫酸钠222-268g/L。保持酸浴温度38-48℃。
(3)纺丝成形牵伸
将纺丝混合液通过计量泵和喷丝头在纺丝机酸浴槽中与酸浴反应，凝固成型，纺丝速度75-80m/min，喷丝头牵伸量为10-15％、纺盘牵伸量为20-25％、后道牵伸量为5-10％。
(4)水洗、离心以及固化工艺处理
经过牵伸后的阻燃粘胶纤维有色长丝经过水洗和离心处理后以丝饼形式进入淋洗或压洗流程并在此进行固化处理。所述的固化处理液温度为75-90℃，采用的固化剂浓度为30-60％。所述固化剂为含Ti4+、Ca2+等阳离子的络合溶液。
(5)再次水洗、上油、烘干、包装等后处理
所得有色长丝规格为70D-500D以及15-60F。
一种无染阻燃粘胶纤维有色短丝的纺丝成形方法，
(1)由阻燃剂和色浆与甲纤粘胶混合制备纺丝混合液
阻燃剂液体、色浆对粘胶中的甲纤添加量按照重量比分别为36-45％、0.7-2％。添加后，强烈搅拌使之成为均相一致的混合胶体；然后进行脱泡和过滤。纺丝混合液粘度为19-36秒，熟成度为9-16mL(10％NH4Cl溶液)。阻燃剂采用氮硅系环保阻燃剂。色浆为直径≤0.4μm的悬浮颜料色浆，由聚乙烯吡咯烷酮作悬浮分散剂，胶体磨研磨分散2-4小时而制成35-50％水性悬浮色浆。
(2)纺丝酸浴的制备
使用纯水配制纺丝酸浴，其中硫酸85-115g/L、硫酸锌9-12g/L、硫酸钠222-232g/L。保持酸浴温度38-48℃。
(3)纺丝成形牵伸
将纺丝混合液通过计量泵和喷丝头在纺丝机酸浴槽中与酸浴反应，凝固成型，纺丝速度35-40m/min，一道牵伸量为45-50％。
(4)切断和固化工艺处理
经过牵伸后的阻燃粘胶纤维有色丝条经过切断后进入精炼机进行固化处理。所述的固化处理液温度为75-90℃，采用的固化剂浓度为30-60％。所述固化剂为含Ti4+、Ca2+等阳离子的络合溶液。
(5)脱水、烘干、包装等后处理
所得有色短丝规格为1.0D-6.0D以及38-120mm。
实施例1：无染阻燃粘胶纤维红色短丝2D/38mm
制备色浆：取红色颜料，经超细研磨至粒径≤0.4μm。上述处理后的颜料30％，聚乙烯吡咯烷酮6％，纯净水64％，加入胶体磨研磨3h，冷却备用。
阻燃剂液体、红色色浆与粘胶按照一定的重量比接触混合；配胶比例：IIF胶(含甲纤8.2％；同样可购自北京赛欧兰阻燃纤维有限公司)16000L；硅氮阻燃剂801#2360L；10％氢氧化钠溶液1200L；分散剂803#200L；红色色浆300kg。加料顺序为：II F胶---分散剂803#---(碱液--阻燃剂801#)---色浆。然后通过机械方式进行混合处理，使之成为均相一致的混合胶体；再对之进行脱泡和过滤，在动力作用下(泵或压缩空气)通过管路送往纺丝，在酸浴中凝固成初生丝条后，经过牵伸，纺丝速度35m/min，一道牵伸45％，后进行切断，再进入精炼机精炼--水洗、固化和上油等，脱水后烘干及精开松，打包即为成品。其中水洗温度70℃，固化处理液温度为75-90℃，固化剂802#浓度为33％，上油浓度1g克/L。
实施例2：无染阻燃粘胶纤维蓝色短丝2D/85mm
制备色浆：取蓝色颜料，经超细研磨至粒径≤0.4μm。上述处理后的颜料35％，聚乙烯吡咯烷酮4％，纯净水61％，加入胶体磨研磨3h，冷却备用。
阻燃剂液体、蓝色色浆与粘胶按照一定的重量比接触混合；配胶比例：IIF胶16000L；硅氮阻燃剂801#2000L；10％氢氧化钾溶液1000L；分散剂803#160L； 蓝色色浆100kg。加料顺序为：II F胶---分散剂803#---(碱液--阻燃剂801#)---色浆。然后通过机械方式进行混合处理，使之成为均相一致的混合胶体；再对之进行脱泡和过滤，在动力作用下(泵或压缩空气)通过管路送往纺丝，在酸浴中凝固成初生丝条后，经过牵伸，纺丝速度40m/min，一道牵伸50％，后进行切断，再进入精炼机精炼--水洗、固化和上油等，脱水后烘干及精开松，打包即为成品。其中水洗温度70℃，固化处理液温度为75-90℃，固化剂802#浓度为33％，上油浓度1g克/L。
实施例3：无染阻燃粘胶纤维红色长丝250D/60F
制备色浆：取红色颜料，经超细研磨至粒径≤0.4μm。上述处理后的颜料30％，聚乙烯吡咯烷酮6％，纯净水64％，加入胶体磨研磨3h，冷却备用。
阻燃剂液体、红色色浆与粘胶按照一定的重量比接触混合；配胶比例：IIF胶(含甲纤8.2％；同样可购自北京赛欧兰阻燃纤维有限公司)16000L；硅氮阻燃剂801#2360L；10％氢氧化钠溶液1200L；分散剂803#200L；红色色浆300kg。加料顺序为：IIF胶---分散剂803#---(碱液--阻燃剂801#)---色浆。然后通过机械方式进行混合处理，使之成为均相一致的混合胶体；再对之进行脱泡和过滤，在动力作用下(泵或压缩空气)通过管路送往纺丝，在酸浴中凝固成初生长丝后，经过牵伸，纺丝速度80m/min，喷丝头牵伸量10％、纺盘牵伸量为25％、后道牵伸量为5％，后进行水洗、离心成丝饼、固化、压洗/淋洗和上油等，脱水后烘干及成筒，打包即为成品。其中水洗温度70℃，固化处理液温度为75-90℃，固化剂802#浓度为33％，上油浓度1g克/L。
实施例4：无染阻燃粘胶纤维蓝色长丝75D/32F
制备色浆：取蓝色颜料，经超细研磨至粒径≤0.4μm。上述处理后的颜料35％，聚乙烯吡咯烷酮4％，纯净水61％，加入胶体磨研磨3h，冷却备用。
阻燃剂液体、蓝色色浆与粘胶按照一定的重量比接触混合；配胶比例：IIF胶16000L；硅氮阻燃剂801#2000L；10％氢氧化钾溶液1000L；分散剂803#160L；蓝色色浆100kg。加料顺序为：II F胶---分散剂803#---(碱液--阻燃剂801#)---色浆。然后通过机械方式进行混合处理，使之成为均相一致的混合胶体；再对之进行脱泡和过滤，在动力作用下(泵或压缩空气)通过管路送往纺丝，在酸浴中凝固成初生长丝后，经过牵伸，纺丝速度80m/min，喷丝头牵伸量15％、纺盘牵伸量为20％、后道牵伸量为10％，后进行水洗、离心成丝饼、固化、压洗/淋洗和上油等，脱水后烘干及成筒，打包即为成品。其中水洗温度70℃，固化处理液温度为75-90℃，固化剂802#浓度为33％，上油浓度1g克/L。
经检测，本发明方法制备得到的产品主要性能如下。
Figure PCTCN2016082486-appb-000001
Figure PCTCN2016082486-appb-000002
可以看出，本发明方法制得的产品具有更优的性能。
本领域技术人员可以理解，上述实施例中先后列出的各个方法步骤只是为了起到说明本发明的目的而非用以对其进行限制。因此这些步骤并无必然先后次序，也并非不可或缺。本发明仅由各个权利要求所具体限定。

Claims (6)

  1. 一种无染阻燃粘胶纤维有色长丝的纺丝成形方法，包括：
    提供由硅氮阻燃剂、色浆与甲纤粘胶混合制备的纺丝混合液，其中色浆为直径≤0.4μm的悬浮颜料色浆，并且硅氮阻燃剂与甲纤粘胶中所含甲纤之重量比为36-45％，色浆与甲纤粘胶中所含甲纤之重量比为0.7-2％；
    提供由硫酸、硫酸锌与硫酸钠混合制备的纺丝酸浴，其中硫酸浓度为85-115g/L、硫酸锌浓度为9-12g/L、硫酸钠浓度为222-268g/L；将纺丝混合液脱泡、过滤后通过计量泵和喷丝头送入纺丝酸浴中进行凝固成型和纺丝牵伸以得到有色连续长丝并将其缠绕在纺盘上，
    其中纺丝酸浴温度为38-48℃，纺丝速度为75-80m/min，并且喷丝头牵伸量为10-15％、纺盘牵伸量为20-25％、后道牵伸量为5-10％；
    提供含Ti4+、Ca2+阳离子络合溶液的固化处理液；
    将有色连续长丝经过水洗和离心处理以形成丝饼状长丝；
    将丝饼状长丝送入固化处理液进行固化处理，其中固化处理液温度为75-90℃；以及对固化处理后的长丝分别再进行水洗、烘干和包装处理以得到成品有色长丝。
  2. 一种无染阻燃粘胶纤维有色短丝的纺丝成形方法，包括：
    提供由硅氮阻燃剂、色浆与甲纤粘胶混合制备的纺丝混合液，其中色浆为直径≤0.4μm的悬浮颜料色浆，并且硅氮阻燃剂与甲纤粘胶中所含甲纤之重量比为36-45％，色浆与甲纤粘胶中所含甲纤之重量比为0.7-2％；
    提供由硫酸、硫酸锌与硫酸钠混合制备的纺丝酸浴，其中硫酸浓度为85-115g/L、硫酸锌浓度为9-12g/L、硫酸钠浓度为222-232g/L；
    将纺丝混合液脱泡、过滤后通过计量泵和喷丝头送入纺丝酸浴中进行凝固成型和纺丝牵伸以得到有色连续丝条，其中纺丝酸浴温度为38-48℃，纺丝速度为35-40m/min，并且一道牵伸量为45-50％；
    提供含Ti4+、Ca2+阳离子络合溶液的固化处理液；
    将有色连续丝条切断成38-120mm的短丝后送入固化处理液进行固化处理，其中固化处理液温度为75-90℃；以及
    对固化处理后的短丝分别再进行脱水、烘干和包装处理以得到成品有色短丝。
  3. 根据权利要求1或2所述的方法，其中纺丝混合液粘度为19-36秒，熟成度为16-19mL(10％NH4Cl溶液)。
  4. 根据权利要求1或2所述的方法，其中色浆的制备如下：
    将天然颜料或人工合成颜料研磨为粒径≤0.4μm；
    提供聚乙烯吡咯烷酮作为悬浮分散剂；以及
    将上述研磨后的颜料加入悬浮分散剂和水中以形成水性悬浮色浆，其中颜料比重为35-50％，聚乙烯吡咯烷酮比重为3-8％，余量为水。
  5. 一种无染阻燃粘胶纤维有色长丝，其通过权利要求1或3或4的方法获得。
  6. 一种无染阻燃粘胶纤维有色短丝，其通过权利要求2或3或4的方法获得。
PCT/CN2016/082486 2015-05-20 2016-05-18 一种无染阻燃粘胶纤维有色长丝和短丝的纺丝成形方法 WO2016184390A1 (zh)

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