WO2021136411A1 - Acid low-temperature dip dyeing method for polyamide 56 fiber and fabric - Google Patents

Acid low-temperature dip dyeing method for polyamide 56 fiber and fabric Download PDF

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WO2021136411A1
WO2021136411A1 PCT/CN2020/141542 CN2020141542W WO2021136411A1 WO 2021136411 A1 WO2021136411 A1 WO 2021136411A1 CN 2020141542 W CN2020141542 W CN 2020141542W WO 2021136411 A1 WO2021136411 A1 WO 2021136411A1
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nylon
dye
acid
dyeing
fiber
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PCT/CN2020/141542
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French (fr)
Chinese (zh)
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郝新敏
郭亚飞
梁高勇
李茂辉
刘阳
闫金龙
乔荣荣
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军事科学院***工程研究院军需工程技术研究所
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Publication of WO2021136411A1 publication Critical patent/WO2021136411A1/en

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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
    • D06P1/39—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 acid dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • D06L1/12—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents
    • D06L1/16—Multi-step processes
    • 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
    • D06P1/0032—Determining dye recipes and dyeing parameters; Colour matching or monitoring
    • 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
    • D06P1/36—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 mordant dyes ; using metallisable dyes
    • 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
    • D06P1/38—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 reactive dyes
    • 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
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/24—Polyamides; Polyurethanes
    • D06P3/241—Polyamides; Polyurethanes using acid dyes
    • 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
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/24—Polyamides; Polyurethanes
    • D06P3/245—Polyamides; Polyurethanes using metallisable or mordant dyes
    • 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
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/24—Polyamides; Polyurethanes
    • D06P3/248—Polyamides; Polyurethanes using reactive dyes

Definitions

  • the invention relates to an acid low-temperature dip dyeing method for nylon 56 fibers and fabrics, and belongs to the field of textile dyeing and finishing.
  • Nylon fiber commonly known as nylon (PA)
  • PA is a general term for thermoplastic resins containing repeating amide groups (-NHCO-) on the main chain of the molecule.
  • nylon came out in 1935 and was the first synthetic fiber to be industrialized.
  • polyester has developed rapidly in recent years, nylon still competes among synthetic fibers with its excellent strength, abrasion resistance, elastic recovery rate, moisture absorption and other excellent properties, and it still occupies an important position for more than half a century.
  • nylon 66 and nylon 6 are the most commonly used and widely used.
  • most of their synthetic raw materials are derived from fossil resources. With the increasing demand for nylon materials in industrial production and the depletion of fossil resources, coupled with people's increasing attention to environmental protection issues, replacing non-renewable fossil raw materials with renewable biomass resources to prepare chemicals is the main trend of future development.
  • the purpose of the present invention is to provide an acid bath ultra-low temperature and high-efficiency dip dyeing method for nylon 56 fiber or its fabric.
  • the invention adopts acid dyes, neutral dyes and reactive dyes to realize the dip dyeing of nylon 56 fiber or its fabric.
  • the acid bath dip dyeing method of nylon 56 fiber or its fabric provided by the present invention includes the following steps:
  • the nylon 56 fiber may specifically be filament or staple fiber
  • the content of the terminal amino group of the nylon 56 fiber may be 20 to 80 mol/10 6 gr, preferably 30 to 60 mol/10 6 gr, more preferably 45 to 55 mol/10 6 gr;
  • Nylon 56 content of the terminal carboxyl group of fibers may be 50 ⁇ 110mol / 10 6 gr, preferably 60 ⁇ 90mol / 10 6 gr, more preferably 65 ⁇ 75mol / 10 6 gr.
  • the crystallinity of the nylon 56 fiber may be 30-70%, preferably 45-65%, more preferably 45-60%.
  • the nylon 56 fabric is formed of the above nylon 56 fiber, and specifically may be a nylon 56 knitted fabric, a nylon 56 woven fabric or a nylon 56 non-woven fabric.
  • the nylon 56 fiber can be prepared by a melt direct spinning method or a melt batch spinning method
  • the steps for dyeing with the acid dye or the neutral dye are as follows:
  • the acid dye or the neutral dye is prepared into a dye solution, the bath ratio is 1:2-10, the pH value is adjusted to be 2.0-6.8, and dyeing auxiliaries are added, and the nylon 56 fiber or its fabric is added at room temperature. After dyeing, the temperature is raised to 30-80°C at a heating rate of 5-10°C/min, and the temperature is kept for 1-20 minutes, and then it is reduced to room temperature for post-dying treatment.
  • the reactive dye is prepared into a dyeing solution with a bath ratio of 1:2 ⁇ 10, 1 ⁇ 10g/L sodium sulfate is added (additional liquid or constant temperature process can be added), and dyeing auxiliaries are added to adjust the pH to 2.0 ⁇ 6.5.
  • the fixing agent can be a surface active agent (cationic), a non-surface-active quaternary ammonium salt, a resin type fixing agent, a crosslinking fixing agent, a formaldehyde-free fixing agent, etc., and specifically can be a fixing agent Y, Soda ash or caustic soda.
  • the acid dye may be at least one of azo acid dyes, anthraquinone acid dyes, triarylmethane acid dyes, xanthene acid dyes, and nitro acid dyes;
  • the acid dye may specifically be acid red NHFS, acid yellow NHFS, acid blue NHFS, F type weak acid dye, acid scarlet FG, acid yellow G, acid yellow AD, acid red AD, acid gray AD, weak acid scarlet FG or Weak acid blue 5R.
  • the neutral dye may be a 1:2 type metal complex dye in an acid mordant dye, and specifically may be an Annoset M-type metal complex dye or an S-type metal complex dye;
  • the neutral dye can specifically be neutral dark yellow GL, neutral gray 2BL, neutral yellow 2R, neutral sauce red B, neutral blue 2R, neutral brown B, neutral gray G, neutral red GAL, Neutral Vietnamese BR, Neutral Black AW200%, Neutral Yellow TB, Neutral Yellow R, Neutral Red 3B, Neutral Red 10B, Neutral Red 3G, Neutral Turquoise Blue G, Neutral Blue R or Neutral Blue RAWL etc.
  • the reactive dye can be a chloros-triazine reactive group reactive dye, a vinylsulfone reactive group reactive dye, a multiple reactive group reactive dye, a bromoacrylamide reactive group reactive dye, an epoxy reactive dye or Azide reactive dyes;
  • Chlorine s-triazines reactive dye K-6G; vinyl sulfones: reactive dye K-NR; multiple reactive groups: reactive brilliant red M-3BE; bromoacrylamides: Lannasol blue 3G, reactive red 83, Reactive Yellow 39, Reactive Blue 69, Anofix Red ARC, Anofix Yellow/Golden ARC, Anofix Blue ARC; Reactive dye activity of unknown structure: Bright Yellow WG, Reactive Scarlet WG, Reactive Brilliant Blue WR, reactive black WG.
  • the dyeing auxiliary agent may be a pH adjusting agent and a leveling agent
  • the pH adjusting agent may specifically be acid, alkali, acidic oxide, basic oxide, weak acid and strong base salt, strong acid and weak base salt, etc., such as acetic acid, sodium hydroxide, calcium oxide, sodium carbonate, ammonium chloride, etc. , Such as using a 1% concentration aqueous solution;
  • the dosage of the pH adjuster can be 0.5-5 g/L;
  • the leveling agent can specifically be leveling plus O, leveling agent JV-905, leveling agent JV-1, leveling agent SET, leveling agent HJ-219 or leveling agent NL;
  • the dosage of the leveling agent can be 0.1 to 5% (o.w.f.).
  • the post-treatment after dyeing with the acid dye and the neutral dye includes the following steps: washing with hot water, washing with water and drying;
  • the hot water washing 40 ⁇ 60°C hot water washing 1 ⁇ 3 times;
  • the water washing washing with room temperature water for 1 to 3 times;
  • the post-treatment after dyeing with the reactive dyes includes the following steps: washing with hot water, washing with water, soaping, washing with water, and drying;
  • the hot water washing 40-60°C hot water washing 1 to 3 times;
  • the water washing washing with room temperature water for 1 to 3 times;
  • soap powder 1-5g/L The conditions of the soaping are as follows: soap powder 1-5g/L, temperature 40-80°C, time 5-10min, bath ratio 1:15.
  • Figure 1 shows the dyeing effect of nylon 56 fibers with different amino terminal content.
  • Figure 2 shows the dyeing rate curve of nylon fiber dyed with acid dye (acid blue NHFS) at 70°C.
  • Figure 3 shows the dyeing rate curve of nylon fiber dyed with neutral dye (Neutral Dark Yellow GL) at 65°C.
  • Figure 4 shows the dyeing rate curve of nylon fiber dyed with reactive dye (Reactive Brilliant Blue D-RV) at 60°C.
  • the nylon 66 used in the following examples is a commercially available product, and the test terminal amino group content is 46 mol/10 6 gr.
  • the nylon 56 fiber used in the embodiment of the present invention was prepared according to the following method:
  • the pressure drop will take about 1h.
  • the temperature of the reactor will rise to 270°C and the vacuum will be pumped for about 10 minutes.
  • the temperature in the kettle will rise to 275°C, and the polymerization reaction will be completed.
  • the pelletizer cuts to obtain nylon 56 slices.
  • the slices were dried at 80°C for 22h, and spinning conditions were set: spinning temperature 288°C, metering pump speed 16rpm/min, spinning speed 1000m/min, side blowing pressure 450pa, winding oil F5103 concentration 5% ,
  • the drafting ratio and heating temperature are: one-drawing ratio 2.5 ⁇ 3.5; two-drawing ratio 1.01 ⁇ 1.42; drafting box temperature 170; second-drawing temperature 180; hot plate temperature 200; three-drawing temperature 180.
  • the nylon 56 fiber is obtained by winding.
  • the different pH values of the saline solution correspond to the different end groups and carboxyl content of the fibers as shown in Table 1 (control draft ratio is 3.5).
  • the dyeing effect is shown in Figure 1.
  • the left image is 1# sample, and the right image is 3# sample.
  • the dye uptake rates of the two samples were tested, respectively: the dye uptake rate of the 1# sample was 68.3%, and the dye uptake rate of the 3# sample was 83.6%.
  • nylon 56 fiber has a high content of amino groups and a good dyeing effect.
  • the nylon 56 fiber obtained was dyed according to the above method, and the dye uptake rate is shown in Table 2.
  • the pH of the salt solution is 7.85
  • the first-stage draft is 3.15 times
  • the second-stage draft is 1.12 times (the total draft is 3.53 times) nylon 56 fiber
  • its terminal amino content is measured to be 45.2mol/10 6 gr
  • the terminal carboxyl group content is 74.3mol/10 6 gr
  • the crystallinity is 65.2%
  • the following dyeing treatment is performed.
  • Example 1 Determination of the dyeing rate curve of nylon 56 and nylon 66 dyed with acid dyes
  • Figure 2 shows the dyeing rate curve of nylon 56 and nylon 66 dyed with acid dyes.
  • Table 3 shows the balance dyeing percentage of nylon 56 and nylon 66.
  • Figure 3 shows the dyeing rate curve of nylon 56 and nylon 66 dyed with neutral dyes. Table 3 shows the balance dyeing percentage of nylon 56 and nylon 66.
  • Figure 4 shows the dyeing rate curve of nylon 56 and nylon 66 dyed with reactive dyes.
  • Table 3 shows the balance dyeing percentage of nylon 56 and nylon 66.
  • nylon 56 and nylon 66 dyed with different types of dyes were dyed with nylon 56 and nylon 66 fibers under low temperature conditions.
  • the balance dyeing percentage can basically be reached within 20 minutes of dyeing, while nylon 66 needs at least 60 minutes to achieve a higher dyeing percentage, and the balance dyeing percentage of nylon 56 is significantly higher than that of nylon 66.
  • Select dye acid blue NHFS prepare 2% (o.w.f.) dye solution, dye solution pH is 4.67, and add leveling agent to 0.5% (o.w.f.), dyeing bath ratio 1:5. Under normal temperature conditions, add 2g of the dyed fabric; then heat up to 70°C at a heating rate of 5.5°C/min, keep it for 15 minutes, and finish dyeing. Cool the dye solution to room temperature. Take out the sample and wash it with hot water at 70°C for 3 times, and wash it with water at room temperature once. , Let dry.
  • Example 5 Nylon 56 fiber impregnated with neutral dye
  • the dye solution is cooled to room temperature, and the sample is washed once with hot water at 40°C, washed once with water at room temperature, soaping (2g/L soap flakes, 45°C, 10min, bath ratio 1:10), washing with room temperature water 1 Let dry.
  • the acid bath dyeing method of nylon 56 fiber provided by the present invention has the following advantages:
  • the dyeing effect is good, the color is deep, and the dye uptake rate is high;
  • the color fastness is good, and the color fastness test results of the dyed fabrics such as rubbing resistance, washing resistance and sunlight resistance can meet the requirements of use.
  • the washing resistance can reach above level 4, and the sunlight resistance can reach above level 6.
  • This method has simple process flow, energy saving and emission reduction, and is a dyeing method that dyes quickly in a short time at low temperature. Low temperature dyeing is effective Reduce fiber damage during the dyeing process, reduce fiber weight loss rate, and help improve the production rate of post-process products.

Abstract

The present invention discloses an acid low-temperature dip dyeing method for a polyamide 56 fiber and fabric. The dyeing method of the present invention comprises the following step: using an acidic dye, a neutral dye or an active dye to dye a polyamide 56 fiber or a fabric thereof. The method has the following advantages: (1) a good dyeing effect, a deep color yield, and a high dye uptake rate; (2) a good color fastness, and the level of rub resistance and wash resistance reaching up to four or above, and the level of color fastness to sunlight reaching up to six or above; and (3) a simple process flow, energy-saving and emission reduction, and being a dyeing method for quick dye uptake at a low temperature and within a short time, low-temperature dyeing effectively reducing damage to a fiber during dyeing, reducing the weight loss rate of the fiber, and facilitating increasing the production rate of a post-process product.

Description

一种锦纶56纤维及织物的酸性低温浸染染色方法Acidic low-temperature dip dyeing method for nylon 56 fiber and fabric 技术领域Technical field
本发明涉及一种锦纶56纤维及织物的酸性低温浸染染色方法，属于纺织染整领域。The invention relates to an acid low-temperature dip dyeing method for nylon 56 fibers and fabrics, and belongs to the field of textile dyeing and finishing.
背景技术Background technique
锦纶纤维俗称尼龙(简称PA)，是分子主链上含有重复酰胺基团(-NHCO-)的热塑性树脂的总称。锦纶作为主要的化学纤维品种之一，于1935年问世，是最早实现工业化生产的合成纤维。近年来虽然涤纶的发展很快，但锦纶仍以其优异的强力、耐磨性、弹性回复率、吸湿性等优良性能竞争于合成纤维之中，半个多世纪仍占有重要的地位。目前，锦纶应用最普遍、最广泛的是锦纶66和锦纶6，然而，它们的合成原料大部分来自于化石资源的衍生品。随着工业生产对锦纶材料的需求日益增长和化石资源的日渐枯竭，加之人们对于环境保护问题的日益关注，以可再生生物质资源替代不可再生化石原料制备化学品是未来发展的主要趋势。Nylon fiber, commonly known as nylon (PA), is a general term for thermoplastic resins containing repeating amide groups (-NHCO-) on the main chain of the molecule. As one of the main chemical fiber varieties, nylon came out in 1935 and was the first synthetic fiber to be industrialized. Although polyester has developed rapidly in recent years, nylon still competes among synthetic fibers with its excellent strength, abrasion resistance, elastic recovery rate, moisture absorption and other excellent properties, and it still occupies an important position for more than half a century. At present, nylon 66 and nylon 6 are the most commonly used and widely used. However, most of their synthetic raw materials are derived from fossil resources. With the increasing demand for nylon materials in industrial production and the depletion of fossil resources, coupled with people's increasing attention to environmental protection issues, replacing non-renewable fossil raw materials with renewable biomass resources to prepare chemicals is the main trend of future development.
传统锦纶66在纤维制造过程中，由于加工工艺变化，分子量较高，分子间的氢键较多，结晶度，取向度较高，无定形区结构较紧密，纤维之间的差异在染色时反映明显，极易产生不匀，造成“经柳”“横档”等疵病。传统锦纶通常在高温条件下，采用酸性染料染色，并且染色后需要固色处理，这是因为酸性染料上染锦纶大部分依靠染料分子与织物之间的范德华力和氢键结合，从而导致色牢度差等问题。生物基锦纶56纤维是一种新型生物基纤维，目前还没有针对锦纶56纤维的超低温高效浸染方法。In the traditional nylon 66 fiber manufacturing process, due to changes in processing technology, the molecular weight is higher, the hydrogen bonds between molecules are more, the crystallinity, the degree of orientation are higher, the structure of the amorphous region is tighter, and the difference between the fibers is reflected in the dyeing Obviously, it is easy to produce unevenness, causing defects such as "jingliu" and "horizontal stalls". Traditional nylon is usually dyed with acid dyes under high temperature conditions, and it needs fixing treatment after dyeing. This is because the dyeing of nylon with acid dyes mostly relies on the van der Waals force and hydrogen bonding between the dye molecules and the fabric, resulting in fast color Poor degree and other issues. Bio-based nylon 56 fiber is a new type of bio-based fiber, and there is no ultra-low temperature and high-efficiency dip dyeing method for nylon 56 fiber.
发明内容Summary of the invention
本发明的目的是提供一种锦纶56纤维或其织物的酸性浴超低温高效浸染染色方法，本发明采用酸性染料、中性染料和活性染料实现对锦纶56纤维或其织物的浸染。The purpose of the present invention is to provide an acid bath ultra-low temperature and high-efficiency dip dyeing method for nylon 56 fiber or its fabric. The invention adopts acid dyes, neutral dyes and reactive dyes to realize the dip dyeing of nylon 56 fiber or its fabric.
本发明所提供的锦纶56纤维或其织物的酸性浴浸染染色方法，包括 如下步骤：The acid bath dip dyeing method of nylon 56 fiber or its fabric provided by the present invention includes the following steps:
采用酸性染料、中性染料或活性染料对锦纶56纤维或锦纶56织物进行染色；Use acid dyes, neutral dyes or reactive dyes to dye nylon 56 fibers or nylon 56 fabrics;
上述酸性浴浸染染色方法中，所述锦纶56纤维具体可为长丝或短纤；In the above acid bath dip dyeing method, the nylon 56 fiber may specifically be filament or staple fiber;
所述锦纶56纤维的端氨基的含量可为20～80mol/10 6gr，优选30～60mol/10 6gr，更优选45～55mol/10 6gr； The content of the terminal amino group of the nylon 56 fiber may be 20 to 80 mol/10 6 gr, preferably 30 to 60 mol/10 6 gr, more preferably 45 to 55 mol/10 6 gr;
所述锦纶56纤维的端羧基的含量可为50～110mol/10 6gr，优选60～90mol/10 6gr，更优选65～75mol/10 6gr。 Nylon 56 content of the terminal carboxyl group of fibers may be 50 ~ 110mol / 10 6 gr, preferably 60 ~ 90mol / 10 6 gr, more preferably 65 ~ 75mol / 10 6 gr.
所述锦纶56纤维的结晶度可为30～70％，优选45～65％，更优选45～60％。The crystallinity of the nylon 56 fiber may be 30-70%, preferably 45-65%, more preferably 45-60%.
所述锦纶56织物由上述锦纶56纤维形成，具体可为锦纶56针织物、锦纶56机织物或锦纶56无纺布。The nylon 56 fabric is formed of the above nylon 56 fiber, and specifically may be a nylon 56 knitted fabric, a nylon 56 woven fabric or a nylon 56 non-woven fabric.
上述酸性浴浸染染色方法中，所述锦纶56纤维可由熔体直接纺丝法或熔体间歇纺丝法制备得到；In the above acid bath dip dyeing method, the nylon 56 fiber can be prepared by a melt direct spinning method or a melt batch spinning method;
调节锦纶56盐液的pH值为7.5～8.5，优选7.5～8.0。Adjust the pH of the nylon 56 salt solution to 7.5-8.5, preferably 7.5-8.0.
调节牵伸倍数为1.1～5倍，以实现结晶度的调节。Adjust the draft ratio from 1.1 to 5 times to achieve the adjustment of crystallinity.
上述酸性浴浸染染色方法中，采用所述酸性染料或所述中性染料染色时的步骤如下：In the above acid bath dip dyeing method, the steps for dyeing with the acid dye or the neutral dye are as follows:
将所述酸性染料或所述中性染料配成染液，浴比为1：2～10，调控pH值为2.0～6.8，并加入染色助剂，加入所述锦纶56纤维或其织物常温入染，然后以5～10℃/min的升温速率升温至30～80℃，保温1～20min即可，降至室温，进行染色后处理。The acid dye or the neutral dye is prepared into a dye solution, the bath ratio is 1:2-10, the pH value is adjusted to be 2.0-6.8, and dyeing auxiliaries are added, and the nylon 56 fiber or its fabric is added at room temperature. After dyeing, the temperature is raised to 30-80°C at a heating rate of 5-10°C/min, and the temperature is kept for 1-20 minutes, and then it is reduced to room temperature for post-dying treatment.
上述酸性浴浸染染色方法中，采用所述活性染料染色时的步骤如下：In the above acid bath dip dyeing method, the steps for dyeing with the reactive dye are as follows:
将所述活性染料配成染液，浴比1：2～10，加入1～10g/L元明粉(配液或恒温过程加入均可)，并加入染色助剂，调控pH值为2.0～6.5，常温下加入所述锦纶56纤维或其织物升温至30～60℃，保温1～20min，然后继续升温至50～80℃后加入固色剂进行固色10～30min即可，降至室温，进行染色后处理。The reactive dye is prepared into a dyeing solution with a bath ratio of 1:2～10, 1～10g/L sodium sulfate is added (additional liquid or constant temperature process can be added), and dyeing auxiliaries are added to adjust the pH to 2.0～ 6.5. Add the nylon 56 fiber or its fabric at room temperature and increase the temperature to 30～60℃, keep it for 1～20min, then continue to increase the temperature to 50～80℃, add the fixing agent to fix the color for 10～30min, then drop to room temperature , Carry out post-dyeing treatment.
所述固色剂可为表面活性剂(阳离子型)、无表面活性的季铵盐、树脂型固色剂、交联固色剂、无甲醛固色剂等，具体可为固色剂Y、纯碱或烧碱。The fixing agent can be a surface active agent (cationic), a non-surface-active quaternary ammonium salt, a resin type fixing agent, a crosslinking fixing agent, a formaldehyde-free fixing agent, etc., and specifically can be a fixing agent Y, Soda ash or caustic soda.
具体地，所述酸性染料可为偶氮类酸性染料、蒽醌类酸性染料、三芳甲烷类酸性染料、氧杂蒽类酸性染料和硝基类酸性染料中至少一种；Specifically, the acid dye may be at least one of azo acid dyes, anthraquinone acid dyes, triarylmethane acid dyes, xanthene acid dyes, and nitro acid dyes;
所述酸性染料具体可为酸性红NHFS、酸性黄NHFS、酸性蓝NHFS、F型弱酸性染料、酸性大红FG、酸性黄G、酸性黄AD、酸性红AD、酸性灰AD、弱酸性大红FG或弱酸性兰5R。The acid dye may specifically be acid red NHFS, acid yellow NHFS, acid blue NHFS, F type weak acid dye, acid scarlet FG, acid yellow G, acid yellow AD, acid red AD, acid gray AD, weak acid scarlet FG or Weak acid blue 5R.
具体地，所述中性染料可为酸性含媒染料中1:2型金属络合染料，具体可为安诺赛特M型金属络合染料、S型金属络合染料；Specifically, the neutral dye may be a 1:2 type metal complex dye in an acid mordant dye, and specifically may be an Annoset M-type metal complex dye or an S-type metal complex dye;
所述中性染料具体可为中性深黄GL、中性灰2BL、中性黄2R、中性酱红B、中性蓝2R、中性棕B、中性灰G、中性红GAL、中性藏BR、中性黑AW200％、中性黄TB、中性黄R、中性红3B、中性红10B、中性红3G、中性翠蓝G、中性蓝R或中性蓝RAWL等。The neutral dye can specifically be neutral dark yellow GL, neutral gray 2BL, neutral yellow 2R, neutral sauce red B, neutral blue 2R, neutral brown B, neutral gray G, neutral red GAL, Neutral Tibetan BR, Neutral Black AW200%, Neutral Yellow TB, Neutral Yellow R, Neutral Red 3B, Neutral Red 10B, Neutral Red 3G, Neutral Turquoise Blue G, Neutral Blue R or Neutral Blue RAWL etc.
具体地，所述活性染料可为氯均三嗪活性基类活性染料、乙烯砜活性基类活性染料、多活性基类活性染料、溴代丙烯酰胺活性基类活性染料、环氧类活性染料或叠氮类活性染料；Specifically, the reactive dye can be a chloros-triazine reactive group reactive dye, a vinylsulfone reactive group reactive dye, a multiple reactive group reactive dye, a bromoacrylamide reactive group reactive dye, an epoxy reactive dye or Azide reactive dyes;
氯均三嗪类：活性染料K-6G；乙烯砜类：活性染料K-NR；多活性基类：活性艳红M-3BE；溴代丙烯酰胺类：兰纳素蓝3G、活性红83、活性黄39、活性蓝69、安诺菲克斯红ARC、安诺菲克斯黄/金黄ARC、安诺菲克斯蓝ARC；未知结构活性染料活性：嫩黄WG、活性大红WG、活性艳兰WR、活性黑WG。Chlorine s-triazines: reactive dye K-6G; vinyl sulfones: reactive dye K-NR; multiple reactive groups: reactive brilliant red M-3BE; bromoacrylamides: Lannasol blue 3G, reactive red 83, Reactive Yellow 39, Reactive Blue 69, Anofix Red ARC, Anofix Yellow/Golden ARC, Anofix Blue ARC; Reactive dye activity of unknown structure: Bright Yellow WG, Reactive Scarlet WG, Reactive Brilliant Blue WR, reactive black WG.
具体地，所述染色助剂可为pH调节剂和匀染剂；Specifically, the dyeing auxiliary agent may be a pH adjusting agent and a leveling agent;
所述pH调节剂具体可为酸、碱、酸性氧化物、碱性氧化物、弱酸强碱盐、强酸弱碱盐类等，如醋酸、氢氧化钠、氧化钙、碳酸钠、氯化铵等，如采用1％浓度的水溶液；The pH adjusting agent may specifically be acid, alkali, acidic oxide, basic oxide, weak acid and strong base salt, strong acid and weak base salt, etc., such as acetic acid, sodium hydroxide, calcium oxide, sodium carbonate, ammonium chloride, etc. , Such as using a 1% concentration aqueous solution;
所述pH调节剂用量可为0.5～5g/L；The dosage of the pH adjuster can be 0.5-5 g/L;
所述匀染剂具体可为平平加O、匀染剂JV-905、匀染剂JV-1、匀染剂SET、匀染剂HJ-219或匀染剂NL；The leveling agent can specifically be leveling plus O, leveling agent JV-905, leveling agent JV-1, leveling agent SET, leveling agent HJ-219 or leveling agent NL;
所述匀染剂的用量可为0.1～5％(o.w.f.)。The dosage of the leveling agent can be 0.1 to 5% (o.w.f.).
上述酸性浴浸染染色方法中，所述染色步骤后，还包括后处理步骤；In the above acid bath dip dyeing method, after the dyeing step, a post-treatment step is further included;
采用所述酸性染料和所述中性染料染色后的后处理包括如下步骤：热水洗、水洗和晾干；The post-treatment after dyeing with the acid dye and the neutral dye includes the following steps: washing with hot water, washing with water and drying;
所述热水洗：40～60℃热水冲洗1～3次；The hot water washing: 40～60℃ hot water washing 1～3 times;
所述水洗：室温水冲洗1～3次；The water washing: washing with room temperature water for 1 to 3 times;
采用所述活性染料染色后的后处理包括如下步骤：热水洗、水洗、皂洗、水洗、晾干；The post-treatment after dyeing with the reactive dyes includes the following steps: washing with hot water, washing with water, soaping, washing with water, and drying;
所述热水洗：40～60℃热水洗涤1～3次；The hot water washing: 40-60°C hot water washing 1 to 3 times;
所述水洗：室温水冲洗1～3次；The water washing: washing with room temperature water for 1 to 3 times;
所述皂洗的条件如下：皂粉1～5g/L，温度为40～80℃，时间为5～10min，浴比为1：15。The conditions of the soaping are as follows: soap powder 1-5g/L, temperature 40-80°C, time 5-10min, bath ratio 1:15.
附图说明Description of the drawings
图1为不同端氨基含量的锦纶56纤维的染色效果。Figure 1 shows the dyeing effect of nylon 56 fibers with different amino terminal content.
图2为70℃条件下，酸性染料(酸性蓝NHFS)上染锦纶纤维的上染速率曲线。Figure 2 shows the dyeing rate curve of nylon fiber dyed with acid dye (acid blue NHFS) at 70°C.
图3为65℃条件下，中性染料(中性深黄GL)上染锦纶纤维的上染速率曲线。Figure 3 shows the dyeing rate curve of nylon fiber dyed with neutral dye (Neutral Dark Yellow GL) at 65°C.
图4为60℃条件下，活性染料(活性艳兰D-RV)上染锦纶纤维的上染速率曲线。Figure 4 shows the dyeing rate curve of nylon fiber dyed with reactive dye (Reactive Brilliant Blue D-RV) at 60°C.
具体实施方式Detailed ways
下述实施例中所使用的实验方法如无特殊说明，均为常规方法。The experimental methods used in the following examples are conventional methods unless otherwise specified.
下述实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。The materials, reagents, etc. used in the following examples can be obtained from commercial sources unless otherwise specified.
下述实施例中所用的锦纶为66为市售产品，测试端氨基含量为46mol/10 6gr。 The nylon 66 used in the following examples is a commercially available product, and the test terminal amino group content is 46 mol/10 6 gr.
下述实施例中上染百分率的测定方法为：用分光光度计在最大吸收波 长处分别测定染色前后染液的吸光度，根据下式计算上染百分率：Ct＝(1–A 1/A 0)×100％(式中：A 0为原染液吸光度；A 1为染色后残液的吸光度) The method for measuring the dye uptake percentage in the following examples is: use a spectrophotometer to measure the absorbance of the dye solution before and after dyeing at the maximum absorption wavelength, and calculate the dye uptake percentage according to the following formula: Ct = (1-A 1 /A 0 ) ×100% (where: A 0 is the absorbance of the original dye solution; A 1 is the absorbance of the residual solution after dyeing)
本发明实施例所采用的锦纶56纤维，按照下述方法制备：The nylon 56 fiber used in the embodiment of the present invention was prepared according to the following method:
在盐液罐中配制50wt％浓度的锦纶56盐水溶液，具体步骤：取锦纶56干盐90kg，加入到55kg脱盐水中，完全溶解，调节盐液pH值7.5～8.5。配好盐液后将盐液罐加热至50℃，待温度达到设定温度，打开供料阀将盐液注入聚合反应釜中开始预聚合，预聚合试验条件：反应釜内设定温度212℃，压力1.75MPa，搅拌速度60r/min，反应2h，然后升温到250℃。当温度达到250℃后即开始降压，降压时间约1h，降压同时反应釜温度升到270℃，抽真空约10min，此时釜内温度约升至275℃，聚合反应完成，直接排料，经过冷水、吹风冷却，切粒机切断得到锦纶56切片。切片在80℃条件下，烘干22h，设置纺丝条件：纺丝温度288℃，计量泵转速16rpm/min，纺丝速度1000m/min，侧吹风压为450pa，卷绕油剂F5103浓度5％，牵伸倍数及加热温度为：一牵倍率2.5～3.5；二牵倍率1.01～1.42；牵伸箱温度170；二牵温度180；热板温度200；三牵温度180。卷绕得到锦纶56纤维。Prepare a 50wt% nylon 56 salt aqueous solution in a salt tank. The specific steps are: take 90 kg of nylon 56 dry salt and add it to 55 kg of demineralized water to completely dissolve it, and adjust the pH of the salt solution to 7.5-8.5. After the salt solution is prepared, heat the salt solution tank to 50°C. When the temperature reaches the set temperature, open the feed valve and inject the salt solution into the polymerization reactor to start pre-polymerization. The pre-polymerization test condition: the set temperature in the reactor is 212°C , The pressure is 1.75MPa, the stirring speed is 60r/min, the reaction is 2h, and then the temperature is raised to 250°C. When the temperature reaches 250°C, the pressure will start to drop. The pressure drop will take about 1h. At the same time, the temperature of the reactor will rise to 270°C and the vacuum will be pumped for about 10 minutes. At this time, the temperature in the kettle will rise to 275°C, and the polymerization reaction will be completed. After cooling by cold water and air blowing, the pelletizer cuts to obtain nylon 56 slices. The slices were dried at 80℃ for 22h, and spinning conditions were set: spinning temperature 288℃, metering pump speed 16rpm/min, spinning speed 1000m/min, side blowing pressure 450pa, winding oil F5103 concentration 5% , The drafting ratio and heating temperature are: one-drawing ratio 2.5～3.5; two-drawing ratio 1.01～1.42; drafting box temperature 170; second-drawing temperature 180; hot plate temperature 200; three-drawing temperature 180. The nylon 56 fiber is obtained by winding.
不同盐液pH值对应纤维不同的端基和羧基含量如表1所示(控制牵伸倍数为3.5)。The different pH values of the saline solution correspond to the different end groups and carboxyl content of the fibers as shown in Table 1 (control draft ratio is 3.5).
由表1中的数据可以看出，盐水溶液pH<7.5时，端基含量偏低，盐水溶液pH>8.5时，反应原料酸胺比失衡，无法聚合，因此最适宜的pH值范围为7.5～8.0。It can be seen from the data in Table 1 that when the pH of the saline solution is less than 7.5, the end group content is low, and when the pH of the saline solution is greater than 8.5, the ratio of acid to amine of the reaction raw material is unbalanced and cannot be polymerized. Therefore, the most suitable pH range is 7.5~ 8.0.
表1不同盐液pH值对锦纶56纤维的端氨基含量的影响Table 1 The influence of different pH values of salt solution on the terminal amino content of nylon 56 fiber
Figure PCTCN2020141542-appb-000001
Figure PCTCN2020141542-appb-000001
Figure PCTCN2020141542-appb-000002
Figure PCTCN2020141542-appb-000002
采用1#样品和3#样品进行染色，选取染料中性灰2BL，配制1％(o.w.f.)的染液，染液pH值为6.8，并加入匀染剂平平加O 0.5％(o.w.f.)，染色浴比1:10。常温条件下，加入具有不同端氨基含量的被染物(1#和3#)；然后以2℃/min升温速率升温至70℃，保温20min，染色完成。染液冷却到常温，取出样品80℃温水洗涤1次，常温冷水洗涤1次，风干。Use 1# sample and 3# sample for dyeing, select the dye neutral gray 2BL, prepare 1% (owf) dye solution, dye solution pH is 6.8, and add leveling agent to 0.5% (owf), dye The bath ratio is 1:10. Under normal temperature conditions, add the dyes (1# and 3#) with different terminal amino content; then heat up to 70°C at a heating rate of 2°C/min, keep it for 20 minutes, and finish dyeing. The dye solution is cooled to normal temperature, and the sample is taken out and washed once with 80°C warm water, once with cold water at normal temperature, and dried in air.
染色效果如图1所示，左图为1#样品，右图为3#样品。The dyeing effect is shown in Figure 1. The left image is 1# sample, and the right image is 3# sample.
测试两种样品的上染率，分别为：1#样品上染率为68.3％，3#样品上染率为83.6％。The dye uptake rates of the two samples were tested, respectively: the dye uptake rate of the 1# sample was 68.3%, and the dye uptake rate of the 3# sample was 83.6%.
由表1和图1可以看出，调控pH值为7.5～8.0时，锦纶56纤维的端氨基值含量高，染色效果好。It can be seen from Table 1 and Figure 1 that when the pH is adjusted to 7.5 to 8.0, nylon 56 fiber has a high content of amino groups and a good dyeing effect.
不同牵伸倍数对应纤维不同的结晶度如表2所示(控制锦纶56盐水溶液的pH值为7.85)。The different crystallinity of the fibers corresponding to different drafting ratios is shown in Table 2 (controlling the pH value of the nylon 56 saline solution to 7.85).
按照上述方法对得到的锦纶56纤维进行染色，上染率如表2所示。The nylon 56 fiber obtained was dyed according to the above method, and the dye uptake rate is shown in Table 2.
表2 2#不同牵伸倍数对锦纶56纤维的结晶度的影响Table 2 The influence of 2# different draft multiples on the crystallinity of nylon 56 fiber
2#样品2#sample 结晶度(％)Crystallinity (%) 上染率％Dyeing rate%
①纤维牵伸2倍① Fiber draft is 2 times 56.856.8 84.384.3
②纤维牵伸3.4倍②The fiber draft is 3.4 times 64.064.0 78.978.9
由表2的数据可以看出，纤维的结晶度越大，则纤维的无定型区越小，即可进入纤维内部的染料越少，纤维上染效果越差。It can be seen from the data in Table 2 that the greater the crystallinity of the fiber, the smaller the amorphous area of the fiber, the less dye can enter the fiber, and the worse the dyeing effect of the fiber.
根据上述纤维制备方案，制备盐液pH为7.85，一级牵伸3.15倍，二级牵伸1.12倍(共牵伸3.53倍)的锦纶56纤维，测其端氨基含量为45.2mol/10 6gr、端羧基含量为74.3mol/10 6gr、结晶度为65.2％，进行下述染色处理。 According to the above-mentioned fiber preparation plan, the pH of the salt solution is 7.85, the first-stage draft is 3.15 times, and the second-stage draft is 1.12 times (the total draft is 3.53 times) nylon 56 fiber, and its terminal amino content is measured to be 45.2mol/10 6 gr , The terminal carboxyl group content is 74.3mol/10 6 gr, the crystallinity is 65.2%, and the following dyeing treatment is performed.
实施例1、测定酸性染料上染锦纶56、锦纶66的上染速率曲线Example 1. Determination of the dyeing rate curve of nylon 56 and nylon 66 dyed with acid dyes
配制1g/L酸性蓝NHFS染料标准染液，配制10组2mL标准染液的染浴，纤维0.2g，浴比1:500，调节所得染液的pH值至4.67，同时放入染色 温度设定为70℃的染色机中，分别于染色5min、10min、15min、20min、30min、45min、60min、75min、90min、120min取出样品，常温水冲洗干净，晾干后剥色测试其上染速率曲线。Prepare 1g/L acid blue NHFS dye standard dye solution, prepare 10 groups of 2mL standard dye solution dye bath, fiber 0.2g, bath ratio 1:500, adjust the pH value of the dye solution to 4.67, and put in the dyeing temperature setting at the same time In the dyeing machine at 70℃, take out the samples after dyeing for 5min, 10min, 15min, 20min, 30min, 45min, 60min, 75min, 90min, 120min, rinse with water at room temperature, and peel off after drying to test the dyeing rate curve.
酸性染料上染锦纶56、锦纶66染色速率曲线如图2所示。锦纶56、锦纶66平衡上染百分率如表3所示。Figure 2 shows the dyeing rate curve of nylon 56 and nylon 66 dyed with acid dyes. Table 3 shows the balance dyeing percentage of nylon 56 and nylon 66.
实施例2、测定中性染料上染锦纶56、锦纶66的上染速率Example 2. Determination of the dye uptake rate of nylon 56 and nylon 66 dyed with neutral dyes
配制1g/L中性深黄GL染料标准染液，调节所得染液的pH值至6.8，染色温度65℃，其余染色工艺同实施例1中的酸性染料上染速率方法。Prepare 1g/L neutral deep yellow GL dye standard dye solution, adjust the pH value of the dye solution to 6.8, dyeing temperature 65°C, and other dyeing processes are the same as the method of acid dye uptake rate in Example 1.
中性染料上染锦纶56、锦纶66染色速率曲线如图3所示。锦纶56、锦纶66平衡上染百分率如表3所示。Figure 3 shows the dyeing rate curve of nylon 56 and nylon 66 dyed with neutral dyes. Table 3 shows the balance dyeing percentage of nylon 56 and nylon 66.
实施例3、测定活性染料上染锦纶56、锦纶66的上染百分率Example 3. Determination of the percentage of dye uptake of nylon 56 and nylon 66 on reactive dyes
配制1g/L活性艳兰D-RV染料标准染液，染液中加入5g/L元明粉，调节所得染液的pH值至3.0，染色温度60℃(无固色步骤)，其余染色工艺同实施例1酸性染料上染速率方法。Prepare 1g/L reactive brilliant blue D-RV dye standard dye solution, add 5g/L sodium sulfate to the dye solution, adjust the pH value of the dye solution to 3.0, dyeing temperature 60℃ (no fixation step), and other dyeing process Same as Example 1 for acid dye uptake rate method.
活性染料上染锦纶56、锦纶66染色速率曲线如图4所示。锦纶56、锦纶66平衡上染百分率如表3所示。Figure 4 shows the dyeing rate curve of nylon 56 and nylon 66 dyed with reactive dyes. Table 3 shows the balance dyeing percentage of nylon 56 and nylon 66.
表3酸性染料、中性染料、活性染料染色锦纶56和锦纶66的上染百分率Table 3 Dyeing percentages of acid dyes, neutral dyes, and reactive dyes dyeing nylon 56 and nylon 66
Figure PCTCN2020141542-appb-000003
Figure PCTCN2020141542-appb-000003
由实施例1-3酸性染料、中性染料、活性染料染色锦纶56和锦纶66的上染百分率曲线可知：不同类型染料在低温条件下分别上染锦纶56和锦纶66两种纤维，锦纶56纤维在染色20min以内基本可以达到平衡上染百分率，而锦纶66至少需要60min才能达到较高的上染百分率，并且锦纶56平衡上染百分率明显高于锦纶66。From the dyeing percentage curves of the acid dyes, neutral dyes, and reactive dyes in Examples 1-3, nylon 56 and nylon 66 dyed with different types of dyes were dyed with nylon 56 and nylon 66 fibers under low temperature conditions. Nylon 56 fibers The balance dyeing percentage can basically be reached within 20 minutes of dyeing, while nylon 66 needs at least 60 minutes to achieve a higher dyeing percentage, and the balance dyeing percentage of nylon 56 is significantly higher than that of nylon 66.
实施例4、酸性染料浸染锦纶56纤维Example 4, acid dye dip dyeing nylon 56 fiber
选取染料酸性蓝NHFS，配制2％(o.w.f.)的染液，染液pH值为4.67，并加入匀染剂平平加O 0.5％(o.w.f.)，染色浴比1:5。常温条件下，加入被染织物2g；然后以5.5℃/min升温速率升温至70℃，保温15min，染色完成，染液冷却至室温，取出样品70℃热水洗涤3次，室温水洗涤1次，晾干。Select dye acid blue NHFS, prepare 2% (o.w.f.) dye solution, dye solution pH is 4.67, and add leveling agent to 0.5% (o.w.f.), dyeing bath ratio 1:5. Under normal temperature conditions, add 2g of the dyed fabric; then heat up to 70°C at a heating rate of 5.5°C/min, keep it for 15 minutes, and finish dyeing. Cool the dye solution to room temperature. Take out the sample and wash it with hot water at 70°C for 3 times, and wash it with water at room temperature once. , Let dry.
对比例1：按照上述方法对锦纶66染色，两种纤维实验测试结果如表4所示。Comparative Example 1: Nylon 66 was dyed according to the above method, and the experimental test results of the two fibers are shown in Table 4.
实施例5、中性染料浸染锦纶56纤维Example 5: Nylon 56 fiber impregnated with neutral dye
选取染料中性深黄GL配制3％(o.w.f.)的染液，染液pH值为6.8，并加入1.5％(o.w.f.)匀染剂HJ-219，染色浴比1:10。常温条件下，加入被染织物2g；然后以5℃/min升温速率升温至65℃，保温20min，染色完成，染液冷却至室温，取出样品60℃热水洗涤1次，室温水洗涤1次，晾干。Select the dye neutral deep yellow GL to prepare a 3% (o.w.f.) dye solution, the pH of the dye solution is 6.8, and 1.5% (o.w.f.) levelling agent HJ-219 is added, and the dyeing bath ratio is 1:10. Under normal temperature conditions, add 2g of the dyed fabric; then heat up to 65°C at a heating rate of 5°C/min, keep for 20min, dyeing is completed, the dye solution is cooled to room temperature, take out the sample and wash it with hot water at 60°C once, and wash it with water at room temperature once , Let dry.
对比例2：按照上述方法对锦纶66染色，两种纤维实验测试结果如表4所示。Comparative Example 2: Nylon 66 was dyed according to the above method, and the experimental test results of the two fibers are shown in Table 4.
实施例6、活性染料浸染锦纶56纤维Example 6. Dip dyeing nylon 56 fiber with reactive dyes
选取染料活性艳兰D-RV，配制3％(o.w.f.)的染液，染液pH值为3.0，染色浴比1:8，加入2％(o.w.f.)匀染剂JV-1，元明粉5g/L。常温条件下，加入被染织物2g，染液以1℃/min升温至40℃，浸染15min，然后继续以1℃/min升温至60℃，加入碳酸钠20g/L，进行固色保温20min，染色完成，染液冷却至室温，取出样品40℃热水洗涤1次，室温水洗涤1次，皂洗(2g/L皂片，45℃，10min，浴比1:10)、室温水洗涤1次，晾干。Select dye reactive brilliant blue D-RV, prepare 3% (owf) dye solution, dye solution pH value is 3.0, dyeing bath ratio 1:8, add 2% (owf) levelling agent JV-1, sodium sulfate 5g /L. Under normal temperature conditions, add 2g of the dyed fabric, heat the dye solution to 40°C at 1°C/min, dip-dye for 15min, then continue to heat up to 60°C at 1°C/min, add 20g/L of sodium carbonate, and hold for 20min. After the dyeing is completed, the dye solution is cooled to room temperature, and the sample is washed once with hot water at 40°C, washed once with water at room temperature, soaping (2g/L soap flakes, 45°C, 10min, bath ratio 1:10), washing with room temperature water 1 Let dry.
对比例3、按照上述方法对锦纶66染色，两种纤维实验测试结果如表4所示。Comparative Example 3. Nylon 66 was dyed according to the above method. The experimental test results of the two fibers are shown in Table 4.
表4酸性染料、中性染料、活性染料染锦纶56、锦纶66色牢度测试结果Table 4 Color fastness test results of acid dyes, neutral dyes, and reactive dyes on nylon 56 and nylon 66
Figure PCTCN2020141542-appb-000004
Figure PCTCN2020141542-appb-000004
Figure PCTCN2020141542-appb-000005
Figure PCTCN2020141542-appb-000005
由实施例4-6和对比例1-3的染色效果可以看出，同类染料在相同低温条件下，分别染色锦纶56和锦纶66，锦纶56的表观深度明显高于锦纶66，锦纶56的色牢度优于锦纶66，符合市场应用要求。From the dyeing effects of Examples 4-6 and Comparative Examples 1-3, it can be seen that the same dyes dye nylon 56 and nylon 66 respectively under the same low temperature conditions. The apparent depth of nylon 56 is significantly higher than that of nylon 66 and nylon 56. Color fastness is better than nylon 66, which meets market application requirements.
工业应用Industrial application
本发明提供的锦纶56纤维的酸性浴染色方法，具有如下优势：The acid bath dyeing method of nylon 56 fiber provided by the present invention has the following advantages:
(1)染色效果好，得色深，上染率高；(2)色牢度好，染色织物耐摩擦、耐水洗、耐日晒等色牢度测试结果均可以满足使用要求，耐摩擦、耐水洗可达4级以上，耐日晒色牢可达6级以上；(3)该方法工艺流程简单、节能减排，是一种低温短时间内快速上染的染色方法，低温染色有效地降低纤维在染色过程中受到的损伤，降低纤维失重率，有利于提高后工艺产品制成率。(1) The dyeing effect is good, the color is deep, and the dye uptake rate is high; (2) The color fastness is good, and the color fastness test results of the dyed fabrics such as rubbing resistance, washing resistance and sunlight resistance can meet the requirements of use. The washing resistance can reach above level 4, and the sunlight resistance can reach above level 6. (3) This method has simple process flow, energy saving and emission reduction, and is a dyeing method that dyes quickly in a short time at low temperature. Low temperature dyeing is effective Reduce fiber damage during the dyeing process, reduce fiber weight loss rate, and help improve the production rate of post-process products.

Claims (10)

  1. 一种锦纶56纤维或其织物的酸性浴浸染染色方法，包括如下步骤：A method for acid bath dip dyeing of nylon 56 fiber or its fabric, comprising the following steps:
    采用酸性染料、中性染料或活性染料对锦纶56纤维或锦纶56织物进行染色；Use acid dyes, neutral dyes or reactive dyes to dye nylon 56 fibers or nylon 56 fabrics;
    所述锦纶56纤维的端氨基的含量为20mol/10 6gr～80mol/10 6gr，端羧基的含量为50mol/10 6gr～110mol/10 6gr，结晶度为30～70％。 The content of terminal amino groups of the nylon 56 fiber is 20 mol/10 6 gr to 80 mol/10 6 gr, the content of terminal carboxyl groups is 50 mol/10 6 gr to 110 mol/10 6 gr, and the crystallinity is 30 to 70%.
  2. 根据权利要求1所述的酸性浴浸染染色方法，其特征在于：所述锦纶56纤维由熔体直接纺丝法或熔体间歇纺丝法制备得到；The acid bath dip dyeing method according to claim 1, wherein the nylon 56 fiber is prepared by a melt direct spinning method or a melt batch spinning method;
    调节锦纶56盐液的pH值为7.5～8.5；Adjust the pH of nylon 56 salt solution to 7.5～8.5;
    调节牵伸倍数为1.1～5倍。Adjust the draft ratio from 1.1 to 5 times.
  3. 根据权利要求1或2所述的酸性浴浸染染色方法，其特征在于：采用所述酸性染料或所述中性染料染色时的步骤如下：The acid bath dip dyeing method according to claim 1 or 2, characterized in that the steps for dyeing with the acid dye or the neutral dye are as follows:
    将所述酸性染料或所述中性染料配成染液，浴比为1：2～10，加入染色助剂，调控pH值为2.0～6.8，加入所述锦纶56纤维或其织物常温入染，然后以5～10℃/min的升温速率升温至30～80℃，保温1～20min即可，降至室温，进行染色后处理。The acid dye or the neutral dye is prepared into a dye liquor, the bath ratio is 1:2-10, dyeing auxiliary agent is added, the pH value is adjusted to 2.0-6.8, and the nylon 56 fiber or its fabric is dyed at room temperature , And then heat up to 30-80°C at a heating rate of 5-10°C/min, keep it for 1-20 minutes, and then lower to room temperature for post-dyeing treatment.
  4. 根据权利要求1或2所述的酸性浴浸染染色方法，其特征在于：采用所述活性染料染色时的步骤如下：The acid bath dip dyeing method according to claim 1 or 2, characterized in that the steps of dyeing with the reactive dye are as follows:
    将所述活性染料配成染液，浴比为1：2～10，加入1～10g/L元明粉，并加入染色助剂，调控pH值为2.0～6.5，常温下加入所述锦纶56纤维或其织物升温至30～60℃，浸染1～20min，然后继续升温至50～80℃后加入固色剂进行固色10～30min即可，降至室温，进行后处理。The reactive dye is prepared into a dye solution, the bath ratio is 1:2-10, 1-10g/L sodium sulfate is added, and dyeing auxiliaries are added to adjust the pH to 2.0-6.5, and the nylon 56 is added at room temperature. The fiber or its fabric is heated to 30-60°C, impregnated for 1-20min, then the temperature is increased to 50-80°C, and the fixing agent is added to fix the color for 10-30min, then it is lowered to room temperature for post-treatment.
  5. 根据权利要求1-4中任一项所述的酸性浴浸染染色方法，其特征在于：所述酸性染料为偶氮类酸性染料、蒽醌类酸性染料、三芳甲烷类酸性染料、氧杂蒽类酸性染料和硝基类酸性染料中任一种。The acid bath dip dyeing method according to any one of claims 1 to 4, wherein the acid dyes are azo acid dyes, anthraquinone acid dyes, triarylmethane acid dyes, and xanthenes. Any of acid dyes and nitro acid dyes.
  6. 根据权利要求1-4中任一项所述的酸性浴浸染染色方法，其特征在于：所述中性染料为酸性含媒染料中1:2型金属络合染料。The acid bath dip dyeing method according to any one of claims 1 to 4, wherein the neutral dye is a 1:2 metal complex dye in the acid mordant dye.
  7. 根据权利要求1-4中任一项所述的酸性浴浸染染色方法，其特征在 于：所述活性染料为氯均三嗪活性基类活性染料、乙烯砜活性基类活性染料、多活性基类活性染料、溴代丙烯酰胺活性基类活性染料、环氧类活性染料或叠氮类活性染料。The acid bath dip dyeing method according to any one of claims 1 to 4, wherein the reactive dyes are chloros-triazine reactive group reactive dyes, vinyl sulfone reactive group reactive dyes, and multiple reactive group reactive dyes. Reactive dyes, bromoacrylamide reactive dyes, epoxy reactive dyes or azide reactive dyes.
  8. 根据权利要求3-7中任一项所述的酸性浴浸染染色方法，其特征在于：所述染色助剂为pH调节剂和匀染剂。The acid bath dip dyeing method according to any one of claims 3-7, wherein the dyeing auxiliary agent is a pH adjusting agent and a leveling agent.
  9. 根据权利要求8所述的酸性浴浸染染色方法，其特征在于：所述pH调节剂为酸、碱、酸性氧化物、碱性氧化物、弱酸强碱盐或强酸弱碱；The acid bath dip dyeing method according to claim 8, wherein the pH adjusting agent is acid, alkali, acidic oxide, alkaline oxide, weak acid and strong alkali salt or strong acid and weak alkali;
    所述匀染剂为平平加O、匀染剂JV-905、匀染剂JV-1、匀染剂SET、匀染剂HJ-219或匀染剂NL。The leveling agent is Pingping plus O, leveling agent JV-905, leveling agent JV-1, leveling agent SET, leveling agent HJ-219 or leveling agent NL.
  10. 根据权利要求1-9中任一项所述的酸性浴浸染染色方法，其特征在于：所述锦纶56纤维长丝或短纤；The acid bath dip dyeing method according to any one of claims 1-9, wherein the nylon 56 fiber filament or staple fiber;
    所述锦纶56织物为锦纶56针织物、锦纶56机织物或锦纶56无纺布。The nylon 56 fabric is a nylon 56 knitted fabric, a nylon 56 woven fabric or a nylon 56 non-woven fabric.
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Families Citing this family (4)

* Cited by examiner, † Cited by third party
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CN111778739A (en) * 2020-01-02 2020-10-16 军事科学院***工程研究院军需工程技术研究所 Acid low-temperature dip dyeing method for chinlon 56 fiber and fabric
CN112853574B (en) * 2021-02-05 2022-08-09 淄博大染坊丝绸集团有限公司 Warp-willow prevention screening method and application of real silk fabric
CN115478444B (en) * 2021-05-31 2023-12-08 上海凯赛生物技术股份有限公司 Uniform dyeing system and dyeing method for polyamide 56 fabric
CN116590939A (en) * 2023-06-05 2023-08-15 常州裕源灵泰面料科技有限公司 High-reproducibility high-level-dyeing-property high-efficiency dyeing process combining acid dyes with different dyeing rates

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105887518A (en) * 2016-06-17 2016-08-24 优纤科技（丹东）有限公司 Dyeing method for nylon-56 fibers
CN105970688A (en) * 2016-06-17 2016-09-28 优纤科技（丹东）有限公司 Acid bath dyeing method of chinlon 56 fiber fabric
CN109763359A (en) * 2019-01-02 2019-05-17 鲁泰纺织股份有限公司 A kind of colouring method of 56 yarn of biology base nylon
CN111778739A (en) * 2020-01-02 2020-10-16 军事科学院***工程研究院军需工程技术研究所 Acid low-temperature dip dyeing method for chinlon 56 fiber and fabric

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5454191B2 (en) * 2010-02-09 2014-03-26 東レ株式会社 Crimped yarn and fiber structure
CN102199884A (en) * 2011-03-07 2011-09-28 浙江理工大学 Method for dip-dyeing polyamide/cotton (viscose) fabrics with acid or neutral and reactive dyes in one-bath way
CN105019266A (en) * 2015-08-14 2015-11-04 太仓市诚乐化纤有限公司 Polyamide fabric modifying, dyeing and finishing process
CN105887230A (en) * 2016-06-17 2016-08-24 优纤科技（丹东）有限公司 Nylon 56 short fiber and melt direct spinning preparation method thereof
CN108049213B (en) * 2018-01-21 2019-08-27 新兴纺织（深圳）有限公司 A kind of colouring method of polyamide fibre
CN110344266B (en) * 2018-04-08 2021-05-14 上海凯赛生物技术股份有限公司 One-step dyeing method for cotton/polyamide 56 fiber blended fabric by using reactive dye and acid or neutral dye in one bath
CN109112854B (en) * 2018-07-20 2021-05-25 互太(番禺)纺织印染有限公司 Dyeing process of polyamide fabric
CN109881503A (en) * 2019-03-06 2019-06-14 江阴职业技术学院 A kind of nylon fabric reactive dyeing processing method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105887518A (en) * 2016-06-17 2016-08-24 优纤科技（丹东）有限公司 Dyeing method for nylon-56 fibers
CN105970688A (en) * 2016-06-17 2016-09-28 优纤科技（丹东）有限公司 Acid bath dyeing method of chinlon 56 fiber fabric
CN109763359A (en) * 2019-01-02 2019-05-17 鲁泰纺织股份有限公司 A kind of colouring method of 56 yarn of biology base nylon
CN111778739A (en) * 2020-01-02 2020-10-16 军事科学院***工程研究院军需工程技术研究所 Acid low-temperature dip dyeing method for chinlon 56 fiber and fabric

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CAO SHIHUI, LI HONG-WEI;HAO XIN-MIN: "Dyeing process of bio-based PA56 fabric with vat dyes", DYEING & FINISHING, FANG ZHI GONG YE BU YIN RAN HANG YE JI SHU KAI FA ZHONG XIN; QUAN GUO YIN RAN GONG YE KE JI QING BAO ZHAN BIAN JI, CN, no. 24, 1 January 2019 (2019-01-01), CN, pages 31 - 34, XP055826895, ISSN: 1000-4017 *
YU WEICAI: "Explore and analysis on the physical performance and spinnability of Nylon 56", POLYESTER INDUSTRY, CHINA, vol. 27, no. 1, 1 January 2014 (2014-01-01), China, pages 38 - 39, XP055826898, ISSN: 1008-8261, DOI: 10.3969 /j.issn.1008-8261.2014.01.011 *

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