WO2016119483A1 - 锦纶纺丝用添加剂 - Google Patents

锦纶纺丝用添加剂 Download PDF

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WO2016119483A1
WO2016119483A1 PCT/CN2015/091551 CN2015091551W WO2016119483A1 WO 2016119483 A1 WO2016119483 A1 WO 2016119483A1 CN 2015091551 W CN2015091551 W CN 2015091551W WO 2016119483 A1 WO2016119483 A1 WO 2016119483A1
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additive
spinning
nylon
oil
agent
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French (fr)
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陈文凤
龚剑兵
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江苏文凤化纤集团有限公司
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Publication of WO2016119483A1 publication Critical patent/WO2016119483A1/zh

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic Table; Zincates; Cadmates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
    • D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
    • D—TEXTILES; PAPER
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    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/144—Alcohols; Metal alcoholates
    • D06M13/148—Polyalcohols, e.g. glycerol or glucose
    • D—TEXTILES; PAPER
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    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D—TEXTILES; PAPER
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    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
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    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35—Heterocyclic compounds
    • D06M13/352—Heterocyclic compounds having five-membered heterocyclic rings
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    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/368—Hydroxyalkylamines; Derivatives thereof, e.g. Kritchevsky bases
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    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/392—Nitroso compounds; Nitro compounds
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    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/53—Polyethers

Definitions

  • the invention relates to the technical field of auxiliary chemicals in synthetic fiber processing technology, in particular to an additive for nylon spinning.
  • Nylon is the trade name of polycaprolactam fiber in China.
  • the foreign trade name is nylon.
  • DuPont Company applied for a patent for spinning nylon at a speed of 5,500 m/min.
  • the nylon fiber has excellent performance, in addition to the common corrosion resistance, mildew resistance, high wet strength, no fear of insects, moisture absorption.
  • the main feature is the high breaking strength.
  • aramid it is almost the most powerful fiber; it has excellent wear resistance and is the best abrasion resistance fiber in textile fibers; since the 12th century In the mid-1980s, the development of chemical fiber oils began in foreign countries.
  • Chinese invention patent 201010284459.0 discloses a nylon FDY oil agent and a preparation method thereof, wherein the oil agent is composed of the following components: isooctyl stearate, scouring Agent, oleic acid, coconut oil diethanolamine, hydrogenated castor oil polyoxyethylene ether, fatty alcohol polyoxyethylene ether, oleic acid sarcosine, hypophosphorous acid, hydrogen Potassium oxide, humectant.
  • the oil has good thermal stability, low volatilization and no coking.
  • due to the addition of a lot of vegetable oil and mineral oil these oils are easily deteriorated during use, and bacteria are generated, which may lead to oil spoilage and affect the performance of the oil.
  • Chinese invention patent 201210237550.6 discloses a non-emulsion type nylon 6 filament high speed spinning pure oil agent, wherein the smoothing agent is composed of three polyether type nonionic surfactants, respectively It is a fatty alcohol ethylene oxide propylene oxide copolyether, a fatty alcohol polyoxyethylene ether, a polyoxyethylene alkyl phenol ether.
  • the sizing agent is a nonionic surfactant fatty acid polyoxyethylene ether ester
  • the antistatic agent is a fatty alcohol polyoxyethylene ether phosphate, an alkyl phosphate amine (potassium) salt
  • the binding additive is Ac
  • the conditioning agent is water.
  • the oil has small smoke, no gelation, no aggregation, no precipitation, good thermal stability and good chemical properties, but the oil agent only has the smoothness and antistatic property of the common oil agent, and does not impart some functional properties to the chemical fiber.
  • the components are relatively single.
  • Chinese invention patent 201010278753.0 discloses a nylon oil agent which is composed of mineral oil, potassium cetyl phosphate, dodecyl phosphate diethanol ammonium salt, castor oil Polyoxyethylene (40) ester, sorbitan monostearate.
  • the invention has reasonable formula, good use effect and low production cost.
  • the formulation of the oil is relatively simple, and only the smoothing agent and the antistatic agent as well as the conventional functions of emulsification are included in the formulation, and the addition of the mineral oil causes an increase in volatile substances and has a great influence on the environment.
  • the first aspect of the invention relates to an additive for nylon spinning, the additive consisting of the following parts by weight:
  • Titanium dioxide 3-5 Titanium dioxide 3-5
  • Dispersing agent 1-3 Dispersing agent 1-3.
  • the present invention relates to an oily agent for spinning, the spinning oil composition comprising the following parts by weight:
  • the invention solves the problem that the nylon oil agent has a relatively simple function, and the nano additive according to the invention has better dispersibility, and the oil can be made after adding the oil agent.
  • the agent has good heat resistance, smoothness and antistatic property, can increase the cohesion of the tow, reduce the friction coefficient, and most importantly, the addition of the nano additive can increase the antibacterial property of the oil agent, and can adjust the oil agent.
  • the viscosity greatly improves the stability and makes the processed nylon yarn have anti-ultraviolet characteristics.
  • This embodiment provides an additive for nylon spinning, and the composition of the additive is expressed by parts by weight:
  • the preparation process of the nano additive includes the following steps:
  • Step 1 First, 5 parts of zinc oxide, 3 parts of titanium dioxide, and 1 part of polyvinylpyrrolidone were added to a ball mill and ground for 6 hours to obtain a dry powder A.
  • Step 2 Mix dry powder A in a ratio of 1 g of dry powder to 5 ml of ethanol, add to a ball mill, continue grinding, ball milling for 5 hours, remove anhydrous ethanol, and dry in vacuum to obtain nano dry powder B.
  • Step 3 2 parts of montmorillonite, 3 parts of vermiculite together with 1 part of sodium dodecylbenzene sulfonate added to absolute ethanol, the content of dispersant and inorganic mineral salt in the mixture is controlled at 50%, and the mixture is added Ultrasonic dispersion and stripping were carried out for 3 hours. After dispersion, the ethanol was removed, together with the dry powder B, and the nano additive was compounded by further adding to the ball mill for 4 hours.
  • the present embodiment provides an additive for spinning nylon.
  • the preparation method is the same as in the first embodiment.
  • the composition of the additive is expressed in parts by weight:
  • This embodiment provides an additive for spinning a nylon.
  • the preparation method is the same as in the first embodiment.
  • the composition of the additive is expressed in parts by weight:
  • the nylon high-speed spinning oil agent is prepared by the following method: under stirring conditions (1000 rpm), 70 parts of isooctyl stearate, 6 parts of scouring agent, 15 parts of oleic acid, 3 parts of coconut oil diethanolamine, 2 parts of hypophosphorous acid, 2 parts of oleic acid sarcosine, 1 part of potassium hydroxide, and 1 part of a wetting agent were mixed and stirred for 30 minutes.
  • the spinning oil agent in Comparative Example 1 was not added with a nano additive, and it was used as Comparative Example 1, and the effect of using the nano additive in the test example after adding the spinning oil agent, the oil additive added by the nano additive in the example
  • the composition is expressed in parts by weight:
  • the oil smoke point is one of the important indicators. As can be seen from Table 1, the smoke point of Comparative Example 1 is 135 ° C, and the smoke points of Examples 1-3 are all greater than 140 ° C, which may be because The addition of the micro-nano additive can form micro-nano micelles in the oil agent, and the smoothing agent and the emulsifier are coated in the micelle system, thereby increasing the smoke temperature of the oil agent.
  • Flame retardant finishing flame retardant finishing: 45 ° C tilting method, the instrument is specified to be placed at an angle of 45 ° C, measuring the intensity of burning of nylon filaments after ignition, the less severe the better, the slower the better.
  • UV radiation protection index is the ratio of the time required for UV radiation to reach the critical dose of erythema and the time value of the same degree of injury when no protective products are used. The greater the value, the better the protective effect.
  • the nylon filaments are neatly wrapped around the cardboard to test the UV protection function of the alignment plane.
  • the dynamic friction coefficient ⁇ K is an important indicator of the smoothness of the oil. The smaller the ⁇ K, the smaller the smoothness.
  • the volume specific resistance ⁇ V is an index of the antistatic property of the oil, and the smaller the ⁇ V, the better the antistatic property.
  • Wet cohesion means the cohesiveness of the oily wire on the wet state. The larger the value, the better the clustering property of the upper slurry and the better the falling performance.
  • Table 2 shows the effect of the addition of each functional additive on the fibers after oiling.
  • the Applicant has further found that the antistatic properties of the fibers of Examples 1-3 can be improved because the micro-nano additive and the antistatic agent can have a synergistic antistatic effect because the addition of the micro-nano additive can be on the fiber surface.
  • the formation of a micro-nano film can reduce the repulsive force of the nylon and the antistatic agent, make the cationic surfactant easier to adhere to the surface of the nylon, and increase the antistatic property of the nylon.
  • the applicant has optimized the formulation of the micro-nano additive.
  • the compounding between the micro-nano additives can increase the antistatic and antibacterial properties of the oil agent.
  • the good micro-nano additive is titanium dioxide and zinc oxide.
  • the best compounding ratio is titanium dioxide: the weight ratio of zinc oxide is 2:1, which can effectively improve the antistatic property and antibacterial property of the oil.
  • Table 3 As can be seen from Table 3, when the other conditions are the same, when the addition ratio of the micro-nano additive is 2:1, the oil fiber has the highest antibacterial property and antistatic property.
  • micro-nano-titanium dioxide and zinc oxide are photocatalysts, but they are active against light of different wavelengths. Therefore, after compounding the two, the response range of visible light can be maximized, and the range is wide. Sterilization.
  • the sterilization mechanism is that in the presence of visible light, it can release free radicals with strong oxidizing properties, and the bacteria in the solution can be oxidized and killed, thereby further improving the antibacterial property of the oil agent.
  • the micro-nano additive and the antistatic agent can have a synergistic antistatic effect, because the addition of the micro-nano additive forms a micro-nano film on the surface of the fiber, which can reduce the repulsive force of the nylon and the antistatic agent, and make the cationic surfactant It is easier to adhere to the surface of nylon and increase the antistatic properties of nylon.
  • the invention solves the problem that the nylon oil agent has a relatively simple function, and the nano additive according to the invention has good dispersibility, and the oil agent can have good heat resistance and smoothness after adding the oil agent. And antistatic property, can increase the cohesion force of the tow, reduce the friction coefficient, and most importantly, the addition of the nano additive can increase the antibacterial property of the oil agent, and can adjust the viscosity of the oil agent, greatly improving the stability thereof, and
  • the processed nylon yarn is made to have ultraviolet protection properties.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Artificial Filaments (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

本发明提供一种锦纶纺丝用添加剂，添加剂由如下重量份数的各组分组成：氧化锌5-10份，二氧化钛3-5份，蒙脱土2-6份，蛭石3-6份，分散剂1-3份。本发明制备的添加剂，粒径较小，分散性能好，加入纺丝油剂后，可以增加纺丝油剂的稳定性，且可以增加纺丝油剂的防紫外性以及抗菌性能。

Description

锦纶纺丝用添加剂 技术领域
本发明涉及合成纤维加工技术中助剂技术领域，尤其涉及一种锦纶纺丝用添加剂。
背景技术
锦纶是我国聚己内酰胺纤维的商品名称，国外商品名称为尼龙，1938年，德国施拉克研究成功了用单一己内酰胺为原料，加热聚合制成的聚己内酰胺，并申请了专利。早在1955年美国杜邦公司就申请了用5500米/分的速度纺制锦纶的专利，锦纶纤维性能优良，除了具有各合成纤维共有的耐腐蚀，耐霉烂，湿强度高，不怕虫蛀，吸湿率低外，其主要特点还是断裂强度高，除芳纶外，几乎是强力最高的一种纤维；耐磨性优异，是纺织纤维中耐磨性最好的一种纤维；自十二世纪三十年代中期，国外就开始了化纤油剂的研发，由于国外油剂的开发都是由大企业完成，加之其研究成果商业价值很好，所以公开的油剂配方很少，油剂的开发与生产以日本最为活跃，开发油剂的公司有松本，帝人，旭化成，花王，以及德国的汉高，美国的大祥美华等公司。二十世纪五十年代，为适应锦纶长丝的普通纺丝工艺，开发了以矿物质油为主题，添加乳化剂与防静电剂的油剂。六十年代中期开始，化纤生产发展到以大卷装和以锭子式变形为主的的生产工艺，生产了以脂肪酸和PO/EO聚醚并用的油剂。八十年代到九十年代，化纤长丝发展到高速、超高速及多功能化。开发了改性的PO/EO聚醚以及具有低摩擦，超耐热，易润湿等特殊功能和添加剂的油剂。到了二十一世纪后，化纤生产向大型化，高速化，差别化，功能化发展，单线能力扩大，聚合物质量改善，对油剂也提出了新的要求。
经对现有技术的检索，中国发明专利201010284459.0(公开日2011年1月19日)披露了一种锦纶FDY油剂及制备方法，其中油剂由以下成分组成：硬脂酸异辛酯，精练剂，油酸，椰子油二乙醇胺，氢化蓖麻油聚氧乙烯醚，脂肪醇聚氧乙烯醚，油酸肌氨酸，次磷酸，氢 氧化钾，湿润剂。这种油剂热稳定性好、挥发少、不结焦。但是由于加入了很多植物油以及矿物质油，在使用过程中，这些油脂很容易变质，产生细菌，会导致油剂腐败，影响油剂的使用性能。
中国发明专利201210237550.6(公开日：2012年11月14日)披露了一种非乳液型锦纶6长丝高速纺丝纯油剂，其中平滑剂由三种聚醚型非离子表面活性剂组成，分别是脂肪醇环氧乙烷环氧丙烷共聚醚、脂肪醇聚氧乙烯醚、聚氧乙烯烷基酚醚。集束剂是非离子表面活性剂脂肪酸聚氧乙烯醚酯，防静电剂是脂肪醇聚氧乙烯醚磷酸盐、烷基磷酸酯胺(钾)盐，粘结添加剂是Ac，调整剂是水。这种油剂发烟小、不凝胶、不集结、不沉淀、热稳定性和化学性能好，但是此油剂只具有普通油剂的平滑性以及防静电性，并没有赋予化纤一些功能性质，组分比较单一。
中国发明专利201010278753.0(公开日:2012年04月04日)公开了一种锦纶油剂，该油剂由矿物油、十六烷基磷酸钾、十二烷基磷酸酯二乙醇铵盐、蓖麻油聚氧乙烯(40)酯、失水山梨醇单硬脂酸酯组成。本发明配方合理，使用效果好，生产成本低。但是该油剂配方相对简单，配方中只有平滑剂和抗静电剂以及乳化的常规功能，且矿物油的加入会引起挥发物质的增加，对环境造成很大的影响。
发明内容
在下文中给出关于本发明的简要概述，以便提供关于本发明的某些方面的基本理解。应当理解，这个概述并不是关于本发明的穷举性概述。它并不是意图确定本发明的关键或重要部分，也不是意图限定本发明的范围。其目的仅仅是以简化的形式给出某些概念，以此作为稍后论述的更详细描述的前序。
第一方面本发明涉及一种锦纶纺丝用添加剂，所述添加剂由如下重量份数的各组分组成：
氧化锌 5-10，
二氧化钛 3-5，
蒙脱土 2-6，
蛭石 3-6，
分散剂 1-3。
第二方面，本发明涉及一种纺丝用油剂，所述纺丝用油剂由下列重量份数的各组分组成：
脂肪醇磷酸酯 55，
十八醇磷酸酯钾盐 4，
蓖麻油聚氧乙烯醚 7，
聚乙二醇月桂酸双酯 4，
季戊四醇 2，
三乙醇胺 2，
聚乙烯基正丁基醚 4，
溴硝醇 5，
苯并三唑 3，
四羟甲基氯化磷 2，
前述的锦纶纺丝用添加剂 3-8。
与现有技术相比，本发明具有如下的有益效果：本发明解决了锦纶油剂功能较为单一的问题，本发明所述的纳米添加剂，具有较好的分散性，加入油剂后可以使油剂具有良好的耐热性，平滑性和防静电性，能够增加丝束的抱合力，降低摩擦系数，最重要的是通加入纳米添加剂可以使增加油剂的防菌性，并可以调整油剂的粘度，大大提高其稳定性，并且使加工后的锦纶丝具有防紫外的特性。
具体实施方式
下面来说明本发明的实施例。在本发明的一种实施方式中描述的元素和特征可以与一个或更多个其它实施方式中示出的元素和特征相结合。应当注意，为了清楚的目的，说明中省略了与本发明无关的、本领域普通技术人员已知的部件和处理的表示和描述。
实施例1
本实施例提供了一种锦纶纺丝用添加剂，该添加剂的组成按照重量份数表示为：
氧化锌 5，
二氧化钛 3，
蒙脱土 2，
蛭石 3，
聚乙烯吡咯烷酮 1，
十二烷基苯磺酸钠 1。
此纳米添加剂的制备工艺包括以下步骤：
步骤一：首先，将氧化锌5份，二氧化钛3份，1份聚乙烯吡咯烷酮加入球磨机，研磨6h，得到干粉A。步骤二：将干粉A按照1g干粉加入5ml乙醇的比例混合，加入球磨机，继续研磨，球磨5小时，除去无水乙醇，真空干燥，得到纳米干粉B。步骤三：将蒙脱土2份，蛭石3份连同1份十二烷基苯磺酸钠加入无水乙醇，此混合物中分散剂与无机矿物盐含量控制在在50％，将此混合物加入超声波中进行超声分散剥分3h，分散后，去除乙醇，连同干粉B，一起继续加入球磨机中研磨4h即得复配纳米添加剂。
实施例2
本实施例提供了一种锦纶纺丝用添加剂，制备方法参照实施例1，该添加剂的组成按照重量份数表示为：
氧化锌   10，
二氧化钛 5，
蒙脱土 6，
蛭石 6，
油酸 1。
实施例3
本实施例提供了一种锦纶纺丝用添加剂，制备方法参照实施例1，该添加剂的组成,按照重量份数表示为：
氧化锌    7，
二氧化钛  3.5，
蒙脱土 3，
蛭石 4，
油酸 2。
对比例1
常规技术中，锦纶高速纺丝用油剂是采用如下的方法制备而得：搅拌条件下(1000转/分)，取硬脂酸异辛酯70份、精练剂6份、油酸15份、椰子油二乙醇胺3份、次磷酸2份、油酸肌氨酸2份、氢氧化钾1份、润湿剂1份进行混合，搅拌30分钟，即得。
实施效果
对比例1中的纺丝用油剂并未加入纳米添加剂，将其作为对比例1，测试实施例中的纳米添加剂加入纺丝油剂后的使用效果，实施例中的纳米添加剂加入的油剂的组成按照重量份数表示为：
脂肪醇磷酸酯 55，
十八醇磷酸酯钾盐 4，
蓖麻油聚氧乙烯醚 7，
聚乙二醇月桂酸双酯 4，
季戊四醇 2，
三乙醇胺 2，
聚乙烯基正丁基醚 4，
溴硝醇 5，
苯并三唑 3，
四羟甲基氯化磷 2。
表1对比例与实施例测试结果
Figure PCTCN2015091551-appb-000001
如表1所示，申请人发现加入纳米添加剂后制备的锦纶高速纺丝用油剂效果均优于对比例，具体而言：
乳液常温稳定性，由表1可知，对比例1制备的油剂在25度下， 7天后就会呈现牛奶状，有挂壁现象出现，稳定性较差，影响其使用与保存；而实施例1-3制备的油剂均呈现半透明状，无任何挂壁现象出现，具有非常好的稳定性；尤其是实施例3，申请人发现，再放置更长的时间，也不会出现挂壁现象，而其他实施例则会出现少许挂壁现象，从表1中可以看出，对比例1在高温稳定性测试中有少量破乳的产生，证明该体系乳化效果并不理想，而从实施例1-3可知，加入纳米添加剂后，纺丝油剂的高温稳定性能较好，80℃，8h并未发生破乳现象。
油剂发烟点是重要的指标之一，从表1中可以看出，对比例1的发烟点为135℃，而实施例1-3的发烟点均大于140℃，这可能是因为微纳米添加剂的加入，可以在油剂中形成微纳米胶束，将平滑剂以及乳化剂包覆在胶束体系中，从而提高油剂的发烟温度。
从以上数据可以看出，加入纳米添加剂后，其可以与油剂中的功能化助剂进行很好的协同作用，在增加抗静电性以及平滑性的额基础上，赋予油剂更好的抗菌性，阻燃性和防紫外性能。以及油剂的功能性。
为验证本发明对上油后纤维之实施效果，进行如下指标的测试：
阻燃整理性：阻燃整理性:45℃倾斜法，仪器规定试样以45℃倾斜放置，测量锦纶长丝点燃后燃烧的剧烈程度，剧烈程度越小越好，速度越慢越好。
防紫外线性：紫外辐射防护指数(UPF)是紫外辐射使皮肤达到出现红斑的临界剂量所需时间值和不用防护品时达到同样伤害程度的时间值之比，值越大，防护效果越好。将锦纶长丝整齐缠绕在纸板上，测试排列平面的紫外防护功能。
平滑性：动摩擦系数μK是油剂平滑性的重要指标，μK越小，平滑性越小。
抗静电性：体积比电阻ρV是油剂抗静电性的指标，ρV越小，抗静电性越好。
集束性：湿抱合力表示湿态上油浆丝的抱合性，其值越大，代表上油浆集束性越好，落浆性能越好。
表2显示了添加各功能助剂后对上油后纤维的影响结果。
表2上油后纤维性能测试结果
Figure PCTCN2015091551-appb-000002
Figure PCTCN2015091551-appb-000003
从表2中申请人发现，加入微纳米添加剂后，相应的指标均有所增加，其中上油后纤维的阻燃性，提高明显，实施例1-3的燃烧测试表明，上油纤维的燃烧性能提升明显，从表2中申请人发现，加入微纳米助剂后，并不会对织物的平滑性产生影响，这是因为在制备油剂过程中，申请人将各种功能助剂进行了充分的搅拌及分散，使其均匀的分布在油剂中。
申请人还进一步发现，实施例1-3的纤维抗静电性可以有所提升，这是由于微纳米助剂与抗静电剂可以具有协同抗静电效果，因为微纳米助剂的加入会在纤维表面形成一种微纳米薄膜，可以减少锦纶与抗静电剂的排斥力，使阳离子表面活性剂更容易附着在锦纶表面，增加锦纶的抗静电性。
为了进一步提高油剂的功能性，申请人对微纳米添加剂的配方进行了优化设计，申请人意外发现，微纳米助剂之间的复配可以增加油剂的抗静电性以及抗菌性，效果最好的微纳米添加剂为二氧化钛和氧化锌，最佳的复配比例为二氧化钛：氧化锌重量比为2:1时可以有效的提升油剂的抗静电性以及抗菌性。结果见表3，从表3中可以看出，在其他条件均一致的情况下，当微纳米添加剂的添加比例为2:1时，上油纤维的抗菌性和防静电性均最高。这是因为，微纳米二氧化钛与氧化锌属于光触媒，但两者对不同波长的光具有活性，所以将二者进行复配后，可以最大化的增加可见光的响应范围，在很大的范围内进行杀菌作用。其杀菌机理为，在有可见光存在下，其可以释放出具有强氧化性质的自由基，将溶液中的菌种进行氧化杀灭，从而可以进一步的提高油剂的抗菌性。
而微纳米助剂与抗静电剂可以具有协同抗静电效果，因为微纳米助剂的加入会在纤维表面形成一种微纳米薄膜，可以减少锦纶与抗静电剂的排斥力，使阳离子表面活性剂更容易附着在锦纶表面，增加锦纶的抗静电性。
表3复配微纳米添加剂对上油纤维的抗菌性以及抗静电性能的影响
Figure PCTCN2015091551-appb-000004
综上所述，本发明解决了锦纶油剂功能较为单一的问题，本发明所述的纳米添加剂，具有较好的分散性，加入油剂后可以使油剂具有良好的耐热性，平滑性和防静电性，能够增加丝束的抱合力，降低摩擦系数，最重要的是通加入纳米添加剂可以使增加油剂的防菌性，并可以调整油剂的粘度，大大提高其稳定性，并且使加工后的锦纶丝具有防紫外的特性。最后应说明的是：以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。

Claims (7)

  1. 一种锦纶纺丝用添加剂，其特征在于，所述锦纶纺丝用添加剂由如下重量份数的各组分组成：
    氧化锌 5-10，
    二氧化钛 3-5，
    蒙脱土 2-6，
    蛭石 3-6，
    分散剂 1-3。
  2. 根据权利要求1所述的锦纶纺丝用添加剂，其特征在于，所述氧化锌粒径大小为10-100nm。
  3. 根据权利要求1所述的锦纶纺丝用添加剂，其特征在于，所述二氧化钛的粒径大小为50-100nm。
  4. 根据权利要求1所述的锦纶纺丝用添加剂，其特征在于，所述蒙脱土的粒径大小为100-200nm。
  5. 根据权利要求1所述的锦纶纺丝用添加剂，其特征在于，所述蛭石的粒径大小为50-150nm。
  6. 根据权利要求1所述的锦纶纺丝用添加剂，其特征在于，所述分散剂为油酸，聚乙烯吡咯烷酮，十二烷基苯磺酸钠中的一种或者多种。
  7. 一种纺丝用油剂，其特征在于，所述纺丝用油剂由下列重量份数的各组分组成：
    脂肪醇磷酸酯 55，
    十八醇磷酸酯钾盐 4，
    蓖麻油聚氧乙烯醚 7，
    聚乙二醇月桂酸双酯 4，
    季戊四醇 2，
    三乙醇胺 2，
    聚乙烯基正丁基醚 4，
    溴硝醇 5，
    苯并三唑 3，
    四羟甲基氯化磷 2，
    权利要求1所述的锦纶纺丝用添加剂 3-8。
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