铜改性抗菌防螨聚酰胺6纤维的制备及其性能

doi:10.13475/j.fzxb.20220900701

纺织学报 ›› 2024, Vol. 45 ›› Issue (03): 19-27.doi: 10.13475/j.fzxb.20220900701

铜改性抗菌防螨聚酰胺6纤维的制备及其性能

郑晓頔¹, 盛平厚¹(), 蒋佳岑², 李睿¹, 焦红娟¹, 邱志成¹

1.中国纺织科学研究院有限公司生物源纤维制造技术国家重点实验室, 北京 100025
2.内蒙古工业大学轻工与纺织学院, 内蒙古呼和浩特 010081

收稿日期:2022-12-02 修回日期:2023-03-12 出版日期:2024-03-15 发布日期:2024-04-15
通讯作者: 盛平厚
作者简介:郑晓頔(1991—),女,高级工程师,博士。主要研究方向为纤维用功能粉体制备、应用与性能调控。

Preparation and performance of copper modified antimicrobial and anti-mite polyamide 6 fiber

ZHENG Xiaodi¹, SHENG Pinghou¹(), JIANG Jiacen², LI Rui¹, JIAO Hongjuan¹, QIU Zhicheng¹

1. State Key Laboratory of Biobased Fiber Manufacturing Technology, China Textile Academy, Beijing 100025, China
2. College of Light Industry and Textiles, Inner Mongolia University of Technology, Hohhot, Inner Mongolia 010081, China

Received:2022-12-02 Revised:2023-03-12 Published:2024-03-15 Online:2024-04-15
Contact: SHENG Pinghou

摘要/Abstract

摘要：

为解决纳米铜抗菌剂在纤维中分散性、界面相容性差的问题,采用油酸对纳米球形铜抗菌剂进行包覆处理,并与聚酰胺6(PA6)基体共混挤出造粒制得抗菌防螨PA6切片,再经熔融单组分纺丝和熔融复合纺丝制得铜改性抗菌防螨PA6纤维。对铜抗菌剂的形貌结构和界面相容性,抗菌防螨PA6切片的热稳定性和可纺性以及纤维的铜含量、力学性能和抗菌防霉防螨性能进行分析。结果表明:油酸包覆球形铜抗菌剂的分散性较好,且与PA6基体相容性良好,抗菌防螨PA6切片的热稳定性、可纺性良好;铜改性抗菌防螨PA6纤维的颜色均匀性一致,纤维制成率高达88%,铜改性PA6拉伸变形丝的断裂伸长率为29.95%,断裂强度达到4.43 cN/dtex;洗涤50次前后铜改性抗菌防螨PA6纤维对白色念珠菌、金黄色葡萄球菌、大肠杆菌的抑菌率均大于99%,其织物防霉等级达到0级,螨虫驱避率达到89%,抗菌防霉防螨性能高效耐久。

关键词: 球形铜抗菌剂, 聚酰胺6纤维, 油酸, 可纺性, 抗菌性能, 防螨性能

Abstract:

Objective The application of copper antimicrobial agent in fiber materials is faced with three major problems. Firstly, the functional nano powder has serious agglomeration and poor compatibility with polymer materials, which makes it difficult to disperse evenly. Secondly, copper is easy to be oxidized and discolored, resulting in poor stability and uniformity of fiber color. Thirdly, spinnability and mechanical properties of fiber decrease with the increase of antimicrobial agent content, therefore it is difficult to increase the content of copper antimicrobial agent in the fiber. It is important to improve the dispersion, interfacial compatibility, and antioxidant properties of copper antimicrobial agent in fibers.

Method In this study, the nano spherical copper antimicrobial agent was coated with oleic acid. Two types of copper modified PA6 antimicrobial masterbatch containing 1.1% and 2.1% copper antimicrobial agent were obtained by squeezing granulation. Copper modified PA6 antimicrobial and anti-mite fibers were obtained by melt spinning and composite spinning, respectively. The structure, morphology and interfacial compatibility of copper antimicrobial agent, thermal stability and spinnability of antimicrobial masterbatch, copper content, mechanical properties, antimicrobial, and anti-mite properties of fiber and fabric samples were analyzed.

Results The diffraction peaks were found sharp with no other impurity peaks appearing, indicating that the sample was well crystallized and was still pure after modification. No obvious weight loss is found during the dehydration at about 100 ℃, which indicated satisfactory hydrophobicity of the sample. Sample C1 showed about 0.4% of weight loss at 300 ℃, and its thermal stability met the requirement of melt spinning, and the dispersion was good without large-size agglomeration under the electron microscope and showed good hydrophobicity with water contact angle of 146°, which was consistent with the TG results. Whether it is melted spinning or composite spinning, pre-oriented yarn sample had high fiber yield of 94%. The fiber yield of draw textured yarn sample is 93% and 94%, respectively. The modified spherical copper antimicrobial agent hardly affected the mechanical properties of PA6, which could be attributed to the reduced agglomeration and improved dispersion of the oleic acid modified spherical copper antimicrobial agent, resulting in fewer large rigid particles in the fiber. The interfacial interaction between PA6 and copper particles was enhanced with the help of oleic acid. The elongation at break of the copper modified PA6 fiber was 29.95% and the tensile breaking strength was 4.43 cN/dtex. For Candida albicans, Staphylococcus aureus and Escherichia coli, copper modified PA6 DTY sample (X1') and copper modified PA6 sheath-core DTY sample (X2') both have high bacteriostasis rate of 99%. The bacteriostasis rate was still over 99% after washing for 50 cycles, indicating that the samples had good resistance to washing and superior long-lasting antibacterial performance. After washing, the copper content of the X1' sample was 1.26% and that of the X2' sample was 1.11%. Compared with the copper content of the two fiber samples before washing, the copper content remained basically the same within the allowable testing error. For mixed test, fungi colony consists of Aspergillus niger, Trichoderma viride, Penicillium funiculosum and Chaetomium globosum, the mildew proof grade of the fiber reached grade 0, meaning no obvious mildew colony under magnifier. X2' samples were woven into fabric for the anti-mite performance test. The result showed that the average number of mites in the test group was 22 and that in control group was 194, suggesting the repellent rate of mites of 89%.

Conclusion The dispersibility of oleic acid coated spherical copper antimicrobial agent and its compatibility with PA6 are good. Copper modified PA6 antimicrobial masterbatch has good thermal stability and spinnability. Copper modified PA6 antimicrobial and anti-mite fiber has high fiber yield of 88% and excellent color consistency at a high antimicrobial addition of 1.1%. The mechanical property of the fiber is adjustable. The antimicrobial, mildewproof and anti-mite properties of fiber samples are strong and durable. Therefore, copper modified PA6 antimicrobial and anti-mite fibers have broad industrial application potentiality in military personal protective equipment, fiber products for medical and health industry and textiles for civil clothing and home decoration.

Key words: spherical copper antimicrobial agent, polyamide 6 fiber, oleic acid, spinnability, antimicrobial property, anti-mite property

中图分类号:

TS102.6

郑晓頔, 盛平厚, 蒋佳岑, 李睿, 焦红娟, 邱志成. 铜改性抗菌防螨聚酰胺6纤维的制备及其性能[J]. 纺织学报, 2024, 45(03): 19-27.

ZHENG Xiaodi, SHENG Pinghou, JIANG Jiacen, LI Rui, JIAO Hongjuan, QIU Zhicheng. Preparation and performance of copper modified antimicrobial and anti-mite polyamide 6 fiber[J]. Journal of Textile Research, 2024, 45(03): 19-27.

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扫描区域	质量百分比/%			原子百分比/%
扫描区域	C	O	Cu	C	O	Cu
纤维表面颗粒点扫描	61.47	28.08	10.46	72.72	24.94	2.34
纤维表面区域扫描	65.07	34.61	0.32	71.42	28.52	0.07

样品编号	牵伸倍数	线密度/ dtex	断裂强度/ (cN·dtex^-1)	断裂伸长率/%	取向因子
X3	1.0	118.91	3.04	86.94	0.57
X4	1.2	100.72	3.34	46.67	0.67
X5	1.3	94.04	3.88	39.67	0.72
X6	1.5	82.22	4.46	21.67	0.74

扫描区域	质量百分比/%
扫描区域	C	O	Cu	Pt	K	Cl
纤维断裂处颗粒点扫描	52.67	18.37	-1.79	12.84	9.75	8.15
纤维断裂处区域扫描	59.44	22.79	-0.51	18.28	—	—

样品编号	洗涤处理	抑菌率%
样品编号	洗涤处理	对大肠杆菌	对金黄色葡萄球菌	对白色念珠菌
X1'	未洗涤	>99	>99	>99
	洗涤50次	>99	>99	>99
X2'	未洗涤	>99	>99	>99
	洗涤50次	>99	>99	>99

样品编号	洗涤处理	抑菌率/%
样品编号	洗涤处理	对大肠杆菌	对金黄色葡萄球菌	对白色念珠菌
S1	未洗涤	>99	>99	92
	洗涤50次	>99	>99	93
S2	未洗涤	>99	>99	>99
	洗涤50次	>99	>99	>99
S3	未洗涤	>99	>99	>99
	洗涤50次	>99	>99	>99

铜改性抗菌防螨聚酰胺6纤维的制备及其性能

Preparation and performance of copper modified antimicrobial and anti-mite polyamide 6 fiber

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样品编号	断裂强度/ (cN·dtex^-1)	断裂伸长率/ %	POY 制成率/%	POY-DTY 制成率/ %	DTY总制成率/ %
X1	3.80	62.28	94	—	—
X2	3.45	76.96	94	—	—
X1'	4.43	29.95	—	94	88
X2'	4.36	28.76	—	93	87

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