纺织学报 ›› 2025, Vol. 46 ›› Issue (12): 152-162.doi: 10.13475/j.fzxb.20250402801

• 染整工程 • 上一篇    下一篇

高色牢度反应性聚合物包覆炭黑直喷墨水制备及其印花性能

沈昕怡1,2, 李家炜1,2,3(), 邵宇1,2, 郭丁滔1,2, 何贵平4, 赵磊4, 戚栋明1,2,3, YOUSSEF Yehya Abel-Gawad5, KAFAFY Hany Hassan Ahmed Mohamed5   

  1. 1.浙江理工大学 生物基纤维材料全国重点实验室, 浙江 杭州 310018
    2.绿色低碳染整技术浙江省工程研究中心, 浙江 杭州 310018
    3.浙江省现代纺织技术创新中心, 浙江 绍兴 312000
    4.浙江纳美新材料股份有限公司, 浙江 湖州 313000
    5.国家研究中心纺织品研究部, 埃及 吉萨 12311
  • 收稿日期:2025-04-16 修回日期:2025-08-20 出版日期:2025-12-15 发布日期:2026-02-06
  • 通讯作者: 李家炜(1985—),男,副研究员,博士。主要研究方向为纺织品绿色低碳染整加工。E-mail:jiaweili@zstu.edu.cn
  • 作者简介:沈昕怡(2001—),女,硕士生。主要研究方向为聚合物包覆颜料墨水的制备和应用。
  • 基金资助:
    国家自然科学基金项目(51703200);浙江省“尖兵领雁+X”研发攻关计划项目(2024C01199);绍兴市产业关键技术攻关专项项目(2024B11007)

Preparation and printing properties of reactive polymer encapsulated carbon black direct printing ink with high color fastness

SHEN Xinyi1,2, LI Jiawei1,2,3(), SHAO Yu1,2, GUO Dingtao1,2, HE Guiping4, ZHAO Lei4, QI Dongming1,2,3, YOUSSEF Yehya Abel-Gawad5, KAFAFY Hany Hassan Ahmed Mohamed5   

  1. 1. State Key Laboratory of Bio-based Fiber Materials, Zhejiang Sci-Tech University, Hangzhou, Zhejiang 310018, China
    2. Zhejiang Provincial Engineering Research Center for Green and Low-carbon Dyeing & Finishing, Hangzhou, Zhejiang 310018, China
    3. Zhejiang Provincial Innovation Center of Advanced Textile Technology, Shaoxing, Zhejiang 312000,China
    4. Zhejiang Namei New Material Technology Co., Ltd., Huzhou, Zhejiang 313000, China
    5. Textile Research Division National Research Center, Giza 12311, Egypt
  • Received:2025-04-16 Revised:2025-08-20 Published:2025-12-15 Online:2026-02-06

摘要: 为提高炭黑(CB)分散稳定性与喷墨印花色牢度,采用无皂无硫可逆加成-断裂链转移聚合法,在CB微细粒子表面原位合成反应性聚合物包覆的CB乳胶,并将其配制成墨水用于免前处理和后水洗的涤纶/棉混纺织物数码喷墨印花;重点考察了环氧基单体甲基丙烯酸缩水甘油酯(GlyMA)质量分数对喷墨印花织物色深、色牢度、手感和透气性的影响。结果表明:所制备的纳米反应性聚合物包覆CB乳胶具有核壳结构,其平均粒径和最大粒径分别为107.9、396 nm;聚合物层通过空间位阻和静电排斥作用提升了墨水稳定性,在60 ℃下经5 d的热稳定性测试后,CB乳胶墨水的平均粒径增长率较CB色浆墨水降低59.2%;将CB乳胶墨水直喷涤纶/棉混纺织物,当GlyMA质量分数为5%时,喷墨印花织物的耐干、湿摩擦和耐水洗色牢度分别达4~5、4和5级,硬挺度较原涤纶/棉混纺织物提高23.0%,透气性降低21.5%。CB乳胶墨水不仅具有高色牢度和优异服用性能,且喷墨工序流程短,省去上浆和后水洗,符合纺织印染绿色低碳发展需求。

关键词: 炭黑, 数码印花喷墨墨水, 喷墨印花, 短流程, 涤纶/棉混纺织物, 核壳结构, 色牢度, 印花性能

Abstract:

Objective Digital inkjet printing technology has the advantages of low energy consumption and less sewage discharge, which is a new way to solve the problems of high water consumption, high energy consumption, and high pollution in the printing and dyeing industry. Carbon black (CB) is the key pigment of printing inks, but CB is easy to agglomerates and cannot be dispersed in aqueous media. Improving the dispersion stability of CB in water is a difficult and hot topic in the field of digital inkjet printing. To solve the above problems, we synthesized reactive polymer encapsulated CB latex inks, to meet the demand for printing inks with environmental considerations.

Method Polyacrylate encapsulated CB latexes with varying glycidyl methacrylate (GlyMA) contents were synthesized by sulfur-free reversible addition-fragmentation chain transfer (SF-RAFT) polymerization without surfactant on the CB particle surface, and their particle size, Zeta potential, apparent morphology and thermal stability were tested. Subsequently, CB latexes were prepared into inks, with their thermal stability and storage stability tested. The CB latex inks were used for digital inkjet printing of polyester/cotton blended fabrics, and the printed fabrics were characterized for morphology, color performance, hand feel and color fastness.

Results The optimum CB color paste milling conditions were found to be 30% allyloxy polyoxyethylene (10) nonyl ammonium sulfate (DNS-86) of the pigment's mass fraction and 5 h milling, yielding small particles, with an average and maximum particle size of 52.0 nm and 121.8 nm, respectively. The reactive P(methyl methacrylate-co-DNS-86)-b-P(benzyl methacrylate-co-butyl methacrylate-co-GlyMA [P(MMA-co-DNS-86)-b-P(BzMA-co-BA-co-GlyMA)]/CB latexes were successfully synthesized by in situ polymerization on the CB particle surfaces after milling, and the color fastness of inkjet printing fabric was adjusted by changing the mass fraction of GlyMA. It was found that the average and maximum particle size of CB latex (5% GlyMA) were 107.9 nm and 396 nm, respectively, and the Zeta potential was -53.14 mV, indicating that the CB latex displayed excellent dispersion with high stability. In addition, TEM images showed that the CB latex had a typical core-shell structure, with small and well dispersed particles, consistent with the size data. The gel permeation chromatography (GPC) curve of CB latex revealed the number average molecular weight (Mn) was 38 426 g/mol, the polymer dispersibility index was 1.83, and a single-peak distribution, suggesting good polymerization control in preparing reactive polymer encapsulated CB latexes. The viscosity, conductivity and surface tension of the CB latexes were modulated using 10% glycerol and 0.02% 104e to prepare CB latex inkjet printing inks. After a 5-day thermal stability test at 60 ℃, the average particle size of CB color paste inks increased by 85.1% from 82.8 nm to 153.3 nm, and that of reactive polymer encapsulated CB latex inks increased by 29.5% from 107.9 nm to 139.8 nm, with the increase rate 59.2% lower than that of the former. The prepared reactive polymer encapsulated CB latex inks were directly inkjet printed on polyester/cotton blended fabric without pre-treatment and post-washing. When the mass fraction of GlyMA was 5%, the dry/wet rubbing and washing fastness of the inkjet printing fabric reached levels 4-5, 4 and 5. However, it was noted that the stiffness was increased by 23.0%, and the air permeability was reduced by 21.5% compared with the original fabric.

Conclusion In this research, reactive P(MMA-co-DNS-86)-b-P(BzMA-co-BA-co-GlyMA)/CB latexes with GlyMA of different mass fraction were synthesized and prepared as inks for inkjet printing of polyester/cotton blended fabrics. The CB latex inks were directly inkjet printing onto the polyester/cotton blended fabrics without pre-treatment and post-washing. When the mass fraction of GlyMA was 5%, inkjet printing fabrics dry/wet rubbing and washing color fastness reached levels 4-5, 4 and 5, compared with the original fabrics, stiffness increased by 23.0%, air permeability reduced by 21.5%. This inkjet printing process has a short process and meets the demand for green and low-carbon development in textile printing and dyeing.

Key words: carbon black, digital printing inkjet ink, inkjet printing, short process, polyester/cotton blended fabric, core-shell structure, color fastness, printing property

中图分类号: 

  • TS193.5

图1

反应性聚合物包覆CB乳胶制备过程"

表1

反应性聚合物包覆CB乳胶的配方"

样品组 BzMA
质量/
g
BA
质量/
g
GlyMA
质量/
g
KPS
质量/
mg
GlyMA质量
占总单体的
质量分数/%
0% GlyMA 1.74 1.74 69.6 0
1% GlyMA 1.72 1.72 0.04 69.6 1
3% GlyMA 1.69 1.69 0.10 69.6 3
5% GlyMA 1.65 1.65 0.17 69.6 5
7% GlyMA 1.63 1.62 0.24 69.6 7
10% GlyMA 1.57 1.57 0.35 69.6 10

图2

DNS-86质量分数及研磨时间对CB色浆粒径的影响"

图3

CB和反应性聚合物包覆CB乳胶的红外光谱图"

图4

反应性聚合物包覆CB乳胶的1H NMR图"

图5

反应性聚合物包覆CB乳胶(5% GlyMA)的GPC和TGA曲线"

表2

反应性聚合物包覆CB乳胶的转化率、Zeta电位、粒径大小及分布"

样品 转化率/
%
平均粒
径/nm
最大粒
径/nm
多分散
指数
Zeta电位/
mV
0% GlyMA 96.0 94.18 295 0.141 -60.55
1% GlyMA 94.8 99.04 295 0.157 -54.58
3% GlyMA 87.3 104.2 342 0.165 -52.87
5% GlyMA 93.2 107.9 396 0.179 -53.14
7% GlyMA 89.7 110.5 459 0.191 -50.92
10% GlyMA 87.4 117.4 396 0.200 -59.47

图6

CB、CB色浆和反应性聚合物包覆CB乳胶(5% GlyMA)的TEM照片"

图7

反应性聚合物包覆CB乳胶的理化性能"

图8

CB色浆墨水与反应性聚合物包覆CB乳胶墨水的热稳定性能"

表3

CB色浆墨水与反应性聚合物包覆CB乳胶墨水的储存稳定性能"

样品 原始 储存12个月
平均粒径/
nm
Zeta电位/
mV
平均粒径/
nm
Zeta电位/
mV
CB色浆墨水 82.8 -36.46 152.9 -24.87
CB乳胶墨水 107.9 -53.14 108.4 -50.42

图9

涤纶/棉混纺织物的SEM照片"

图10

喷墨印花涤纶/棉混纺织物的照片"

表4

喷墨印花织物性能"

样品组 K/S 不匀度 颜色参数 耐摩擦色牢度/级 耐水洗色
牢度/级
硬挺度 透气率/
(mm·s-1)
L* a* b* 湿
原布 34.60 245.95
0% GlyMA印花 6.02 0.035 40.42 2.34 -1.29 3 3 2~3 38.79 200.83
1% GlyMA印花 5.85 0.097 37.16 2.11 -1.82 4 3 4~5 40.13 198.43
3% GlyMA印花 5.80 0.088 42.17 2.45 -1.50 4~5 3~4 5 40.21 194.45
5% GlyMA印花 5.63 0.075 42.46 2.64 -2.03 4~5 4 5 42.57 193.11
7% GlyMA印花 4.80 0.046 45.67 2.69 -1.91 4~5 3 5 48.87 189.38
10% GlyMA印花 2.83 0.160 56.70 2.96 -4.61 4~5 3 5 51.27 188.15
市售炭黑墨水印花 3.88 0.096 49.13 2.57 6.48 2~3 1 2 43.48 190.26
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