Bio-based self-stratifying waterborne coatings via silicone-induced phase separation for enhanced hardness and anti-graffiti performance

IF 7.3 2区材料科学 Q1 CHEMISTRY, APPLIED

Progress in Organic Coatings Pub Date : 2025-09-01 DOI:10.1016/j.porgcoat.2025.109622

Yuchen Zhang , Gonghao Wang , Die Yang , Yongbo Ding , Yinxiu Zuo , Liang Shen

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引用次数: 0

Abstract

This study developed a green and bio-based waterborne coating system that self-stratifies via silicone-induced phase separation. The system is built on a rosin acid-modified epoxy ester/acrylate hybrid resin and includes a small amount of vinyl-terminated silicone oil to promote phase separation. Two resin formulations were prepared, namely a silicone oil-free epoxy ester/acrylate hybrid resin (designated as EAR20, rosin acid constitutes 20 % of the total carboxylic acid content of epoxy ester) and a counterpart containing 2.5 wt% vinyl-terminated silicone oil (designated as EAR80–2.5, rosin acid constitutes 80 % of the total carboxylic acid content of epoxy ester). Self-stratifying coatings were fabricated by blending these two resins, with optimal performance observed at a 2:1 (EAR20:EAR80–2.5) mass ratio. During curing, the silicone-containing resin phase preferentially migrated to the surface, forming a distinct silicone-rich upper layer in a one-step process. This stratified architecture yields a hard, hydrophobic surface while preserving robust adhesion and mechanical integrity in the bulk. Compared to the silicone-free coating (with pure EAR20), the self-stratifying coating exhibited a markedly higher surface hardness (pencil hardness increased from B to H) and significantly improved durability. Water resistance in an immersion test extended from 7 days to 12 days without failure, and abrasion resistance increased from 5 ± 1 to 41 ± 2 cycles. The static water contact angle also rose from 75 ± 2° to 89 ± 2°, indicating a more hydrophobic surface. Furthermore, the silicone-rich top layer imparted anti-graffiti functionality, enabling sprayed ink to be easily wiped off without residue. Overall, this silicone oil-induced stratification strategy synergistically enhances both mechanical robustness and surface properties, offering a promising and sustainable route for developing high-performance waterborne coatings.

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生物基自分层水性涂料通过硅诱导相分离提高硬度和抗涂鸦性能

本研究开发了一种绿色和生物基水性涂料系统，该系统通过硅诱导相分离自分层。该系统是建立在松香酸改性环氧酯/丙烯酸酯杂化树脂和包括少量的乙烯基端硅油，以促进相分离。制备了两种树脂配方，即无硅油环氧酯/丙烯酸酯混合树脂（编号为EAR20，松香酸占环氧酯总羧酸含量的20%）和含有2.5 wt%端乙烯硅油的对应物（编号为EAR80-2.5，松香酸占环氧酯总羧酸含量的80%）。将这两种树脂混合制备自分层涂层，在2:1 （EAR20: EAR80-2.5）的质量比下，涂层性能最佳。在固化过程中，含硅树脂相优先迁移到表面，在一步过程中形成明显的富含硅的上层。这种分层结构产生了坚硬的疏水表面，同时保持了强大的附着力和机械完整性。与无硅涂层（纯EAR20）相比，自分层涂层的表面硬度明显提高（铅笔硬度从B提高到H），耐久性显著提高。浸没试验的耐水性从7天延长到12天不失效，耐磨性从5±1次增加到41±2次。静水接触角也从75±2°上升到89±2°，表明表面更疏水。此外，富含有机硅的顶层赋予了防涂鸦功能，使喷涂的墨水可以很容易地擦掉而不会残留。总的来说，这种硅油诱导的分层策略协同提高了机械坚固性和表面性能，为开发高性能水性涂料提供了一条有前途和可持续的途径。

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来源期刊

Progress in Organic Coatings 工程技术-材料科学：膜

CiteScore

11.40

自引率

15.20%

发文量

577

审稿时长

48 days

期刊介绍： The aim of this international journal is to analyse and publicise the progress and current state of knowledge in the field of organic coatings and related materials. The Editors and the Editorial Board members will solicit both review and research papers from academic and industrial scientists who are actively engaged in research and development or, in the case of review papers, have extensive experience in the subject to be reviewed. Unsolicited manuscripts will be accepted if they meet the journal''s requirements. The journal publishes papers dealing with such subjects as: • Chemical, physical and technological properties of organic coatings and related materials • Problems and methods of preparation, manufacture and application of these materials • Performance, testing and analysis.