1. Introduction
Microcapsule technology is a kind of technology used to store core materials (usually in the form of solid, liquid, and gas) in polymer wall materials [
1]. The wall materials are composed of film-forming materials that are mainly natural or synthetic materials in a solid state [
2]. A core material is a material coated with a wall material, which is the hinge to determine the function of microcapsules [
3]. In self-healing paint films, the core material of microcapsules achieves the repair effect through external stimulation and slow release [
4]. Therefore, the good fluidity, proper curing speed, and good compatibility with paint film substrate are the necessary conditions for selecting core materials [
5]. Compared with the traditional repair technology, the key for microcapsule technology lies in its simple synthesis, low cost, and self-healing of materials without the aid of external conditions [
6].
Xu et al. [
7] prepared urea formaldehyde (UF) microcapsules to ameliorate the spontaneous cure property of coral sand cementitious materials. The study revealed that the optimization particle size distributions and volume fractions of microcapsules are 450 rpm and 3%. The results show that the spontaneous cure effect of microcapsules synthetized under this condition was about 75%. Sun et al. [
8] prepared sunflower oil microcapsules to enhance the technical and self-repairing performance of bitumen-based sealants, which were added into the bitumen-based sealants. The self-healing properties of microcapsule sealant was obviously superior to the original sealant. Sunflower oil microcapsules could heighten the repeated self-repairing capability and fatigue life of the sealants at −20 °C. Mirabedini et al. [
9] prepared polyurea-formaldehyde-based microcapsules loaded with linseed oil. The conclusions showed amelioration in tensile strength abilities and corrosion resistance via the simultaneous use of 3-aminopropyltrimethoxy silane (APS)-treated microcapsules and nanoclay. APS-treated microcapsules more easily ruptured during scratching, resulting in better corrosion resistance and self-repairing capabilities. The above studies all focus on the self-healing efficiency and anti-corrosion of coral sand cementitious materials, bitumen-based sealants, and nanocomposite paint film. However, the studies on the self-healing of waterborne wood paint films are few.
Shellac is a natural resin secreted by rubber insects after absorbing sap from host trees [
10]. After removing impurities from the rubber block collected from the tree [
11], it was crushed, screened, mixed, rinsed with water, and dried with a dryer to form shellac [
12]. Shellac is a natural product, is non-toxic, provides environmental protection, and has good film-forming ability, fast drying and curing speed, unique solubility, and excellent thermal performance [
13]. Shellac paint is also widely used in the field of wood furniture [
14]. Shellac resin is selected as the repair agent which can realize room temperature curing [
15]. UF resin is translucent after curing and has a certain level of toughness and strength [
16,
17]. Its preparation cost is low, and its raw materials are rich and its performance is stable [
18]. Waterborne paint films have become newly popular in the territory of paint films as a result of their low or no volatile organic compounds (VOCs) and harmful air pollutants [
19,
20].
In the preliminary work [
21], epoxy resin coated with UF resin microcapsules were fabricated. The morphology and structure of microcapsules were determined by orthogonal experiments with five factors and four levels. The yield, optimal repair rate, and coverage rate of microcapsules were analyzed. Nevertheless, once the microcapsule breaks, epoxy resin as a repair agent of microcapsules for paint films on wood substrate needs to be cured via heating or adding curing agent. This is obviously unrealistic for intelligent self-healing wood products.
In this paper, UF resin (wall material) and shellac (core material) were used to prepare microcapsules via in situ polymerization. The optimal core-wall ratio was determined by studying the effect of different core-wall ratios on microcapsules. Using Tilia amurensis Rupr. as a wood substrate, the effect of UF resin-coated shellac microcapsules on the mechanical and optical properties of waterborne paint films was studied. The self-healing effect of the prepared microcapsules on the Tilia amurensis Rupr. surface was observed by simulating the damage of the paint film in the process of day-to-day operations. This was a new attempt to realize self-healing waterborne paint films, which provided a new possibility for the application of microcapsule self-healing technology in the territory of wood furniture.
2. Materials and Methods
2.1. Test Materials
The main raw materials for preparing the shell of microcapsules are urea (Mw: 60.06 g/mol, CAS No.: 57-13-6) and 37.0% formaldehyde solution (Mw: 30.03 g/mol, CAS No.: 50-00-0). The pH regulators are triethanolamine (Mw: 149.19 g/mol, CAS No.: 102-71-6) and citric acid monohydrate (CAM, Mw: 210.14 g/mol, CAS No.: 5949-29-1). The emulsifier is sodium dodecyl benzene sulfonate (SDBS, MW: 348.48 g/mol, CAS No. 25155-30-0). The solvent for dissolving shellac is anhydrous ethanol (Mw: 46.07 g/mol, CAS No.: 64-17-5). The above materials were offered by Qiming Chemical Co., Ltd., Shandong, China. Shellac resin was offered by Jinan Dahui Chemical Technology Co., Ltd., Shandong, China. Waterborne wood coating was offered by Akzo Nobel Swire Paint Co., Ltd., Shanghai, China. Waterborne wood coating was composed of waterborne acrylic copolymer dispersion, matting agent, additive, and water. The solid matter of waterborne coating exceeded 30.0%. Tilia amurensis Rupr. (100.0 mm × 65.0 mm × 5.0 mm) was offered by Shantou Yihua Life Technology Co., Ltd., Guangdong, China. All reagents used in the experiment were not further treated.
2.2. Preparation of Microcapsules
The core-wall ratios of microcapsules were 0.42:1, 0.67:1, and 0.75:1, respectively. The materials for preparing microcapsules are exhibited in
Table 1. The mass of core material was 12.5 g, 20.0 g, and 22.5 g, respectively, and the wall material quality remained unchanged. Three kinds of UF resin-coated shellac resin microcapsules were prepared. The preparation process of microcapsules with a 0.42:1 core-wall ratio was as follows:
Synthesis of UF prepolymer for wall material: 20.0 g urea and 27.0 g of 37.0% formaldehyde solutions were mixed thoroughly by stirring. The pH was adjusted to 8.0–9.0 via adding triethanolamine gradually. A magnetic stirring rotor was added and the mixture was mixed continuously in a 70 °C temperature water bath for 1 h, then the obtained emulsion was a wall material solution. The prepared wall material solution was naturally cooled to room temperature for use.
Synthesis of shellac resin core material emulsion: 62.5 g anhydrous ethanol and 12.5 g shellac resin were added into a beaker and stirred until completely dissolved. The 0.975 g SDBS white powder was added to 96.52 mL distilled water, stirred evenly, and 1.0% SDBS emulsifier solution was obtained. The emulsifier solution was added into the dissolved shellac solution and the magnetic stirring rotor was added for magnetic stirring. The uniform core emulsion was obtained after continuous stirring for 30 min at 1200 rotations per minute (rpm).
Microencapsulation: at the speed of 300 rpm, the cooling UF prepolymer was dropped into the core material emulsion, the CAM was added, and the pH was adjusted to 2.5–3.0. After the reaction was finished, the product was aged for 7 days and then washed and filtered by deionized water and anhydrous ethanol repeatedly. Finally, the residual product was dried at 80 °C for 4 h, and the resulting yellow powder was the microcapsules. The fabrication technique of microcapsules with core-wall ratios of 0.67:1 and 0.75:1 was the same as above.
2.3. Preparation of Paint Films
Three grams of waterborne primer were weighed in a beaker, and the substrate was evenly coated with waterborne primer once along the direction of the substrate texture with an SZQ tetrahedral fabricator (Guojing Electronic Co., Ltd., Jiangsu, China). The waterborne primer was placed in the front of the fabricator. The fabricator slid at a speed of 150 mm/s to obtain the required thickness of the coating. The film was first dried at room temperature for 30 min and then at 35 °C for 30 min. After drying, the paint film was polished with 800 mesh sandpaper, and then the dust was wiped off with a dry cloth. The above process is the process of applying the primer once, and the primer needs to be applied twice. Therefore, the above process needs to be repeated once more before the primer coating is completed. Three kinds of core-wall ratios (0.42:1, 0.67:1, and 0.75:1) of microcapsules were added to the topcoat to fabricate a self-healing topcoat with microcapsule concentrations of 0, 5.0%, 10.0%, 15.0%, and 20.0%. The composition is shown in
Table 2. The topcoat was applied on
Tilia amurensis Rupr. twice. The drying and grinding process of the topcoat paint film was the same as the primer. The thickness of all the obtained waterborne paint films was approximately 60 µm.
2.4. Performance Test
A conical hole with a sharp angle of 120 °C was drilled in the coating. The wall of the hole was imaged with a microscope magnified by 40 times. The length of the coating part of the bus bar was measured. Then, in accordance with the trigonometric function, the coating thickness was half of the bus coating length. The thickness of waterborne paint film was evaluated by the three-point arithmetic average method.
An HP-2136 portable colorimeter (Hanpu Testing Instrument Co., Ltd., Shenzhen, China) was used to detect the chroma value of paint film. The 60° gloss of the film was measured by an HG268 glossmeter (3NH Technology Co., Ltd., Shenzhen, China). Due to the wet expansion and dry shrinkage of wood, it easily cracks under high temperature. Therefore, the maximum temperature of 140 °C was selected as the limit value of thermal aging [
22]. In order to simulate the aging phenomenon of paint films after long-term use, the coatings were heated at 120 °C for 7 h and then heated to 140 °C for 7 h. The color value, gloss, and stability of the film before and after aging were tested.
The film hardness was measured by a 6H-6B pencil (Dongguan Huaguo Precision Instrument Co., Ltd., Dongguan, China). The adhesion was evaluated by a QFH-HG600 film classifier (Yueqing Liushi Li Chuang Measurement Equipment Firm, Zhejiang, China). When the adhesion grade of the paint film was 0, the adhesion was the best. The impact resistance was evaluated by a QCJ impactor (Yemao Instrument Co., Ltd., Shanghai, China). Impact resistance refers to the maximum fall height to the test plate without causing film cracking.
The morphology of microcapsules and coatings was analyzed by a Quanta 200 environmental scanning electron microscope (SEM) (FEI company (Hillsboro, OR, USA)). The composition of the film was analyzed by a Vertex 80 V infrared spectrophotometer (Germany Bruker Co., Ltd., Karlsruhe, Germany). All experiments were repeated four times, and the error was less than 5.0%.
4. Conclusions
UF resin-coated shellac resin microcapsules, with favorable morphology, uniform particle size, and less damage, have been fabricated with a 0.75:1 core-wall ratio. At the 0.42:1 core-wall ratio, when the concentration was 5.0%, the impact resistance was better, which was 140 N·cm−2. At the 0.75:1 core-wall ratio, the gloss of paint films with a 5.0% microcapsule concentration was 11.2 G.U. The hardness of paint films with a 20.0% microcapsule concentration reached the maximum value of HB. The adhesion of paint films with microcapsules with a 0.75:1 core-wall ratio was good at different microcapsule concentrations, which were all grade 1. When the concentration of microcapsules was 5.0% and 10.0%, the microstructure of paint films was good. The results revealed that when the core-wall ratio was 0.75:1 and the concentration of microcapsules was 10.0%, the paint film could obtain excellent gloss, hardness, impact resistance, adhesion, and self-healing properties without reducing the original performance of the paint film. At this time, the general properties of the paint film were better, that is, the color difference value was 1.3, the gloss at 60° was 7.8 G.U., adhesion was grade 1, the hardness was B, and the impact resistance was 90 N·cm−2. The gloss after the aging process was reduced by 0.8 G.U. and the color difference was 13.3. The results provide the technical reference for the application of self-healing wood paint films.