Applied Surface Science Advances 19 (2024) 100557

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Applied Surface Science Advances

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Advances in waterborne polyurethane matting resins: A review

Ge Li a, b, 1, Ying Tan a, 1, Zhuojun Li a, Guangliang Zhou a, Xiaomeng Yu a, Qiang Nie b,
Junhua Chen c, Qiwen Yong a, d, e, *, Zhihui Xie a, *
a
Institute of Applied Chemistry, Chemical Synthesis and Pollution Control Key Laboratory of Sichuan Province, College of Chemistry and Chemical Engineering, China
West Normal University, Nanchong 637009, China
b
Sichuan Xingcheng Gongzhu New Building Materials Co., Ltd, Guangyuan 628021, China
c
School of Environmental and Chemical Engineering, Zhaoqing University, Zhaoqing, Guangdong 526061, China
d
Innovation Center for Chenguang High Performance Fluorine Material, Sichuan University of Science and Engineering, Zigong, Sichuan 643000, China
e
Material Corrosion and Protection Key Laboratory of Sichuan Province, Zigong 643000, China

A R T I C L E I N F O A B S T R A C T

Keywords: Water-based or waterborne polyurethane matting resins find extensive application in surface coating to diminish
Waterborne polyurethane gloss, offering a pleasant tactile experience and a matte aesthetic. This review represents the inaugural effort to
Self-matting consolidate the recent advancements in waterborne polyurethane matting resins, encompassing both physical
Matting agents
and chemical matting types. The exploration commences with an introduction to a range of innovative matting
Low gloss
Resin
agents tailored for the formulation of physical matting waterborne polyurethane resins. Subsequently, a thor­
Coating ough analysis and discussion unfold, delving into the synthesis, characterization, and matting mechanisms of
chemical matting waterborne polyurethane resins. This comprehensive discussion draws upon a decade of
dedicated research work by our group, contributing fresh perspectives to the evolution of chemical matting
techniques. In conclusion, the review not only addresses the current state but also outlines potential challenges
and future trends. This forward-looking perspective is intended to offer guidance for the design and synthesis of
innovative waterborne polyurethane matting resins.

1. Introduction the case of the same material, a smoother surface intensifies the reflected
light, whereas a rougher surface scatters light, diminishing the intensity
Waterborne polyurethane (WPU) is a polymer derived from of reflection and achieving a superior matting effect. Measured by a
condensation polymerizations involving isocyanates and polyols [1,2]. gloss meter at a 60◦ incident angle, the gloss of paint is categorized into
Distinguished from traditional solvent-based polyurethane, WPU em­ five grades, as illustrated in Fig. 1: high gloss (exceeding 70 gloss units),
ploys water as its dispersion medium, mitigating the emission of harmful medium gloss (30–70 gloss units), eggshell gloss (6–30 gloss units), plain
substances during production, transportation, storage, and application. gloss (2–6 gloss units), and matte (less than 2 gloss units) [7].
This not only effectively reduces environmental pollution but also High-gloss WPU resin coatings, renowned for their vibrant and
showcases high safety performance, promising positive application lustrous colors, have found widespread application in daily life. How­
prospects [3–5]. ever, their propensity to generate robust mirror reflections often leads to
Gloss, an optical characteristic of a coating surface, serves as an in­ inconveniences and contributes to severe light pollution in urban areas.
dicator of the coating’s ability to reflect light. A coating exhibiting high In contrast, low-gloss WPU or WPU matting resins exhibit a subtle sheen,
gloss implies a substantial amount of incident light being reflected, providing warm and gentle visual effects that alleviate visual fatigue.
resulting in a luminous surface. Conversely, a coating with low gloss With versatile applications spanning decorative coatings, industrial
suggests minimal light reflection, yielding a more refined surface [6]. coatings, building materials, furniture coatings, flow aids, and more,
The gloss of a coating is primarily influenced by surface roughness. In these resins play a pivotal role in the fabric of human society (Fig. 2) [8].

Notes: The authors declare no competing financial interest.

* Corresponding authors at: Institute of Applied Chemistry, Chemical Synthesis and Pollution Control Key Laboratory of Sichuan Province, College of Chemistry
and Chemical Engineering, China West Normal University, Nanchong 637009, China.
E-mail addresses: [email protected] (Q. Yong), [email protected] (Z. Xie).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.apsadv.2023.100557
Received 18 July 2023; Received in revised form 7 December 2023; Accepted 8 December 2023
Available online 12 December 2023
2666-5239/© 2023 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
G. Li et al. Applied Surface Science Advances 19 (2024) 100557

The research and development of WPU matting resins have garnered resulting in a thinner coating. Simultaneously, sub-micron particles of
extensive attention across diverse fields, addressing both technological the matting agent are deposited on the coating surface, creating
and fundamental perspectives. Analyzing Web of Science data (Fig. 3) microscopic roughness. This uneven surface causes incident light to be
from 2000 to the end of May 2023, particularly post-2010, reveals a diffusely reflected and scattered, leading to a reduction in light reflec­
significant surge in the number of published papers on polyurethane tion and achieving the desired matting effect [12]. Matting agents can
matting resins. generally be categorized into organic and inorganic types. Common
Currently, the fabrication of WPU matting resins primarily involves organic matting agents include polymeric waxes, metal soap com­
incorporating specific matting materials or implementing a series of pounds, tung oils, and emerging options such as polyurea, polymethyl
chemical modifications to WPU, categorically falling into physical methacrylate microspheres, and thermosetting polymeric resins re­
matting and chemical self-matting [9]. Physical matting typically entails ported in laboratory studies. However, it is noteworthy that organic
the blending of WPU with matting agents to generate a matting agents often exhibit poor dispersion in WPU resin, and after film
non-homogeneous film. This matting effect is achieved by meticulously formation, they tend to level off on the film surface, making it suscep­
regulating the particle size and distribution of the matting materials, tible to surface floating and uneven gloss [13]. Inorganic matting agents,
thereby controlling microscopic irregularities that lead to diffuse light represented by substances like kaolin, talcum powders, ultrafine silica,
reflection on the film surface [10]. On the other hand, chemical diatomite, titanium dioxides, and montmorillonites, play a significant
self-matting involves altering the inherent nature of WPU itself. This role in matting. Notably, silica, widely utilized in the market, possesses
modification results in distinct particle fixation and stress effects within controlled particle size, a suitable porous structure, and a large specific
the WPU emulsion during film formation, leading to diffuse light surface area, ensuring easy dispersion in WPU dispersion and exhibiting
reflection. Consequently, this process diminishes the surface gloss of the excellent performance across diverse applications [14]. Fig. 4 summa­
film, achieving a notable self-matting effect [11]. rizes all industrialized and reported physical matting agents.
This review aims to provide a comprehensive overview of a range of Sun et al. recently synthesized a novel silica matting agent using
innovative matting agents, encompassing both organic and inorganic liquid phase precipitation. Their orthogonal tests concluded that under
variants. These agents have been introduced into WPU resins to specific conditions—85 ◦ C reaction temperature, 25 min addition time,
formulate physical matting WPU resins in recent years. Subsequently, 60 min holding time, 600 r/min stirring speed, and an 18 mL sulfuric
considerable emphasis is placed on the exploration of new chemical acid acidification volume—the produced silica exhibited amorphous
matting WPU resins. This includes an in-depth examination of WPU self- characteristics and uniform dispersion, with a particle size of approxi­
matting resins, as well as variants like epoxy-modified, silicone-modi­ mately 30 nm. The high stirring speed facilitated increased particle
fied, acrylic-modified, other multi-components modified, and bio-based collision, resulting in a well-developed pore structure for the silica and
modified WPU self-matting resins. These variations demonstrate the excellent overall performance [15]. Clingerman et al. introduced a
capability to manifest self-roughened film features, thereby achieving an modified silica matting agent achieved by treating silica with mercapto
outstanding self-matting effect. Finally, a synthesis of challenges stem­ silane containing thiols. This modification led to lower viscosity
ming from these matting agents and techniques is presented, followed by (Formulation viscosity with silane-treated silicas were roughly 50 % less
suggestions for the future development of WPU matting resins. that of thermal silicas), higher matting efficiency with 60◦ gloss <57,
and enhanced durability with a gloss retention of 76 % at 120 h and 64
2. Physical matting WPU resins % over 360 h compared to commonly used micronized silica in the
market [16]. Zhang et al. developed a novel "intra-droplet phase sepa­
The physical matting of WPU resins primarily involves the addition ration" method for synthesizing hollow mesoporous silica microspheres
of various matting agents. Through the blending or mixing of WPU resin (HMSM) with an average diameter of about 500 nm. This involved
with these agents, water evaporates during the film formation process, exploiting the phase separation between the hydrophobic solvent (HS)

Fig. 1. Gloss degree gradings measured at 60◦ incident angle.

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G. Li et al. Applied Surface Science Advances 19 (2024) 100557

and the silica precursor in the microemulsion droplets. The resulting

HMSM-NH2, obtained by adding 3-aminopropyltriethoxysilane to the oil
phase, was further utilized in the creation of HMSM-NH2-WPU coatings.
These coatings, designed through chemical bonding between the amino
groups provided by HMSM-NH2 and WPU resin, demonstrated excellent
extinction, UV protection, and covering power [17]. Ma et al. utilized
N-(β-aminoethyl)-γ-aminopropyltriethoxysilane (Si-910) to modify sil­
ica in aqueous solution, obtaining an active amino group on its surface.
This modified silica was then introduced into the aqueous polyurethane
prepolymer to synthesize a new modified WPU matting resin. The
resulting aminosiloxane-modified silica was embedded in the WPU film
matrix, creating an uneven corrugated heterogeneous rough surface to
achieve a self-extinguishing effect. The prepared WPU resin exhibited
low viscosity, good storage stability, and excellent mechanical proper­
ties [18]. While silica-based matting agents offer advantages such as a
straightforward preparation method, controlled particle size, excep­
tional matting performance, and low environmental impact, certain
challenges exist. The tendency for silica-based matting agents to
disperse in water as particles may lead to a fluffy phenomenon when
granule filling is not tightly packed, resulting in low mechanical strength
and friction resistance. Additionally, the potential for agglomeration
Fig. 3. The number of papers published per year on polyurethane matting
after compounding can lead to surface peeling and uneven luster [19].
resins from 2000 to the end of May 2023 (Source: Web of Science; Retrieval
In addition to silica-based matting agents, researchers and paint
keywords: “polyurethane” and “matting” or “matte”).
formulators have dedicated significant efforts to investigate alternative
types of matting agents. Gao et al. [20] prepared a multi-hollow poly­
polyurea microsphere was added to the WPU coating, the glossiness of
urea microsphere for matting coatings by precipitation polymerization
the coating surface was significantly reduced. Wang et al. [21] designed
in H2O/Acetonitrile (AN) solution using isophorone diisocyanate (IPDI)
a micron-sized polymethyl methacrylate (PMMA) microsphere with
as the polymerization monomer, 2,4-diaminobenzenesulfonic acid so­
different size distributions by one-step dispersion polymerization using
dium salt as the hydrophilic monomer and polyvinylpyrrolidone (PVP)
methyl methacrylate (MMA), polyvinylpyrrolidone (PVP) and sodium
as the pore-forming agent. The PVP pore-forming agent was essential in
styrene sulfonate (NaSS) as the monomer, stabilizer, and copolymer,
regulating the surface porosity of the microspheres in the experiments
respectively. The experimental results showed that the size of PMMA
and showed excellent perforation properties. When 5 wt% of porous

Fig. 2. Application scenarios of WPU matting resins.

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Fig. 4. Various physical matting agents are commonly used and reported in the literature.

microspheres decreased as the concentration of NaSS or PVP increased. and PMMA microspheres was coated. PMMA microspheres were
The size of PMMA microspheres increased, and the distribution of assembled on the surface of the WPU coating, which markedly increased
PMMA microspheres was wider as the concentration of MMA increased. the surface roughness of the coating. With the particle size increase of
Using artificial leather as the substrate, the mixture of bulk WPU resin microspheres, the gloss degree of the coating layer decreased

Fig. 5. Disadvantages of physical matting WPU resins.

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G. Li et al. Applied Surface Science Advances 19 (2024) 100557

correspondingly. In addition, Ding et al. [22] synthesized a WPU mat­ of the WPU dispersion increased, leading to an increase in film surface
ting resin based on in situ polymerization by assembling large-scale roughness and an improved matting effect. The experimental method
exfoliated montmorillonite (MTM) monolayer nanosheets into an envi­ also avoided using high-boiling solvents, reduced the practical prepa­
ronmentally friendly WPU resin. This highly adhesive multifunctional ration steps, shortened the reaction time, and produced WPU with
WPU nano-coating has remarkable matting proficiency and good flame high-temperature resistance. Sun et al. [34] synthesized a
retardancy. polyester-based self-extinguishing WPU (ESMWPU) for the surface
Generally, the majority of research reports on physical matting treatment of PVC artificial leather using poly(1,3-butanediol) as a chain
agents have centered around the development of innovative agents like extender. At a DMPA of 1.75 wt%, ESMWPU had large size particles of
modified silica, polyurea, and polymethyl methacrylate microspheres. 7–8 µm and maintained the spherical shape of latex particles during film
These alternatives offer superior dispersion, lower required addition formation, creating a rough surface that has good matting properties and
amounts, reduced variation in gloss values, and a broader range of ap­ ensuring adequate wetting and spreading on plasticized PVC with
plications compared to traditional silica matting agents. However, the excellent thermal adhesion. However, the tensile strength of the WPU
inherent issue of compatibility differences between matting agents and film tended to increase as the amount of carboxylic acid-based chain
WPU resins poses a fundamental challenge. This leads to poor stability in extender increased, and the flexibility of the film tended to decrease due
physical matting WPUs, where matting agent particles are prone to to a corresponding decrease in the soft segment. When an extensive
precipitation, consequently elevating resin viscosity [23,24]. Further­ carboxylic acid-based chain extender was introduced, the hardness and
more, the incorporation of physical matting agents into the resin can water resistance of the WPU films were reduced [35].
compromise the overall physical properties of the film. This includes The sulfonic acid group has a high ionization ability, high hydro­
rendering the film more brittle, less polishable, and susceptible to philicity, and a more stable hydrophilic group structure, so the chemical
chipping, as well as diminishing its resistance to water, heat, and sol­ modification of WPU with a sulfonic acid group can increase the solid
vents [25]. Finally, the addition of extra matting agents entails a content of WPU, effectively regulate the particle size distribution of
high-cost investment, encompassing raw material costs for matting emulsion, providing that the resultant WPU self-matting resin has high
agents, as well as equipment and labor input costs during production. hydrolytic and thermal stability, and extraordinary matting perfor­
The shortcomings of physical matting WPU resins are displayed in Fig. 5. mance [36]. Huang et al. [37] introduced both 2,2-Bis(hydroxymethyl)
Therefore, in recent years, Researchers have endeavored to synthesize propionic acid (DMPA) and 1,2-propanediol into the hard chain segment
diverse chemical self-matting WPU resins by engineering specific mo­ of the prepolymer to enable molecular chains to have dispersed hydro­
lecular structures. This design aims to facilitate the spontaneous for­ philicity. 2-[(2amino-ethyl)amino]ethyl sulfonic acid sodium (A95) and
mation of a micro-rough surface during the drying process of the resin, hydrazine hydrate were successively introduced into the hard segment
eliminating the need for additional matting agents. This approach ach­ respectively to adjust the particle size of WPU, and a high solid content
ieves the self-matting effect of WPU resins. WPU with matting or anti-glare effect was successfully prepared. As the
prepared WPU self-extinguishing resin had a bimodal structure, the
3. Chemical self-matting WPU resins viscosity problem caused by high solid content can be effectively solved.
By adjusting the content of A95, the film can be tuned to be matt or
Chemical self-matting WPU resins can be broadly defined as a class of antiglare. And when the emulsion was diluted, the optical property of
waterborne polyurethanes with self-matting characteristics synthesized the WPU self-matting resin remained unchanged. Our research group
through molecular structure design, which do not require additional [38] has also designed a new sulfonate/carboxylate WPU
addition of matting agents but can achieve low gloss on the surface of self-extinguishing resin (CSWPU) using both sulfonic acid and carbox­
the paint film after drying. The chemical matting mechanisms are ylic acid type hydrophilic emulsifying chain expanders, and the reaction
divided into the following categories: (1) Introduction of matting did not require the addition of organic solvents to reduce the viscosity of
groups, such as unsaturated double bonds in the molecular structure of the prepolymer during the polymerization process. The roughness of the
synthetic WPU resins to absorb light, achieving matting purposes [26]. film was observed by 3D-AFM and TEM, and it was found that the
(2) Preparation of sub-micron scale particles of WPU emulsion, which emulsion and the film contained a large number of spherical particles
play a similar role as matting agents in the film formation process. The with diameters of 0.8–3.0 μm, which allowed the film to spontaneously
matting effect can be ascribed to the deposition of large emulsion par­ arrange itself to form a rough surface during the drying process, thus
ticles to create a micro-rough surface [27,28]. (3) Introduction of a resin achieving a self-matting effect (Fig. 6). The CSWPU resin exhibited
with a specific compatibility difference to the main resin to take elevated molecular weight, a diminished swelling rate, and impressive
advantage of the difference in internal stress during film formation, thermal stability. Notably, the temperature of maximum degradation
resulting in the shape of a bumpy or wrinkled film [29,30]. (4) Intro­ rate increased from 390 ◦ C to 407 ◦ C with the augmentation of the
duction of a constituent with a difference in curing temperature into the content of sulfonic acid hydrophilic chain extender or the molecular
main constituent. Uneven shrinkage occurs during the film formation weight of the soft chain segment.
when the two components are cured successively, resulting in a rough In summary, the chemical modification of WPU prepolymers utiliz­
and matted surface [31]. ing carboxylic acid-based or sulfonic acid-based hydrophilic chain ex­
panders, or both in a synergistic action, facilitates the adjustment of
3.1. WPU self-matting resins emulsion particle size. This process enables the creation of sub-micron
emulsion particles, allowing the resulting emulsions to autonomously
WPU self-matting resins usually use both hydrophilic emulsifiers and form self-rough films during the drying process. However, to construct
chain extenders to regulate the particle size of the emulsion so that the large particle-size emulsion particles that remain stable in aqueous en­
molecules are stably dispersed in water, fabricating a wide distribution vironments, it is often necessary to introduce a substantial number of
of WPU emulsions with large particle sizes [32]. Chang et al. [33] pre­ hydrophilic groups. Unfortunately, this practice tends to reduce the
pared a new WPU matting resin by using a macromolecular polyol water resistance, chemical resistance, and mechanical properties of
containing carboxylic acid units in the chain of polycaprolactone (PCLD) WPU films [39]. These drawbacks significantly constrain the application
instead of 2,2-bis(hydroxymethyl)propionic acid (DMPA) to provide scope of WPU self-matting resins. Therefore, in the utilization of various
carboxylic acid groups and introducing hydrophilic units in both the soft hydrophilic groups to control the particle size of WPU emulsions, careful
and hard segments. It was found that the surface gloss of WPU films and consideration of the type and dosage of hydrophilic groups, along with
the particle size of WPU dispersions were closely related to the content the resulting emulsion stability, is essential to achieve the optimal
of hydrophilic groups. As the PCLD content decreased, the particle size comprehensive performance of WPU self-matting resins.

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G. Li et al. Applied Surface Science Advances 19 (2024) 100557

Fig. 6. (a) Particle size distribution and (b) surface roughness of the self-matting CSWPU film calculated based on 3D-AFM pictures; (c) Surface particle accumulation
morphology and (d) tilted surface morphology of the self-matting CSWPU film obtained from the SEM results [38].

3.2. Epoxy-modified WPU self-matting resins strength of EWPUs increased. The experimental results showed that the
overall performance of the E-44 modified WPU self-matting resin was
Epoxy resin is a high molecular compound containing epoxy groups better than that of E-51. Based on the similarity principle, our group
with high strength, heat resistance, adhesion, and chemical stability [45][47] also produced a new type of aqueous polyurethane
[40]. The epoxy group is introduced into WPU through a ring-opening self-matting resin with high crosslink density and assertive gel behavior
reaction, which can increase the cross-linked structures of the poly­ (CPU) by introducing reactive bisphenol A epoxy resin E-44 or E-55 and
urethane molecular chain segments and solve the disadvantages of low castor oil into the WPU backbones. The mechanical mismatch between
cross-link density, poor adhesion, and poor solvent resistance of the the surface and bottom layers of the CPU film and the internal volume
above WPU self-matting resins [41,42]. Li et al. [43] synthesized an contraction caused by the evaporation of large amounts of water led to
epoxy-modified WPU self-matting resin using epoxy resin (EP) as a the formation of a micro-rough surface. As the E-44 or E-51 content
cross-linking modifier for self-emulsifying polyurethane. The structure increased, the surface roughness of the CPU films increased, and the
was determined using infrared spectroscopy, and it was found that both gloss level decreased sharply. The surface morphology and roughness of
epoxy and hydroxyl groups of EP were involved in the cross-linking the CPU films were shown in Fig. 7.
reaction, which significantly enhanced the thermal stability, hydro­ Hence, the introduction of epoxy resin into the molecular chain of
phobicity, and matting proficiency of the WPU resin. When WEP=5 %, WPU can increase the degree of cross-linking of the whole molecular
the corresponding epoxy-modified WPU self-matting resin had the best system, thereby increasing the tensile strength of the epoxy-modified
heat and water resistance. Zhan et al. [44] prepared a series of WPU self-matting resin. The network crosslinking structure increases
epoxy-modified WPU self-extinguishing resins (EWPUs) using 4, the difficulty of diffusion of water molecules in the epoxy-modified WPU
4-diphenyl methane diisocyanate, polyethylene glycol and epoxy film, effectively reducing the film’s water absorption rate and improving
resins (EP-44, EP-51). Due to the injection of epoxy resin, the relative its thermal stability. The resulting epoxy-modified WPU self-matting
molecular mass of EWPUs increased, and the density of molecular resin can spontaneously form micro-rough structures due to micro-
cross-linking increased. With the increase in epoxy resin content, the phase separation or internal stress difference to achieve extinction ef­
thermal decomposition temperature, water resistance and tensile fect. However, the content of epoxy resin has a major influence on the

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G. Li et al. Applied Surface Science Advances 19 (2024) 100557

Fig. 7. SEM images of CPU films by (a) adding castor oil and E-44 resin, and (b) adding only castor oil; (c) Roughness surface scanning and line scanning results of (b)
CPU film by only adding castor oil obtained by 3D profilometer; (d) SEM image and (e) optical surface morphology of CPU film by injecting castor oil and E-51 resin;
(f) Roughness surface scanning and line scanning results of (d) CPU film by adding castor oil and E-51 resin obtained by 3D profilometer [45].

overall performance of WPU self-matting films. If the introduced content silicone-modified WPU emulsion possessed a large particle size, a rough
of epoxy resin is low, the resulting emulsion exhibits a low crosslinking surface, and an excellent matting effect. When the DMBA content was
density, resulting in poor water resistance and mechanical properties. further increased, the particle size of the WPU decreased, and the mat­
On the other hand, a high injection of epoxy resin leads to an excessively ting effect was weakened. Due to the introduction of polysiloxane side
high crosslinking density after curing. This results in elevated emulsion chains, the abrasion resistance and heat resistance of ARSMWPU films
viscosity and reduced emulsion stability. Consequently, the epoxy- increased, and the self-matting capacity did not decrease, which can
modified WPU self-matting film becomes brittle and prone to effectively solve the contradiction between abrasion resistance and
cracking, adversely affecting water resistance and weatherability [46]. matting effect that is usually exhibited. Niu et al. [54] synthesized a
Therefore, the quantity of epoxy resin should be thoroughly considered siloxane-modified WPU self-extinguishing resin by using 2, 2-bis
in the practical synthesis to ensure that the epoxy-modified WPU (hydroxymethyl)propionic acid (DMPA) and terminal hydroxypropyl
self-matting resin attains an appropriate crosslinking density, thereby polydimethylsiloxane (PDMA) as prepolymer raw materials and
enhancing the overall performance of the WPU film. N-2-aminoethyl-3-aminopropyltrimethoxysilane (KH-792) as a chain
extender. Due to the surface migration of siloxane, the surface energy of
the WPU matting film was reduced. Meanwhile, the KH-972 enhanced
3.3. Silicone-modified WPU self-matting resins
the cross-link density of the molecules, which greatly improved the
abrasion resistance of the WPU film. Ding et al. [55] produced an
WPU self-matting resin emulsions are typically synthesized by
aminosiloxane-modified WPU self-extinguishing resin at room temper­
incorporating diverse hydrophilic groups into the main chain structure
ature using γ-aminopropyltriethoxysilane (APTES) as a modifier. The
of polyurethane, imparting a self-emulsifying effect. However, excessive
modified WPU was characterized by FTIR and SEM, and it was found
hydrophilicity may compromise the water resistance of the coating film
that the absorption peaks of Si-O-Si appeared in the polyurethane,
[47]. Silicone is a polar reagent with low surface energy and has certain
indicating that the APTES self-condensation formed a Si-O-Si cross-­
hydrophobicity and thermal stability. By introducing silicone chain
linked network structure, which led to an increase in the particle size of
segments into the WPU matting resin, the hydrophobic chain segments
the emulsion and a decrease in the gloss of the film. With increasing
of silicone migrate to the surface of the coating film, reducing the free
APTES content, the water absorption of the film decreased, the acid and
energy of the WPU film surface and effectively enhancing the water and
alkali resistance increased, and the fracture elongation gradually
heat resistance of the film [48,49]. The modified WPU has both organic
decreased.
and inorganic properties, which can effectively improve the film’s me­
It can be seen that by introducing silicone chain segments into the
chanical properties [50,51].
WPU matting resin, the low surface energy silicone component migrates
Zhang et al. and Pathak et al. [52,53] prepared a silicone-modified
to the surface of the cured film during the film formation process, thus
WPU (ARSMWPU) with both abrasion resistance and self-matting
changing the surface property of the cured film and achieving improved
function by introducing hydroxyl-terminated polydimethylsiloxane
water resistance, abrasion resistance and thermal stability of the film.
(HTPDMS) as a modifier into the side chain of WPU with dihydrox­
The roughness of the siloxane-modified WPU self-matting film can be
ymethylbutyric acid (DMBA) as a hydrophilic chain extender. It was
adjusted by varying the hydrophilic chain extender and silicone content
found that when the weight content of DMBA was less than 1.6 %, the

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during the preparation process, thereby controlling the particle size of matting effect. It was found that the WPUA with the core-shell structure
the emulsion. However, due to the large difference in polarity between had the higher tensile strength (18.35 MPa of tensile strength, 611.61 %
silicones and WPUs, the modified emulsions tend to aggregate into large of elongation at break) and the optimal thermal stability (degradation
particles and undergo phase separation, resulting in poor compatibility temperatures of 5 %, 10 % and 50 % are 273.28 ◦ C, 304.17 ◦ C,
and stability of the emulsions[56]. Therefore, it is also necessary to 406.23 ◦ C, respectively), and the WPUA with the semi-IPN structure had
control the amount of silicone in the preparation process to solve the the highest water resistance (less than 4 % of swelling ratio after 5 h of
incompatibility problem between organic silicon and WPU, and defects immersion) and phase separation degree (3.07 µm of phase zone size).
such as poor stability and shortened storage period. Conversely, the WPUA with the anti-core-shell structure exhibited the
lowest mechanical properties strength (12.25 MPa of tensile strength,
3.4. Acrylic-modified WPU self-matting resins 395.17 % of elongation at break). Our group [61] prepared a series of
low gloss aqueous polyurethane acrylate (WPUA) composites with
WPU matting resins exhibit poor water and solvent resistance, while different soft/rigid monomer weight ratios, and the different surface
acrylics typically demonstrate superior water and weather resistance morphologies of these WPUA composites are shown in Fig. 8. The low
[57]. Modifying WPU with acrylics can address the deficiency in water gloss effect of these WPUA emulsions was achieved by the spontaneous
resistance of WPU matting resins. The resulting acrylic-modified WPU formation of a rough surface during the film formation process without
matting resins boast excellent environmental friendliness, stability, and adding additional matting agents. As the hard/soft weight ratio of the
adhesion. They are characterized by energy efficiency, high perfor­ acrylic monomer increased, the average particle size of the emulsion
mance, and economic benefits, representing a current focal point in decreased, and the film’s roughness increased. At the same time, the
research and development [58]. Liu et al. [59] found that the roughness thermal stability of the WPUA film improved due to the introduction of
of the water-based polyurethane acrylate (PUA) films increased with the the acrylic monomers and showed good hardness, excellent adhesive
increase of the styrene/butyl acrylate weight ratio, thereby decreasing strength.
the gloss level. The PUA dispersion with core-shell structure has a small In addition, UV curing technology has the characteristics of fast
particle size and uniform distribution of granules. It can also improve curing speed at room temperature, high efficiency, low cost, and no
the performance of PUA resin by adjusting the structure of the shell, pollution [62,63]. Sun et al. [64] synthesized a new self-extinguishing
which has potential applications in self-leveling waterborne self-matting polyurethane-acrylate coating by excimer lamp and UV curing pro­
coatings. Lin et al. [60] synthesized three waterborne polyurethane cess. After irradiation with UV-mercury and excimer lamps, the PUA
acrylate (WPUA) emulsions with core-shell, anti-core-shell and coating surface formed folds at the microscopic level to achieve a
semi-interpenetrating network (semi-IPN) structures, using isophorone self-extinguishing effect. By varying the curing energy, the width and
diisocyanate, polytetraethylene ether diol, dihydroxytrimethylsiloxane, height of the folds on the surface of the coating can be controlled. A good
methyl methacrylate and butyl acrylate as the primary raw materials. extinction effect was observed when PUA samples were cured at 25–40
Due to the roughness of the film surface caused by uneven shrinkage mJ cm− 2 by excimer and 250–350 mJ cm− 2 by UV-Hg lamps, respec­
during the film formation process, the synthesized acrylic-modified tively, and the coatings showed good resistance to fingerprints, pencil
WPU self-matting resins with core-shell structure have a specific hardness, adhesion, and wear resistance. Zhang et al. [65] developed a

Fig. 8. SEM photos of the pure WPU (a) and (b), (c), (d) self-matting WPUA films with different soft/rigid monomer weight ratios [61].

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G. Li et al. Applied Surface Science Advances 19 (2024) 100557

self-extinguishing waterborne polyurethane acrylate (UV-WPU) coating effect. The cross-linking of WPU with E-51, which has a rigid benzene
based on the UV curing process. The size of the UV-WPU film wrinkles ring structure, can significantly improve the composite film’s mechan­
can be controlled by regulating the amount of photoinitiator in the ical property, water resistance, heat resistance, and chemical resistance
liquid coating, thereby achieving the target of controlling the extinction while working with the silicone polymer to achieve a synergistic matting
effect. The cured films demonstrate outstanding thermal stability, ten­ effect. Our group [68] also fabricated a new intrinsically matt WPU resin
sile strength, pencil hardness, cross-sectional adhesion, and abrasion composite by combining a silicone-modified waterborne polyurethane
resistance, showcasing significant potential for practical applications. resin (SPU) and a cross-linked waterborne polyurethane (CPU). Due to
In brief, the use of acrylics to modify WPU matting resin can combine the cross-linking reaction between the aqueous polyurethane and the
the abrasion resistance and good mechanical properties of WPU with the bisphenol A epoxy E-44, the synthesized CPU resin was capable of
water and weather resistance of acrylate, resulting in an acrylic- producing a micro-rough surface of the film. The SPU resin can also
modified WPU self-matting resin with significantly improved overall improve the overall properties of the composite film with the addition of
properties. Additionally, the film surface roughness can be adjusted by silane coupling agents. As a result, the CPU/SPU composite resin was
varying the proportion of soft and hard monomers in the acrylate capable of spontaneously forming a micro-roughened surface during the
monomer, allowing for the control of film surface gloss based on specific film formation process and achieving an extinction effect of the film
requirements. The utilization of UV curing technology in the preparation without the addition of any matting agents. In comparison to the pure
of acrylic-modified WPU self-matting resins not only offers the advan­ CPU resin, the composite film exhibited optimal overall performance
tages of being environmentally friendly, rapid, efficient, and easily with a 50 % CPU and 50 % SPU weight ratio. This formulation resulted
scalable but also enables the control of coating film surface roughness by in a delicately textured surface with a delicate rough structure (root
adjusting the curing energy, thus catering to diverse needs in various mean square roughness Rq = 1.28 µm, average surface wavelength λa =
situations. 59 µm), good transparency (transmittance value ≥80 % at 550 nm),
robust stretching ability (20 MPa of tensile strength, 335 % of elongation
3.5. Other multi-components modified WPU self-matting resins at break), excellent storage stability (over 6 months), and outstanding
adhesive strength (5B of pencil hardness) (Fig. 9).
Most of the WPU self-matting resins studied so far are one- Hence, leveraging the design flexibility of polyurethane macromol­
component modifications, and their mechanical properties, film- ecules and harnessing the benefits of multiple modifiers, WPU prepol­
forming effect, water resistance, and heat resistance are limited to ymers can undergo simultaneous multi-component modifications. This
some extent. The co-modification of WPUs with various materials and approach allows for the optimization of the molecular structure of WPU,
the synergistic effect between different materials makes the prepared improvement in the matting performance of WPU matting resins, and
WPU resins multifunctional and high-performance, which is conducive enhancement of the overall performance of WPU composite films.
to improving the all-around performance of WPU self-matting resins and However, the selection of specific modifying materials should align with
expanding their application scopes. Xuan et al. [66] reported a green practical needs, considering the interactions between each component.
flame retardant two-component aqueous polyurethane (2K-WPUs) This molecular-level polyurethane structure design enables continuous
self-matting film consisting of an aqueous hydroxyl component and a optimization and development of WPU performance to meet diverse
poly-isocyanate component. By introducing TiO2 nanoparticles into application requirements and expand application fields.
water-based 2 K polyurethane, the mechanical properties of 2K-WPU
were greatly improved. Moreover, with the increase in TiO2 content, 3.6. Bio-based modified WPU self-matting resins
the glossiness and UV transmittance of the 2K-WPU films decreased.
Tang et al. [67] introduced silicone polymer and epoxy resin (E-51) into Biomass is an organic material derived from nature and has the ad­
the WPU system and synthesized a WPU self-matting resin modified with vantages of being low-cost, renewable, degradable, and environmentally
epoxy resin and silicone polymer together. The silicone polymer friendly. It is widely used in the preparation of new chemical polymers
migrated to the surface during emulsion film formation, resulting in a and is of great significance in alleviating the energy crisis and reducing
microscopic rough structure on the film surface to achieve the matting environmental pollution [69,70]. The use of biomass as a raw material

Fig. 9. SEM images and line scanning curves representing surface roughness of the SPU, 50 %SPU/50 %CPU, and CPU films [68].

9
G. Li et al. Applied Surface Science Advances 19 (2024) 100557

to fully or partially replace chemical products in the preparation of WPU modified silica, polyurea, and polymethyl methacrylate microspheres in
resins is currently increasing and is becoming an important direction in waterborne polyurethane resins, have been succinctly summarized. The
the development of functional WPU coatings [71,72]. Being one of the synthesis, characterization, and matting mechanisms, along with the
most economical and abundant plant biomass raw materials, vegetable merits and demerits, of five distinct chemical self-matting WPU resins
oil harbors numerous active functional groups, including double bonds have been elaborated in intricate detail. These encompass epoxy-
and ester groups, within its molecular structure. These active sites can be modified, silicone-modified, acrylic-modified, other multi-components
effectively employed for chemical modification and incorporation into modified, and bio-based modified WPU self-matting resins. This
polyurethane molecules [73]. Currently, the commonly used vegetable exhaustive exploration provides invaluable guidance for the formulation
oils include castor oil, rapeseed oil, soybean oil, and sunflower oil. Our of pioneering WPU self-matting resins endowed with outstanding
research group [74] synthesized a novel bio-based modified WPU comprehensive properties across various dimensions.
self-matting resin with the cross-linked network in molecular structure The design and development of high-performance WPU self-
and sub-micron scale in particle size by introducing polyhydroxy castor extinction resins present a multifaceted and formidable undertaking.
oil and reactive bisphenol A-type epoxy E-44 or E-55 resin as a Current challenges include achieving glossiness levels surpassing those
cross-linking agent and modifier into the polyurethane prepolymer attainable through physical extinction and addressing the instability
using a self-emulsification technique. The gloss of the film surface observed in the synthesized resin system. Anticipated future trends in
decreased as the castor oil content increased. The results showed that WPU self-matting resins encompass (1) further enhancement of extinc­
the branched and cross-linked density of the WPU emulsion was effec­ tion efficiency and resin system stability, (2) broadening the functional
tively enhanced due to the synergistic effect of the polyhydroxy castor repertoire of WPU self-matting resins by incorporating specialized fea­
oil and reactive bisphenol A-based epoxy E-44 or E-51. The films’ tures such as anti-fingerprint, anti-graffiti, anti-icing, anti-fouling, etc.,
physical properties were assessed and found to have a soft touch and (3) leveraging diverse components, such as epoxy, acrylate, fluorine,
good adhesive strength. Meng et al. [75] synthesized a new reactive and silicon-containing substances, for the modification or co-
water-based polyurethane (RWPU) dispersion containing unsaturated modification of WPU backbones to achieve product diversity and
carbon-carbon double bonds from epoxidized soybean oil. The disper­ expand application domains, and (4) integrating various biomass ma­
sion was copolymerized with hard/soft acrylate monomers of different terials, either partially or entirely replacing petroleum-based compo­
weight ratios to synthesize bio-based polyurethane-acrylate matting nents, to synthesize environmentally friendly WPU self-matting resins,
emulsions, which was capable of spontaneously forming rough surfaces thereby mitigating reliance on petroleum resources and lessening
during film drying due to phase separation caused by the incompatibility environmental impact.
of the emulsions. The resultant polyurethane-acrylate matting films
could afford low gloss, good thermal stability, good tensile strength and CRediT authorship contribution statement
good storage stability, and the raw materials used in the experimental
process were environmentally friendly and inexpensive, which could be Ge Li: Funding acquisition, Investigation, Writing – original draft.
used for a wide range of industrial applications. Ying Tan: Investigation, Formal analysis, Data curation, Writing –
The primary aim of employing bio-based polyols in WPU modifica­ original draft. Zhuojun Li: Writing – review & editing, Investigation.
tion is to diminish energy consumption by substituting traditional pol­ Guangliang Zhou: Writing – review & editing, Investigation. Xiao­
yols with biomass-derived alternatives. Xin et al. [76] synthesized a meng Yu: Writing – review & editing, Investigation. Qiang Nie: Writing
bio-based modified WPU matting resin using natural dimer fatty acid – review & editing, Validation. Junhua Chen: Writing – review &
(DA) based polyester polyol as soft segments via the acetone method. It editing, Validation. Qiwen Yong: Conceptualization, Methodology,
was found that the WPU self-matting films exhibited excellent water Writing – review & editing. Zhihui Xie: Conceptualization, Writing –
resistance, hydrolysis resistance, and thermal stability. However, due to review & editing, Supervision.
DA being a mixture of acyclic, monocyclic, and polycyclic structures, the
synthesized WPU self-matting resin had lower toluene resistance and Declaration of Competing Interest
mechanical property.
In summary, the modification of WPUs using biomass vegetable oil The authors declare that they have no known competing financial
materials is primarily categorized into two aspects: (1) the direct interests or personal relationships that could have appeared to influence
incorporation of natural vegetable oils into polyurethane modification; the work reported in this paper.
(2) the modification of natural vegetable oils to produce bio-based
polyols, which are subsequently introduced into the polyurethane Data availability
modification process. The WPU self-matting resins modified with
biomass not only exhibit an outstanding low gloss effect but also effec­ No data was used for the research described in the article.
tively address the challenges of poor water and chemical resistance in
WPUs while enhancing the mechanical properties of WPU films. Addi­
tionally, the integration of biomass raw materials into the industrial Acknowledgments
polyurethane synthesis process reduces reliance on chemical products,
aligning with the strategic goal of promoting green and sustainable Ge Li received funding from the Key R&D Projects of Guangyuan
development in the chemical industry and offering promising applica­ Science and Technology Plan, China (22ZDYF0001). Qiwen Yong
tion prospects. received funding from the Innovation Center for Chenguang High Per­
formance Fluorine Material, Sichuan University of Science and Engi­
4. Conclusions and perspectives neering, China (No. SCFY2206), the Opening Project of Material
Corrosion and Protection Key Laboratory of Sichuan Province, China
In this comprehensive review, an examination of glossiness grading, (Grant No. 2022CL17), and the Research Fund of China West Normal
application fields, and the research landscape over the past two decades University, China (Grant No. 19B027).
in the realm of WPU matting resins has been meticulously concluded.
Both physical and chemical matting types of WPU resins have been
dissected individually. The utilization and potential challenges associ­
ated with traditional organic and inorganic matting agents, such as
polymeric waxes, SiO2, tung oils, and new type of extinction agents like

10
G. Li et al. Applied Surface Science Advances 19 (2024) 100557

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