Patent Application
20240191049
The present application claims benefits of priority to the prior application with the patent application No. 202110363704.5 and entitled “COMPOSITION OF HEAT-EXPANDABLE MICROSPHERES AND USE THEREOF” filed before China National Intellectual Property Administration on Apr. 2, 2021, which is incorporated herein by reference in its entirety.
The present disclosure belongs to the field of expandable microspheres, and in particular relates to a composition of heat-expandable microspheres and use thereof.
Expandable microspheres (also known as foaming powder) are thermoplastic hollow polymer microspheres, which consist of a thermoplastic polymer shell and a liquid alkane enclosed in the shell. When heated to a certain temperature, the thermoplastic polymer shell softens, the liquid alkane in the shell gradually vaporizes, and the gas expands, so that the pressure in the shell increases, and the microspheres expand in volume and become larger. Based on the aforementioned characteristics of the expandable microspheres, they are usually widely used in fields including thermal expansion coating materials, plastics, wallpapers, adhesives, inks, printing and the like.
However, in the prior art, the expandable microspheres with thin shell walls will rupture under higher temperature and internal pressure, so that the expected expansion ratio of the expandable microspheres cannot be achieved, and it will also lead to a decrease in the adhesion of a coating material, adhesive and the like comprising the expandable microspheres in an application process. Based on this, the expandable microspheres with thin shell walls have long been given up. How to improve the application of the expandable microspheres to reduce the problems of a low expansion ratio, decreased adhesion, and/or low high-temperature resistance caused by thin-walled expandable microspheres in back-end applications, and to optimize the thickness of the shell wall of the expandable microspheres to ensure that the thickness of the shell wall is enough to resist the problems of damage and/or rupture in the process of mixing, stirring, pouring, curing and bonding, and finishing of adhesive substances has become an urgent technical problem to be solved in the art.
In order to improve the aforementioned technical problem, the present disclosure provides a composition of heat-expandable microspheres, comprising heat-expandable microspheres and a solvent, wherein:
According to an embodiment of the present disclosure, an initial thermal expansion temperature T1 of the heat-expandable microspheres is 100° C.≤T1≤200° C. For example, T1 is 125° C.≤T1≤180° C., exemplarily 120° C., 130° C., 150° C., 160° C., 170° C., 190° C., or any value between the enumerated temperature points.
According to an embodiment of the present disclosure, a maximum heat-resistant temperature T2 of the heat-expandable microspheres is 145° C.≤T2≤215° C. For example, T2 is 150° C.≤T2≤205° C., exemplarily 155° C., 160° C., 165° C., 175° C., 185° C., 195° C., 200° C., or any value between the enumerated temperature points.
As can be understood by those skilled in the art, the initial thermal expansion temperature T1 is ≤the maximum heat-resistant temperature T2.
According to an embodiment of the present disclosure, a weight fraction of heat-expandable microspheres with a particle size of 8 μm≤D≤20 μm is no less than 60%, e.g., 60%, 65%, 70%, 72%, 76%, 80%, 90%, or 100% of the total weight of the heat-expandable microspheres; and preferably, a weight fraction of heat-expandable microspheres with a particle size of 10 μm≤D≤15 μm is no less than 50%, e.g., 55%, 56%, 60%, or 70% of the total weight of the heat-expandable microspheres.
According to an embodiment of the present disclosure, the heat-expandable microspheres comprise a thermoplastic polymer shell and a liquid alkane enclosed within the thermoplastic polymer shell.
For example, the material of the thermoplastic polymer shell is made of a heat-melt substance or a substance that will crack when heated and expanded. For example, the material is selected from a copolymer of vinylidene chloride and acrylonitrile, polyvinyl alcohol, polyvinyl butyral, polymethylmethacrylate, polyacrylonitrile, polyvinylidene chloride, polysulfone, a homopolymer of vinylidene chloride, a random terpolymer of vinylidene chloride, acrylonitrile and divinylbenzene, polystyrene or polyvinyl chloride.
According to an embodiment of the present disclosure, the liquid alkane may be one, two or more selected from liquid ethane, liquid propane, liquid isobutane, n-pentane, and isopentane.
According to an embodiment of the present disclosure, the organic solvent having a boiling point of above 220° C. may be selected from a dodecanol ester.
According to an embodiment of the present disclosure, the solvent may comprise one or two of ethylene glycol butyl ether and dipropylene glycol butyl ether, in addition to at least one organic solvent having a boiling point of above 220° C.
In the present disclosure, the “particle size” refers to the median particle diameter D50 of the heat-expandable microspheres before heat expansion, and the “thickness” refers to the thickness of the shell wall of a single heat-expandable microsphere before heat expansion.
The aforementioned particle sizes are volume average diameters, and the diameter of the unexpanded heat-expandable microspheres and the thickness of the shell wall of the microspheres can be determined by any method known in the art.
According to an embodiment of the present disclosure, a weight ratio of the heat-expandable microspheres to the solvent is (4-40):1, preferably (5-20):1, and exemplarily 4:1, 5:1, 6:1, 8:1.2, 7:1, 8:1, 9:1, 10:1, 15:1, or 17:1.
According to an embodiment of the present disclosure, the composition of heat-expandable microspheres may optionally further comprise an inorganic fiber. For example, the inorganic fiber is filamentary or flaky (e.g., lamellar). For example, the inorganic fiber may be one, two or more selected from a nano-aluminosilicate fiber, a carbon fiber and a boron fiber, etc. After the composition is expanded, the inorganic fiber can be infiltrated with the resin in the coating described below, so as to play a role of skeleton support and strength enhancer in the coating described below, thereby improving the strength and shrinkage resistance of the expandable coating.
According to an embodiment of the present disclosure, a weight ratio of the inorganic fiber to the solvent is (0-2):1, e.g., (0.5-1.5):1, and exemplarily 0.5:1, 3:5, 0.7:1, 0.85:1, 0.9:1, 1:1, or 1.2:1.
According to an embodiment of the present disclosure, an expansion ratio of the composition of heat-expandable microspheres is 150%-300%, e.g. 180%-250%.
According to an exemplary embodiment of the present disclosure, the composition of heat-expandable microspheres comprises heat-expandable microspheres, a solvent and an inorganic fiber, wherein:
Exemplarily, the composition of heat-expandable microspheres comprises heat-expandable microspheres, a solvent and an inorganic fiber, wherein:
The present disclosure further provides a method for preparing the aforementioned composition of heat-expandable microspheres, comprising mixing the heat-expandable microspheres and the solvent, as well as the inorganic fiber optionally added to obtain the composition.
Preferably, the heat-expandable microspheres have the particle size range, weight fraction, and wall thickness as described above.
Preferably, the solvent and the inorganic fiber have the meanings and amounts as described above.
According to an embodiment of the present disclosure, the heat-expandable microspheres with the aforementioned particle size range can be obtained by mixing two, three or more types of heat-expandable microsphere raw materials (referred to as “raw material microspheres” for short).
The raw material microspheres may be selected from the types of microspheres known in the art.
For example, the raw material microspheres may at least comprise Q1-type microspheres and Q2-type microspheres. Preferably, the particle size of the Q1-type microspheres is 5 μm≤D≤16 μm, and the weight fraction of the Q1-type microspheres is no less than 50%, e.g. 50%, 60%, or 70% of the weight of the raw material microspheres.
The initial particle size range of the Q2 type and other types of raw material microspheres can be selected by those skilled in the art as needed, so as to obtain the aforementioned particle size range of the heat-expandable microspheres.
The present disclosure further provides use of the aforementioned composition of heat-expandable microspheres in a coating material, preferably in an aqueous coating material, and more preferably for improving the stability of a coating formed by the coating material, for example, by improving the internal void support of the coating to form a coating with a stable structure.
According to an embodiment of the present disclosure, a weight ratio of the composition of expandable microspheres to the coating material is 1:(4-25), e.g. 1:(5-15), and for example 1:5.7, 1:6, 1:8, 1:9, 1:10, or 1:11.
According to an embodiment of the present disclosure, the coating material can be used as an adhesive in the automotive industry, for example as an adhesive for fixing a magnetic material in the assembly of an automobile engine. Preferably, the magnetic material is a neodymium-iron-boron magnet.
According to an embodiment of the present disclosure, the coating material is a water-based coating material.
According to an embodiment of the present disclosure, the coating material is prepared from a coating composition comprising an aqueous thermoplastic resin, an aqueous thermosetting resin and a hot-melt filling resin.
According to an embodiment of the present disclosure, the aqueous thermoplastic resin is at least one selected from an aqueous acrylic resin and a polyurethane resin.
According to an embodiment of the present disclosure, the aqueous thermosetting resin is at least one selected from an aqueous epoxy resin and hydroxyacrylic acid.
According to an embodiment of the present disclosure, the hot-melt filling resin is at least one selected from modified chlorinated polyvinyl chloride, polyester, polyurethane, polyamide, polyethersulfone, an epoxy resin and polymethylmethacrylate.
The present disclosure further provides a method for improving the stability of a heat-expandable coating, comprising the following step: mixing a composition of heat-expandable microspheres with a coating composition, wherein both the composition of heat-expandable microspheres and the coating composition have the meanings and mass ratios as described above.
According to an embodiment of the present disclosure, the method comprises: applying the composition of heat-expandable microspheres mixed with the coating composition onto a substrate body, and then heating the substrate body to obtain the heat-expandable coating.
According to an embodiment of the present disclosure, the substrate body is a magnetic material, preferably a neodymium-iron-boron magnet.
According to an embodiment of the present disclosure, the application may be selected from means known in the art, for example spray coating, roller coating, brush coating, coating, electroplating, dipping, roll coating, and other methods for applying the composition of heat-expandable microspheres mixed with the coating composition to the surface of a substrate body.
The present disclosure further provides a substrate comprising a coating and a substrate body, wherein the coating is prepared from a coating material comprising the aforementioned composition of heat-expandable microspheres.
Preferably, the coating is located on the surface of the substrate body.
Preferably, the substrate body has the meaning as described above.
Preferably, the coating material has the meaning as described above.
The inventors of the present disclosure have found in practice that, due to the uneven shell wall thickness and/or uneven particle size distribution of the heat-expandable microspheres, the spheres with thin shell walls will break preferentially when subjected to the same temperature and internal pressure. Therefore, the microspheres cannot achieve the expected expansion ratio during application, which in turn affects the temperature resistance and adhesion performance of the coating material comprising the expandable microspheres in magnet fixing of automobile engine assembly.
During the heat-expansion process, the composition of heat-expandable microspheres of the present disclosure can rapidly soften and destroy the thin-shell spheres in a short period of time in the secondary heat-expansion process of the coating comprising the composition, and with the volatilization of the organic solvent, it was enabled to be cross-linked with a resin matrix in the coating on the surface and inside of the coating to form a cross-linked network structure, thereby strengthening the void support of the coating, and enabling the coating to achieve stepped expansion, and part of the polymer material after expansion wraps an airbag and hardens to form a stable hollow structure. The resultant heat-expandable coating has a stable structure, relatively high resistance to thermal shrinkage, relatively high mechanical strength and adhesion, can be applied in the fixation of high temperature resistant parts, and can maintain the adhesion stability thereof when placed long-term in a high temperature environment (140-180° C.).
The technical solutions of the present disclosure will be further illustrated in detail with reference to the following specific examples. It will be understood that the following examples are merely exemplary illustrations and explanations of the present disclosure, and should not be construed as limiting the protection scope of the present disclosure. All techniques implemented based on the content of the present disclosure described above are included within the protection scope of the present disclosure.
Unless otherwise stated, the starting materials and reagents used in the following examples are all commercially available products or can be prepared using known methods.
The heat-expandable microspheres adopted in the present disclosure can be commercially available, and for example are selected from two of 920DU80, 920DU20, 909DU80, and 920DU40 in the Expancel series available from AKZO-Nobel and a composition thereof.
Table 1 shows the main parameters of four types of heat-expandable microspheres in the Expancel series available from AKZO-Nobel.
A composition of heat-expandable microspheres as shown in Table 2 comprised:
The particle structure of the heat-expandable microspheres is shown in
[1]the average thickness of the heat-expandable microspheres was tested by a scanning electron microscope (SEM) S-4700 available from Hitachi, Japan, and was the average value of the wall thicknesses of all (≥20) microspheres at the visible interface.
Aqueous coating materials B1-B4 comprising a resin, a composition of heat-expandable microspheres, and water were prepared in the following proportions: the content of the resin in the aqueous coating material was: 25 wt % of an aqueous thermoplastic resin (polyurethane resin) and 35 wt % of an aqueous thermosetting resin (hydroxyl acrylic resin), the content of the composition of heat-expandable microspheres was 15 wt %, and the balance was water.
The above compositions of heat-expandable microspheres contained in the aqueous coating materials B1-B4 corresponded to Examples A1-A4, respectively.
The coating material samples of Examples B1-B4 were each applied onto the surface of a sintered neodymium-iron-boron magnet (not magnetized) with specifications of 40 mm×15 mm×5 mm in a spray coating manner, and oven-dried under a condition of 70° C. for 30 min to make the surface coating be dried and hardened. The hardened coating had a certain anti-corrosion performance, which was convenient for the transportation and protection of a magnetic sheet. The magnet was transported to the workplace, i.e., the assembly site of a motor rotor, the magnet was inserted into a prepared magnetic steel slot with a width of 5.5 mm, and the rotor workpiece was processed by heating it in a high-temperature oven at 190° C. for 10 min. The processing conditions and test results are as shown in Table 3.
As can be seen from
The shell of the microspheres softened and ruptured, and the microspheres were cross-linked with the resin matrix in the coating to generate a cross-linked coating structure (
It can be seen from the experimental data of the coatings obtained from the samples B1-B4 that: the particle size of the heat-expandable microspheres added in the sample B4 was 16.24 μm, the proportion of heat-expandable microspheres with a particle size of 8 μm≤D≤20 μm was 40%, and the Q1 type (5 μm≤D≤16 μm) accounted for 35% of the total weight of the heat-expandable microspheres. The particle size of the heat-expandable microspheres added in the sample B2 was 13.15 μm, and the proportion of heat-expandable microspheres with a particle size of 10 μm≤D≤15 μm was 56%. Due to the poor uniformity of particle size of microspheres in the sample B1, when the microspheres with different particle sizes were heated, the core materials with a low boiling point in the microspheres was heated to generate a pressure, thereby causing the expansion of the shell of the microspheres. The pressure generated by the core materials was not sufficiently balanced with the tension generated by the resin wall material due to stretching, and the stability was slightly poor.
The adhesion thrust of the coating of the final product at both room temperature and high temperature (170° C.) was slightly worse than that of the sample B2. In the sample B4, among the heat-expandable microspheres, the ratio of the microspheres with a thickness ≤5 μm accounted for 51% of the total weight of the microspheres. That is, there were more thick-walled microspheres.
When the shell of the microspheres was too thick, the microspheres were difficult to expand and become larger and thus could not form a cross-linked structure with the thermoplastic resin, and the adhesive force decreased. Similarly, in the samples B3 and B4, no inorganic fiber or high-boiling point organic solvent was added, thus failing to facilitate the thermoplastic resin to form a dense protective film on the surface of the coating with the high-boiling point organic solvent. The stability after expansion was slightly worse, and the adhesion thrust at high and low temperatures after expansion was significantly lower than that of the sample B2. Comparing the sample B3 with the sample B4, the performance of the sample B4 comprising no inorganic fiber was worse than that of the sample B3 comprising dodecanol ester as a high-boiling point solvent.
After 1500 hours of an oil immersion test, the magnet with the coating prepared from the coating material of the composition of heat-expandable microspheres of the present disclosure had no significant decrease in adhesion thrust and had good long-term adhesion stability.
The inventors had further found that when the initial particle size of the expandable microspheres added in the coating material was about 50 μm (with other parameters being the same as those in Example B2), due to the too large particle size of the expandable microspheres, after expansion, the hollow area of the microspheres was too large, and the compressive strength would also decrease, which was not enough to resist the damage and/or rupture in the process of mixing, pouring, curing and bonding, and finishing of an adhesive composition.
The embodiments of the present disclosure have been described above. However, the present disclosure is not limited to the embodiments described above. Any modification, equivalent, improvement, and the like made without departing from the spirit and principle of the present disclosure shall fall within the protection scope of the present disclosure.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202110363704.5 | Apr 2021 | CN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2022/084264 | 3/31/2022 | WO |
