The present technology relates to a self-healing material capable of self-healing cracks.
Adhesives are often used for joining parts, for example. However, minute cracks occur in the adhesive in some cases, for example, due to temperature shock, in a case where a reliability test such as a drop test is performed, or in a case where the adhesive is actually used in the market for a long period of time. The minute cracks gradually grow, which finally lead to semi-destruction or complete destruction of the joined portion and may impair the function of the product.
Adhesion portions are designed and adhesives are selected so that such a phenomenon does not occur, but market and customer demands are increasing year by year and there are cases where it is difficult to guarantee with existing adhesives. Further, with the acceleration of automated driving and the expansion of 5G (5th Generation Mobile Communication System), it is easy to predict that the number of devices installed outdoors and in automobiles will rapidly increase and existing adhesives and adhesion technologies will not be able to meet market demands.
Meanwhile, in recent years, a technology capable of self-healing cracks when cracks occur in adhesives has also been developed. For example, Patent Literature 1 discloses a self-healing agent in which a healing agent encapsulated in a base adhesive and a catalyst that cures the healing agent are combined. In this technology, when a crack occurs in the base adhesive, the capsule is ruptured, the healing agent and the curing agent are mixed, and thus, the healing agent is cured, thereby repairing the crack.
Patent Literature 1: Japanese Patent Application Laid-open No. 2017-218519
However, in the technology described in Patent Literature 1, since a curing agent is added to the base adhesive, it is necessary to select a base adhesive of a system completely different from the healing agent in order to prevent the adhesive from being unintentionally cured or thickened before use (when liquid), which limits the range of application. Further, when a curing agent is added to the base adhesive, there is also a possibility that adverse effects such as shortening of the service life occur. Further, in order to sufficiently mix the healing agent and the curing agent when a crack occurs in the adhesive, it is necessary to disperse a large amount of the capsules and the curing agents uniformly in the base adhesive.
In view of the circumstances as described above, it is an object of the present technology to provide a self-healing material having excellent productivity and self-healing properties.
In order to achieve the above-mentioned object, a self-healing material according to the present technology includes: a base material; a first capsule; and a second capsule.
The first capsule includes a first outer shell having flexibility and a first fluid encapsulated in the first outer shell, and is mixed with the base material.
The second capsule includes a second outer shell having flexibility and a second fluid that is encapsulated in the second outer shell and to be cured by contact with the first material, and is mixed with the base material.
The first outer shell and the second outer shell may be formed of a material having an elastic modulus of 20 MPa or more and 85 MPa or less.
The first outer shell and the second outer shell may be formed of gelatin.
The first outer shell and the second outer shell may be formed of melamine.
The first fluid may be an SGA (Second Generation Acrylic adhesive) main agent, and the second fluid may be an SGA curing agent.
The base material may be joined to the first outer shell and the second outer shell.
The first outer shell and the second outer shell may be formed of gelatin, and the base material may be an epoxy adhesive or an acrylic adhesive.
The first outer shell and the second outer shell may be formed of melamine, and the base material may be an epoxy adhesive or an acrylic adhesive.
The base material may be a material having a Shore D hardness of 60 or more.
A total mixing amount of the first capsule and the second capsule with the base material may be 5% (V/V) or more and 20% (V/V) or less.
A self-healing material according to an embodiment of the present technology will be described. The self-healing material according to this embodiment can be used as an adhesive.
[Configuration of Self-Healing Material]
The base material 101 is a curable material having fluidity. The base material 101 can be curable by heating, ultraviolet irradiation, mixing with a curing agent, or the like.
The first capsule 102 is mixed with the base material 101.
The second capsule 103 is mixed with the base material 101.
[Regarding Material of First Outer Shell and Second Outer Shell]
The first outer shell 121 and the second outer shell 131 are formed of a material having an elastic modulus of 20 MPa or more and 85 MPa or less as described above, and can specifically be formed of gelatin (elastic modulus of 24 MPa) or melamine (elastic modulus of 84 MPa). Note that the gelatin is more suitably heat-resistant gelatin on which heat-resistant treatment has been performed.
The following [Table 1] is a table showing the possible particle size (capsule diameter) range, film strength, and airtightness in the case where the first outer shell 121 and the second outer shell 131 are formed of gelatin or melamine. The materials of the first outer shell 121 and the second outer shell 131 can be selected on the basis of the properties as shown in [Table 1]. Note that the materials of the first outer shell 121 and the second outer shell 131 may be the same or different from each other.
[Regarding First Fluid and Second Fluid]
The first fluid 122 and the second fluid 132 are cured by contact with each other. Specifically, the first fluid 122 can be an SGA (Second Generation Acrylic adhesive) main agent and the second fluid 122 can be an SGA curing agent. The SGA is suitable because the curable mixing ratio of the SGA main agent and the SGA curing agent is as wide as 1:9 to 9:1.
In addition, the first fluid 122 and the second fluid 132 can be formed of a material that is cured by contact with each other. Specifically, the first fluid 122 can be a two-component epoxy main agent, and the second fluid 132 can be a two-component epoxy curing agent. Further, the first fluid 122 may be a metal anaerobic adhesive and the second fluid 132 may be a metal complex (primer). The first fluid 122 may be an instant adhesive and the second fluid 132 may be water. Further, the first fluid 122 may be a moisture-curable silicone and the second fluid 132 may be water.
[Regarding Base Material]
The base material 101 can be a curable material having fluidity as described. Specifically, the base material 101 can be an organic adhesive, for example, an epoxy adhesive or an acrylic adhesive. The base material 101 is suitably a material having a Shore D hardness of 60 or more when cured. This is because cracks described below do not occur in the case where the Shore D hardness is less than 60.
As for the relationship between the first outer shell 121 and the second outer shell 131 and the base material 101, the base material 101 is suitably a material that can be joined to the first outer shell 121 and the second outer shell 131. Specifically, in the case where the first outer shell 121 and the second outer shell 131 are formed of gelatin or melamine, by forming the base material 101 of an organic adhesive such as an epoxy adhesive and an acrylic adhesive, a chemical bond can be generated between the base material 101 and the first outer shell 121 and the second outer shell 131 to strongly join the first outer shell 121 and the second outer shell 131 and the base material 101 together. In addition, as the base material 101, a material that can be joined to the first outer shell 121 and the second outer shell 131 can be selected in accordance with the materials thereof.
[Action of Self-Healing Material]
An action of the self-healing material 100 will be described. The self-healing material 100 is applied to an object to be adhered while the base material 101 has fluidity. When the base material 101 is cured due to the lapse of time, heating, ultraviolet irradiation, or the like, the self-healing material 100 adheres to the object to be adhered.
Here, when the self-healing material 100 is repeatedly expanded and contracted due to temperature changes or deformed by external stress, cracks occur in the self-healing material 100 in some cases.
In this way, in the self-healing material 100, even if a crack has occurred in the self-healing material 100, the crack is filled with a cured product formed by the first fluid 122 and the second fluid 132 and healed by the cured product. Even if another new crack is formed in the self-healing material 100, the crack is filled with a cured product and healed by the cured product, similarly.
[Effects of Self-Healing Material]
In the self-healing material 100, the first capsule 102 includes the first outer shell 121 having flexibility and the second capsule 103 includes the second outer shell 131 having flexibility, as described above. As a result, even if stress is applied to the first capsule 102 and the second capsule 103 during mix stirring when the self-healing material 100 is produced or during application to an object to be adhered, the first capsule 102 and the second capsule 103 are deformed following the stress and are not destructed.
If the first outer shell 121 and the second outer shell 131 are formed of a brittle material such as glass and ceramic, there is a possibility that they are broken during mix stirring or application and the first fluid 132 and the second fluid 132 flow out. In this case, the first fluid 132 and the second fluid 132 are absorbed into the base material 101 and cannot perform healing when a crack occurs. Meanwhile, in the case where the first outer shell 121 and the second outer shell 131 have flexibility, the first fluid 122 and the second fluid 122 are prevented from flowing out when no crack occurs, and healing can be performed by a cured product when a crack occurs. In other words, there is no need to consider breakage of the first capsule 102 and the second capsule 103 during mix stirring and application, which facilitates handling.
Further, in the self-healing material 100, the base material 101 can be an organic adhesive, the first outer shell 121 and the second outer shell 131 can be formed of gelatin, melamine, or the like, and the base material 101 can be joined to the first outer shell 121 and the second outer shell 131. As a result, when a crack has occurred in the base material 101, the first capsule 102 and the second capsule 103 facing the crack are pulled by the base material 101 and reliably ruptured (see Example).
If the first outer shell 121 and the second outer shell 131 are formed of glass or the like, there is a possibility that the first capsule 102 and the second capsule 103 are not broken even when a crack occurs in the base material 101, and the crack cannot be healed. Meanwhile, by joining base material 101 to the first outer shell 121 and the second outer shell 131, the first capsule 102 and the second capsule 103 can be reliably ruptured by cracks. Further, by joining the base material 101 to the first outer shell 121 and the second outer shell 131, it is possible to improve the strength of the self-healing material 100 even in a state in which no crack occurs.
Further, as the first fluid 122 and the second fluid 132, an SGA (Second Generation Acrylic adhesive) main agent and an SGA curing agent can be used. Since the SGA has a wide curable mixing ratio of the SGA main agent and the SGA curing agent, which is 1:9 to 9:1, the first fluid 122 and the second fluid 132 can be entirely cured by contact with each other even if they are not sufficiently mixed. In the case where the first fluid 122 and the second fluid 132 are fluids having a predetermined mixing ratio for curing, high accuracy is required for the mixing ratio of the first capsule 102 and the second capsule 103 and the dispersion in the base material 101 in order to reliably heal cracks. Meanwhile, by using an SGA main agent and an SGA curing agent as the first fluid 122 and the second fluid 132, cracks can be reliably healed even if the mixing ratio of the first capsule 102 and the second capsule 103 and the distribution are not highly accurate.
[Regarding Mixing Amount of First Capsule and Second Capsule]
Although the mixing amount of the first capsule 102 and the second capsule 103 with the base material 101 is not particularly limited, it is suitable to mix the first capsule 102 and the second capsule 103 with the base material 101 at a ratio of 5% (V/V) (volume percent concentration, the same applied hereinafter) or more and 20% (V/V) or less, and more favorably 15% (V/V) or more and 20% (V/V) or less, in order to reliably healing minute cracks without deteriorating the properties of the base material 101 as an adhesive as much as possible. Further, the first capsule 102 and the second capsule 103 may be mixed at a ratio of 20% (V/V) or more in the case where the properties of the base material 101 are not affected or the affection is negligible.
[Regarding Particle Size of First Capsule and Second Capsule]
The particle size (capsule diameter) of each of the first capsule 102 and the second capsule 103 is suitably selected in accordance with the expected size of cracks. A capsule having a large particle size can be used in the case where the expected size of cracks is large, and a capsule having a small particle size can be used in the case where the expected size of cracks is small. Specifically, the particle size of each of the first capsule 102 and the second capsule 103 is suitably 2 to 10 times, more suitably 3 to 5 times, the expected size (width) of cracks.
[Regarding Use as Filler]
The self-healing material 100 can be used as a filler as well as an adhesive.
After mounting the part 152 on the substrate 151, the self-healing material 100 is supplied to the periphery of the part 152 as shown in
The self-healing material 100 can be used an underfill in fields such as mobile devices, outdoor devices, and medical devices (sterilized products). Specifically, the self-healing material 100 can be used for commercial camcorders, mobile phones, medical related equipment, portable audio devices, memory cards, steel plates for automobiles, traffic infrastructure, and the like.
[Study on Cleavage of First Outer Shell and Second Outer Shell]
Experiments were conducted to verify whether or not a first outer shell and a second outer shell would be cleaved when a crack occurred in a base material of the self-healing material according to the present technology.
After the adhesive 203 was cured, a force (50 mm/min) was applied to force points P so as to separate the first slide glass 201 and the second slide glass 204 from each other by a force gauge (manufactured by IMADA Co., Ltd.).
From this result, it can be seen that in the case where the base material is an epoxy adhesive or an acrylic adhesive and the first outer shell and the second outer shell are formed of gelatin, the base material and the first outer shell and the second outer shell are firmly joined together and the first outer shell and the second outer shell are cleaved when cracks occur.
Further, for comparison, as shown in
From this result, it can be seen that in the case where the base material is an epoxy adhesive or an acrylic adhesive and the first outer shell and the second outer shell are formed of glass, the interface between the first outer shell and the second outer shell and the base material is peeled off and the first outer shell and the second outer shell are not cleaved even if cracks occur.
The following [Table 2] is a table showing measurement results. As shown in [Table 2], as a result of three times of measurement, the gelatin 202 caused cohesive failure in a sample (VS. gelatin) to which the gelatin 202 was applied, and peeling occurred at the interface of the first slide glass 205 in a sample (VS. glass) to which the gelatin 202 was not applied. From the above, it can be said that by firmly joining a base material and a first outer shell and a second outer shell together in accordance with the types of materials of the base material and the first outer shell and the second outer shell, the first outer shell and the second outer shell can be reliably cleaved when cracks occur.
[Study on Healing]
A test piece formed of the self-healing material according to the present technology was prepared, and an experiment in which the self-healing material was ruptured and then self-healed was conducted.
When the test piece 300 was ruptured as shown in Part (b) of
[Study on Crack Length]
A test piece formed of the self-healing material according to the present technology was prepared and an experiment in which temperature stress was applied thereto was conducted.
Meanwhile,
[Study on Adhesive Strength]
An experiment in which two sheets of glass were bonded by the self-healing material according to the present technology and the force required for tensile shearing of the self-healing material was measured was conducted. The self-healing material was a capsule in which a first capsule and a second capsule were mixed with a base material formed of an acrylic adhesive. The first capsule was a capsule that includes an outer shell formed of gelatin and an SGA main agent encapsulated in the outer shell, and the second capsule was a capsule that includes an outer shell formed of gelatin and an SGA curing agent encapsulated in the outer shell. The coating area of the self-healing material was 3 mm in diameter, and the total mixing amount of the first capsule and the second capsule was 20 wt % (weight percent concentration) with respect to the base material.
Further, for comparison, two sheets of glass were bonded with only a base material formed of an acrylic adhesive and the force required for tensile shearing of the self-healing material was measured. The coating area of the base material was 3 mm in diameter. The following [Table 3] is a table indicating the measurement results. As shown in [Table 3], the results that the self-healing material had an adhesive strength equivalent to that of the base material and the adhesive strength is not reduced by mixing the first capsule and the second capsule were obtained.
[Study on Coatability]
An experiment in which 1 mg of the self-healing material according to the present technology was applied as one shot and the total weight of the applied self-healing material after 50 shots was measured was conducted. The self-healing material was a mixture of a first capsule and a second capsule in a base material formed of an acrylic adhesive. The first capsule was a capsule that includes an outer shell formed of gelatin and an SGA main agent encapsulated in the outer shell, and the second capsule was a capsule that includes an outer shell formed of gelatin and an SGA curing agent encapsulated in the outer shell. The total mixing amount of the first capsule and the second capsule was 20 wt % (weight percent concentration) with respect to the base material.
Further, for comparison, 1 mg of only a base material formed of an acrylic adhesive was applied as one shot and the total weight of the base material after 50 shots was measured. The following [Table 4] is a table indicating the measurement results. As shown in [Table 4], the results that the self-healing material had a coating weight equivalent to that of the base material and the coatability is not reduced by mixing the first capsule and the second capsule were obtained.
(Regarding Present Disclosure)
The effects described in the present disclosure are merely examples and are not limited, and additional effects may be exerted. The description of the plurality of effects described above does not necessarily mean that these effects are exhibited simultaneously. It means that at least one of the effects described above can be achieved in accordance with conditions or the like, and there is a possibility that an effect that is not described in the present disclosure is exerted. Further, at least two feature portions of the feature portions described in the present disclosure may be arbitrarily combined with each other.
It should be noted that the present technology may also take the following configurations.
Number | Date | Country | Kind |
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2021-039887 | Mar 2021 | JP | national |
Filing Document | Filing Date | Country | Kind |
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PCT/JP2022/000514 | 1/11/2022 | WO |