JP2021070728A - Polymerizable composition, molding and composite member - Google Patents

Abstract

To provide a polymerizable composition that can produce a molding that is easily repaired when damaged and has high hardness, and provide a molding that is easily repaired when damaged and has high hardness.SOLUTION: A polymerizable composition has a polymerizable compound (A) and a metal ion (B). In the polymerizable compound (A), the proportion of a component (a) is 50 mol% or more and 100 mol% or less, the component (a) having a solubility parameter equal to or higher than a first value and equal to or lower than a second value, which is higher than the first value by 2.0. The first and second values are defined so that the proportion becomes the largest. The component (a) contains at least unsaturated carboxylic acid (a1).SELECTED DRAWING: Figure 1

Description

The present disclosure relates to a polymerizable composition, a molded product and a composite member, and more particularly to a polymerizable composition containing an unsaturated carboxylic acid, a molded product produced from the polymerizable composition, and a composite member including the molded product.

Patent Document 1 discloses a laminate having a self-repairing layer on a base material layer that self-repairs generated scratches by heating. The laminate contains a cured active energy ray-curable resin and a thermoplastic resin dispersed therein, and it is said that self-repair is exhibited by softening the thermoplastic resin by heating and filling the scratches.

Japanese Patent Application Laid-Open No. 2006-506471

When the thermoplastic resin is dispersed in the cured active energy ray-curable resin as disclosed in Patent Document 1, it is difficult to increase the hardness of the self-repairing layer. Also, if the scratches on the self-healing layer are deep, it will be difficult to repair.

The subject of the present disclosure is a polymerizable composition capable of producing a molded product that is easily repaired even if scratched and has a high hardness, a molded product that is easily repaired even if scratched and can have a high hardness, and a molded product that is easily repaired even if scratched. It is to provide a composite member provided with this molded body.

The polymerizable composition according to one aspect of the present disclosure contains a polymerizable compound (A) and a metal ion (B). The polymerizable compound (A) contains the component (a) having a solubility parameter value range of 2.0 or less in a proportion of 50 mol% or more and 100 mol% or less. The component (a) contains at least an unsaturated carboxylic acid (a1).

The molded product according to one aspect of the present disclosure includes a cured product of the polymerizable composition.

The molded article according to another aspect of the present disclosure changes from the first state to the second state when a stimulus is applied, and changes from the second state to the first state when the stimulus is removed. Change to a state. The storage elastic modulus in the first state is 1 GPa or more. The storage elastic modulus in the second state is 10 MPa or less.

The composite member according to one aspect of the present disclosure includes a black member and the molded body covering the member.

According to one aspect of the present disclosure, a polymerizable composition capable of producing a molded product that is easily repaired even if scratched and has a high hardness, and a molded product that is easily repaired even if scratched and can have a high hardness. , And a composite member including this molded body can be provided.

It is a graph which shows the relationship curve of the storage elastic modulus-temperature of the molded article about Example 1. FIG. It is a graph which shows the relationship curve of the storage elastic modulus-temperature of the molded article with respect to Examples 3 and 4. It is a graph which shows the relationship between the ratio of the metal ion in a composition, and the glass transition temperature of a molded article. 6 is a chart of IR spectra for samples having different proportions of metal ions in the composition.

Hereinafter, embodiments of the present disclosure will be described. The present disclosure is not limited to the following embodiments. The following embodiment is only one of the various embodiments of the present disclosure, and various modifications can be made according to the design as long as the object of the present disclosure can be achieved.

The polymerizable composition according to the first embodiment of the present disclosure (hereinafter, also referred to as composition (X)) will be described.

The composition (X) contains a polymerizable compound (A) and a metal ion (B). The polymerizable compound (A) contains the component (a) having a solubility parameter value range (range) of 2.0 or less in a proportion of 50 mol% or more and 100 mol% or less. The component (a) contains at least an unsaturated carboxylic acid (a1).

From this composition (X), a molded product containing a cured product of the composition (X) can be produced. Specifically, for example, the composition (X) is molded into an appropriate shape, and the polymerizable compound (A) is polymerized and cured to produce a molded product.

The molded product produced from the composition (X) can change from the first state to the second state when a stimulus is applied, and from the second state to the first state when the stimulus is removed. Can change. The storage elastic modulus of the molded product in the first state is high, so that the molded product is not easily deformed even when a force is applied to the molded product. On the other hand, the storage elastic modulus of the molded body in the second state is low, and therefore, when a force is applied to the molded body, it is easily plastically deformed. Therefore, even if the molded body is damaged in the first state, if the molded body is stimulated to change to the second state, the molded body can be easily deformed and the scratch can be repaired. When the stimulus is removed from the molded body, the molded body is returned to the first state and is less likely to be deformed, so that the repaired state is maintained. When the state changes from the first state to the second state, the storage elastic modulus of the molded product decreases.

In the first embodiment, the amount of change in elasticity during storage tends to be large when the molded product changes from the first state to the second state and from the second state to the first state. .. In other words, the difference in hardness between the first state and the second state tends to be large. As a result, the molded body tends to have high hardness in the first state, and the molded body tends to be plastically deformed in the second state. For example, even if the molded body is greatly and deeply scratched, the scratches are repaired. Cheap. For example, even a scratch having a depth of about 100 μm can be easily repaired.

In the first embodiment, it is easy to realize that the storage elastic modulus in the first state is 1 GPa or more and the storage elastic modulus in the second state is 10 MPa or less. In this case, in the first state, the molded product tends to have high hardness and strength, and it is also possible to realize that the pencil hardness of the molded product is 3H or more. Further, in the second state, the molded body is particularly liable to be plastically deformed, and therefore, in the first embodiment, large and deep scratches are liable to be repaired.

The molded product may be directly changed from the first state to the second state, and the molded body may change from the first state to the second state through a state (transition state) that is neither the first state nor the second state. May change to. Similarly, the molded body may change directly from the second state to the first state, or may change from the second state to the first state through the transition state.

The stimulus is a load required to change the molded product from the first state to the second state. The stimulus comprises at least one selected from the group consisting of, for example, heat, pressure, liquid, and gas. That is, stimulating includes at least one selected from the group consisting of, for example, applying heat, applying pressure, exposing to a liquid, and exposing to a gas. The liquid preferably has an affinity for the unsaturated carboxylic acid (a1), such as water. The gas also preferably has an affinity for the unsaturated carboxylic acid (a1), such as water vapor.

More specifically, for example, by applying heat to the molded body in the first state to raise the temperature, the molded body can be changed to the second state, and the heat is stopped to be applied to the molded body. By lowering the temperature, the molded product can be changed to the first state. Further, for example, by immersing the molded product in the first state in hot water to apply heat and exposing it to water, the molded product can be changed to the second state, and the molded product is taken out from the hot water. This makes it possible to change the molded product to the first state. Further, by heating the molded body by spraying the heated steam on the molded body in the first state and exposing the molded body to the steam, the molded body can be changed to the second state, and the spraying of steam can be performed. By stopping, the molded product can be changed to the first state.

It is presumed that the above-mentioned characteristics of the molded product are exhibited for the following reasons.

The polymer composed by polymerizing the composition (X) containing the component (a) has at least one of a carboxyl group and a carboxylate group derived from the unsaturated carboxylic acid (a1). Hereinafter, the carboxyl group and the carboxylate group are collectively referred to as a coordinating functional group. Coordinating functional groups can coordinate to the metal ion (B). By coordinating a plurality of coordinating functional groups to the metal ion (B), a crosslinked structure via the metal ion (B) is formed in the molded product.

Further, the composition (X) contains a component (a) having a solubility parameter value range of 2.0 or less in a proportion of 50 mol% or more and 100 mol% or less, and this component (a) is at least unsaturated. By containing the saturated carboxylic acid (a), the dispersibility of the unsaturated carboxylic acid (a1) in the composition (X) is high. Therefore, the coordinating functional group derived from the unsaturated carboxylic acid (a1) can be well dispersed in the molded product produced from the composition (X). Therefore, the crosslinked structure via the metal ion (B) can be well dispersed and present in the molded product.

Therefore, the molded product can have a strong structure, and the storage elastic modulus in the first state can be realized to be 1 GPa or more.

When the molded product is stimulated, the metal ion (B) and the coordinating functional group are likely to be dissociated. In other words, the stimulus is a load that facilitates the dissociation of the metal ion (B) and the coordinating functional group. Therefore, the molecular chains constituting the molded product are easily moved, and the molded product is easily plastically deformed. Thereby, it can be realized that the storage elastic modulus in the second state is 10 MPa or less.

For example, when the stimulus contains at least one of heat and pressure, it is considered that the metal ion (B) and the coordinating functional group are likely to be dissociated by increasing the molecular vibration due to the stimulus. Further, when the stimulus contains at least one of a liquid and a gas, the molded product is swollen by the liquid or the gas, and an interaction occurs between the coordinating functional group and the molecule of the liquid or the gas. It is considered that the metal ion (B) and the coordinating functional group are likely to be dissociated.

Although the theory regarding the above mechanism is reasonably derived, the present embodiment is not bound by the above theory.

The composition of the composition (X) will be described in more detail.

As described above, the composition (X) contains the polymerizable compound (A) and the metal ion (B). The polymerizable compound (A) contains the component (a), and the component (a) contains an unsaturated carboxylic acid (a1).

The unsaturated carboxylic acid (a1) preferably has one polymerizable unsaturated group in one molecule. In this case, it is particularly easy to realize that the storage elastic modulus in the second state is 10 MPa or less. The unsaturated carboxylic acid (a1) preferably contains at least one of methacrylic acid (solubility parameter 10.73) and acrylic acid (solubility parameter 11.08). In this case, a high storage elastic modulus in the first state and a low storage elastic modulus in the second state are particularly likely to be realized. The compound that the unsaturated carboxylic acid (a1) can contain is not limited to the above.

The component (a) may contain only the unsaturated carboxylic acid (a1), but may contain a compound other than the unsaturated carboxylic acid (a1). By adjusting the proportion of the compound other than the unsaturated carboxylic acid (a1) in the component (a), the number density of the crosslinked structure in the molded product can be adjusted, whereby the storage elastic modulus in the first state of the molded product can be adjusted. The rate and storage modulus in the second state can be adjusted. In addition, various physical properties of the molded product can be adjusted with a compound other than the unsaturated carboxylic acid (a1). For example, the component (a) may further contain an unsaturated carboxylic acid ester (a2). The unsaturated carboxylic acid ester (a2) can have a solubility parameter close to that of the unsaturated carboxylic acid (a1), and therefore it is easy to realize that the value range of the solubility parameter of the component (a) is within 2.0. .. In addition, the unsaturated carboxylic acid ester (a2) can increase the hydrophobicity of the molded product, which makes it easier to impart water resistance to the molded product.

When the component (a) contains an unsaturated carboxylic acid ester (a2), the unsaturated carboxylic acid ester (a2) preferably has one polymerizable unsaturated group in one molecule. In this case, it is particularly easy to realize that the storage elastic modulus in the second state is 10 MPa or less. The unsaturated carboxylic acid (a1) contains at least one of acrylic acid and methacrylic acid, and the unsaturated carboxylic acid ester (a2) contains at least one of acrylic acid ester and methacrylic acid ester. preferable. In this case, a high storage elastic modulus in the first state is particularly likely to be realized. It is presumed that this is because the main clavicle of the polymer of the component (a) tends to be rigid.

The unsaturated carboxylic acid ester (a2) is, for example, methyl methacrylate (solubility parameter 9.5), ethyl methacrylate (solubility parameter 9.0), butyl methacrylate (solubility parameter 8.8), methyl acrylate (solubility parameter 9.8). 10), contains at least one compound selected from the group consisting of ethyl acrylate (solubility parameter 9.5), propyl acrylate (solubility parameter 9.0), butyl acrylate (solubility parameter 9.0) and the like. To do. The unsaturated carboxylic acid ester (a2) preferably contains at least one compound selected from the group consisting of methyl methacrylate, ethyl methacrylate, methyl acrylate and ethyl acrylate. In this case, a high storage elastic modulus in the first state and a low storage elastic modulus in the second state are particularly likely to be realized. The compound that the unsaturated carboxylic acid ester (a2) can contain is not limited to the above.

When the component (a) contains an unsaturated carboxylic acid (a1) and an unsaturated carboxylic acid ester (a2), the unsaturated carboxylic acid with respect to the total of the unsaturated carboxylic acid (a1) and the unsaturated carboxylic acid ester (a2). The ratio of the acid ester (a2) is preferably 50 mol% or more and 99 mol% or less. In this case, when this ratio is 50 mol% or more, the molded product tends to have particularly high water resistance. When this ratio is 99 mol% or less, high storage viscoelasticity in the first state and low storage viscoelasticity in the second state are likely to be realized. This ratio is more preferably 70 mol% or more, further preferably 80 mol% or more, and particularly preferably 85 mol% or more. Further, this ratio is more preferably 95 mol% or less, and particularly preferably 90 mol% or less. When the improvement of the stored viscoelasticity in the first state and the decrease of the stored viscoelasticity in the second state are emphasized, the ratio of the unsaturated carboxylic acid ester (a2) is 50 mol% or less. You may.

As described above, the ratio of the component (a) to the polymerizable compound (A) is 50 mol% or more. Therefore, it is easy to realize a high storage elastic modulus in the first state and a low storage elastic modulus in the second state of the molded product. This ratio is more preferably 80 mol% or more, and further preferably 95 mol% or more. It is also preferable that the polymerizable compound (A) contains only the component (a).

When the polymerizable compound (A) contains a component other than the component (a) (hereinafter referred to as the component (b)), the component (b) is, for example, an unsaturated carboxylic acid contained in the above component (a). Contains at least one compound selected from the group consisting of acrylic acids other than a1), unsaturated carboxylic acid esters other than unsaturated carboxylic acid ester (a2) contained in component (a), and unsaturated compounds other than the above. To do. For example, the component (b) is styrene (solubility parameter 8.7), lauryl methacrylate (solubility parameter 8.2), stearyl methacrylate (solubility parameter 7.8), ethylene (solubility parameter 8.0), ethylene terephthalate (solubility parameter 8.0). It contains at least one compound selected from the group consisting of solubility 10.7), isoprene (solubility parameter 8.2) and the like.

As described above, the range of the solubility parameter value of the component (a) is within 2.0, and the component (a) contains at least the unsaturated carboxylic acid (a1). That is, when the component (a) contains a plurality of kinds of compounds, the absolute value of the difference in the solubility parameter between the compound having the maximum solubility parameter and the compound having the minimum solubility parameter in the component (a). Is 2.0 or less. The component (a) may contain only a single compound, or may contain only a plurality of types of compounds having the same solubility parameter. In these cases, the range of the solubility parameter of the component (a) is 0. Among the compounds in the polymerizable compound (A), the compound contained in the component (a) is selected so that the proportion of the component (a) is maximized. Therefore, when the polymerizable compound (A) contains a plurality of types of compounds, whether each compound is contained in the component (a) or the component (b) depends on the solubility parameter of each compound and the polymerizable compound. It depends on the ratio to (A). Therefore, the compound that can be contained in the component (a) is not limited to the above description alone, and the compound that can be contained in the component (b) is not limited to the above description alone. That is, even if they are the same compound, they may be contained in the component (a) or may be contained in the component (b). For example, suppose that the polymerizable compound (A) has a solubility parameter of 1 than that of compound α, which is an unsaturated carboxylic acid, compound β, which is an unsaturated carboxylic acid ester having a solubility parameter 1.5 larger than that of compound α, and compound α. .5 It is assumed that the compound γ, which is a small unsaturated carboxylic acid ester, is contained. In this case, if the ratio of the compound α is 30% by mass, the ratio of the compound β is 59% by mass, and the ratio of the compound γ is 1% by mass with respect to the polymerizable compound (A), the ratio of the component (a) is When the compound contained in the component (a) is selected so as to be maximum, the component (a) contains the compound α and the compound β, and the component (b) contains the compound γ. In this case, the unsaturated carboxylic acid (a1) is composed of compound α, and the unsaturated carboxylic acid ester (a2) is composed of compound β. In this case, the range of the solubility parameter values of the component (a) is 1.5, and the ratio of the component (a) is 99% by mass. Further, if the ratio of compound α is 30% by mass, the ratio of compound β is 1% by mass, and the ratio of compound γ is 59% by mass, the component (a) is included in the component (a) so as to maximize the ratio of the component (a). When a compound is selected, the component (a) contains the compound α and the compound γ, and the component (b) contains the compound β. In this case, the unsaturated carboxylic acid (a1) is composed of compound α, and the unsaturated carboxylic acid ester (a2) is composed of compound γ. In this case, the range of the solubility parameter values of the component (a) is 1.5, and the ratio of the component (a) is 99% by mass. When the ratio of the compound β and the ratio of the compound γ are the same, it may be considered that the component (a) contains the compound α and the compound β and the component (b) contains the compound γ, or the component (b) may be contained. It may be considered that a) contains the compound α and the compound γ and the component (b) contains the compound β.

The metal ion (B) is not particularly limited as long as the coordinating functional group derived from the unsaturated carboxylic acid (a1) can be coordinated. It is preferred that the metal ion (B) is classified as a hard acid or an intermediate acid according to HSAB rules. In this case, a high storage elastic modulus in the first state is likely to be realized. This is because the carboxylate group generated by ionizing the carboxyl group of the unsaturated carboxylic acid (a1) is a hard base, so that when the metal ion (B) is a hard acid or an intermediate acid, it is combined with the carboxylate group. It is considered that this is because the affinity with the metal ion (B) is good and the coordination bond is easily formed. It is particularly preferable that the metal ion (B) is classified as a hard acid. In this case, a high storage elastic modulus in the first state is more likely to be realized.

The metal ion (B) preferably contains at least one selected from the group consisting of alkali metal ions and alkaline earth metal ions. In this case, a high storage elastic modulus in the first state and a low storage elastic modulus in the second state are particularly likely to be realized. When the metal ion (B) contains an alkali metal ion, a low storage elastic modulus is particularly likely to be realized. The high storage elasticity in the first state is likely to be realized because the alkali metal ion and the alkaline earth metal ion have relatively large ionic radii, so that the coordinating functional group is easily coordinated, and thus a crosslinked structure is formed. It is presumed that this is because it is easy to do. In addition, low storage elasticity in the second state is likely to be realized because alkali metal ions and alkaline earth metal ions, especially alkali metal ions, easily absorb water at high temperatures, so that the stimulus is heat and water or water vapor. It is presumed that this is because the dissociation of the coordination bond is likely to occur when the above is included.

Specifically, the metal ion (B) preferably contains at least one of a sodium ion and a zinc ion. It is particularly preferable that the metal ion (B) contains sodium ion, which is classified as a hard acid and is an alkali metal.

The ratio of the metal ion (B) to the unsaturated carboxylic acid (a1) is, for example, 1 mol% or more and 100 mol% or less. The ratio of the metal ion (B) to the unsaturated carboxylic acid (a1) is preferably 1 mol% or more and 10 mol% or less. In this case, a low storage elastic modulus in the second state is particularly easy to be realized, and a scratch or the like is particularly easy to be repaired in the second state. It is also preferable that the ratio of the metal ion (B) to the unsaturated carboxylic acid (a1) is more than 10 mol% and 100 mol% or less. In this case, a high storage elastic modulus in the first state is particularly easy to be realized, the molded body is likely to have a high hardness in the first state, and the molded body can have chemical resistance.

The ratio of the metal ion (B) to the coordinating functional group is the ratio of the metal ion (B) to the coordinating functional group in the stable coordination structure formed by the coordinating functional group and the metal ion (B). It is preferable that it is close to. In this case, the number density of the crosslinked structure becomes particularly high, and a high storage elastic modulus in the first state is particularly likely to be realized.

For example, when the metal ion (B) is a sodium ion, a stable coordination structure (six coordination structure) is formed by coordinating one carboxylate group and two carboxyl groups to sodium. Therefore, the ratio of the metal ion (B) to the unsaturated carboxylic acid (a1) is preferably close to 33 mol%, for example, 5 mol% or more and 40 mol% or less. When the amount of metal ions (B) is large, a molded product having repairability can be obtained, but metal ions that do not form a coordination structure are likely to be generated. Therefore, for example, metal ions (B) described later are included. The compound becomes difficult to dissolve sufficiently in the composition (X) and the molded product. Therefore, the composition (X) and the molded product tend to be non-uniform.

When the metal ion (B) is a zinc ion, a stable coordination structure (four-coordination structure) is formed by coordinating two carboxylate groups to one zinc ion, but in reality. A six-coordination structure in which two carboxylate groups and one carboxyl group are coordinated to one zinc ion is also mixed. Therefore, the ratio of the metal ion (B) to the unsaturated carboxylic acid (a1) is preferably close to 35 mol%, for example, 5 mol% or more and 40 mol% or less.

In the composition (X), it is preferable that at least a part of the unsaturated carboxylic acid (a1) is neutralized with the metal ion (B). That is, it is preferable that at least a part of the unsaturated carboxylic acid (a1) forms a salt with the metal ion (B). In this case, a high storage elastic modulus in the first state is particularly likely to be realized. It is presumed that this is because a stable coordination structure due to the coordinating functional group and the metal ion (B) is particularly likely to be formed in the molded body.

The composition (X) may contain a polymerization initiator. The polymerization initiator contains, for example, at least one of a photoradical polymerization initiator and a thermal radical polymerization initiator. The photoradical polymerization initiator can contain, for example, an alkylphenone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, and the like. The thermal radical polymerization initiator can contain, for example, an organic peroxide-based radical polymerization initiator.

The composition (X) may contain additives other than the above. For example, the composition (X) may contain a colorant, a plasticizer, an antibacterial agent, a flame retardant, an antioxidant, a metal inactivating agent, an ultraviolet protective agent, an antistatic agent, a filler and the like.

The method for preparing the composition (X) will be described. The composition (X) can be prepared by mixing the components of the above composition (X).

In preparing the composition (X), first, by mixing an unsaturated carboxylic acid (a1) and a metal ion (B), at least a part of the unsaturated carboxylic acid (a1) is mixed with at least one of the metal ions (B). It may be neutralized in parts and subsequently blended with the remaining ingredients. In neutralizing the unsaturated carboxylic acid (a1), for example, a compound containing an unsaturated carboxylic acid (a1) and a metal ion (B) is mixed. Examples of compounds containing metal ions (B) include salts of metal ions (B) and saturated fatty acids, hydroxides of metal ions, carbonates of metal ions, hydrogen carbonates of metal ions and the like. Examples of saturated fatty acids include acetic acid, formic acid, propionic acid, butyric acid, stearic acid and the like. Further, by blending a salt of an unsaturated carboxylic acid (a1) and a metal ion (B) (for example, sodium methacrylate) in the composition (X), the unsaturated carboxylic acid in the composition (X) At least a part of (a1) may be neutralized with at least a part of the metal ion (B).

When a molded product is produced from the composition (X), for example, the composition (X) is molded into an appropriate shape and cured by polymerizing the polymerizable compound (A) as described above. In molding the composition (X), the molded product may be molded into an appropriate shape using a mold, or may be molded into a film shape by coating. When the polymerizable compound (A) is polymerized, it is polymerized by a method according to the type of the polymerization initiator in the composition (X). When the polymerization initiator is a photoradical polymerization initiator, the composition (X) is irradiated with light, and when the polymerization initiator is a thermal radical polymerization initiator, the composition (X) is heated to obtain a polymerizable compound ( A) is polymerized. The specific conditions for polymerizing the polymerizable compound (A) are appropriately determined according to the type of the component in the polymerizable compound (A).

The glossiness of the molded product produced from the composition (X) may be 10 GU or more and 1000 GU or less at an incident angle of 60 °. The glossiness is defined by JIS K5600-4-7. As a measuring device for measuring the glossiness, for example, a gloss checker (model number IG-331) manufactured by HORIBA, Ltd. can be used. If the glossiness of the molded body is high, the glossiness is lowered and the appearance is likely to deteriorate when the molded body is scratched. However, as described above, even if the molded body is scratched, the scratches are easily repaired, so that the molded body is easily repaired. It is easy to recover the high glossiness of the molded product, and therefore the appearance of the molded product is easily maintained. In other words, if a molded product having a glossiness of 10 GU or more and 1000 GU or less is produced from the composition (X) at an incident angle of 60 °, the appearance of the molded product is likely to be kept good. It is suitable for producing a molded product having an angle of 60 ° and 10 GU or more and 1000 GU or less.

The molded product produced from the composition (X) ^{may have an L *} of 0 or more and 20 or less ^{according to the CIE1976 L *} a ^* b ^* color space (CIELAB). L ^* is defined by JIS Z8781-4. Even when the L ^{* of the} molded body is 0 or more and 20 or less, the scratches are particularly noticeable when the molded body is scratched, but as described above, even if the molded body is scratched, the scratches are easily repaired, so that the molding is performed. It is easy to keep the appearance of the body good. In other words, ^{if a molded product having an L *} of 0 or more and 20 or less of the composition (X) is produced, the appearance of the molded product can be easily maintained. Therefore, the composition (X) is ^{molded with an L *} of 0 or more and 20 or less. Suitable for making a body. In order to adjust the L ^* of the molded product, for example, a black coloring material may be added to the composition (X). The black colorant is at least one material selected from the group consisting of carbon-based black pigments such as carbon black, lamp black, and bone black, and oxide-based black pigments such as iron oxide and composite oxides of copper and chromium. contains.

The glossiness and color that the molded product produced from the composition (X) can have are not limited to the above, and the molded product may have an appropriate glossiness and an appropriate color.

The molded body according to the second embodiment of the present disclosure will be described.

The molded article according to the second embodiment contains a cured product of a polymerizable composition containing the polymerizable compound (A). The molded body changes from the first state to the second state when the stimulus is applied, and changes from the second state to the first state when the stimulus is removed. That is, the molded product can reversibly change between the first state and the second state. The storage elastic modulus in the first state is 1 GPa or more, and the storage elastic modulus in the second state is 10 MPa or less.

In the first state, the molded body can have high hardness and strength and is not easily deformed when a force is applied. On the other hand, in the second state, it is easily plastically deformed when a force is applied. Therefore, even if the molded body is damaged in the first state, if the molded body is stimulated to change to the second state, the molded body can be easily deformed and the scratch can be repaired. When the stimulus is removed from the molded body, the molded body is returned to the first state and is less likely to be deformed, so that the repaired state is maintained.

The molded product may be directly changed from the first state to the second state, and the molded body may change from the first state to the second state through a state (transition state) that is neither the first state nor the second state. May change to. Similarly, the molded body may change directly from the second state to the first state, or may change from the second state to the first state through the transition state. The transition state is a state in which the storage elastic modulus of the molded product is lower than that of the first state and higher than that of the second state.

The stimulus is a load required to change the molded product from the first state to the second state. The stimulus includes at least one selected from the group consisting of, for example, heat, pressure, liquid, gas and light. That is, stimulating includes at least one selected from the group consisting of, for example, applying heat, applying pressure, exposing to a liquid, exposing to a gas, irradiating with light, and the like. The type of stimulus depends on the composition of the part.

As described above, the storage elastic modulus in the first state is 1 GPa or more. Therefore, the molded product in the first state can have particularly high hardness and strength, and it is also feasible that the pencil hardness of the molded product is 3H or more. The storage elastic modulus is more preferably 2 GPa or more, and further preferably 2.5 GPa or more. Further, the storage elastic modulus is, for example, 100 GPa or less, but the storage elastic modulus is not limited to this, and the storage elastic modulus may be higher than this.

As described above, the storage elastic modulus in the second state is 10 MPa or less. Therefore, the molded body in the second state is particularly liable to be plastically deformed, and therefore, even if the molded body is deeply and greatly scratched, the scratches are easily repaired. The storage elastic modulus is more preferably 5 MPa or less, and even more preferably 3 MPa or less. Further, the storage elastic modulus is, for example, 1 MPa or more, but the storage elastic modulus is not limited to this, and the storage elastic modulus may be lower than this.

The molded body is preferably in the first state in the unstimulated state in the standard state. The standard state is the condition of atmospheric atmosphere, temperature 25 ° C., humidity 65%, and 1 atmosphere. Even if the temperature fluctuates within the range of −20 ° C. or higher and 50 ° C. or lower from the standard state, the molded product is preferably in the first state. That is, when the storage elastic modulus in the first state is 1 GPa or more, it is preferable that the storage elastic modulus of the molded product is 1 GPa or more in the standard state. In this case, in the environment in which the molded product is used, the molded product tends to be maintained in the first state, that is, the molded product tends to have high hardness. In the standard state, the storage elastic modulus of the molded product is more preferably 2 GPa or more, and further preferably 2.5 GPa or more.

When the stimulus includes heat, the temperature at which the second state is reached when the molded product in the first state is heated from 25 ° C to raise the temperature is in the range of 100 ° C to 200 ° C. Is preferable. That is, when the storage elastic modulus in the second state is 10 MPa or less, the temperature at which the storage elastic modulus of the molded product decreases to reach 10 MPa when the molded product is heated from 25 ° C. to raise the temperature. Is preferably in the range of 100 ° C to 200 ° C. In this case, in the environment in which the molded product is used, the storage elastic modulus of the molded product is unlikely to be excessively lowered, and the molded product tends to maintain high hardness. Further, when heating the molded product to change it to the second state, it is not necessary to heat the molded product to an excessively high temperature, which facilitates the work of repairing the molded product.

The molded product according to the second embodiment can be produced, for example, from the composition (X) according to the first embodiment. As described above, the molded product produced from the composition (X) according to the first embodiment changes from the first state to the second state when a stimulus is applied, and the stimulus is removed. It is possible to change from the second state to the first state. Further, in the molded product produced from the composition (X), the storage elastic modulus in the first state is 1 GPa · s or more, and the storage elastic modulus in the second state is 10 MPa or less. , Feasible.

The molded article according to the second embodiment can change from the first state to the second state when a stimulus is applied, and can change from the second state to the first state when the stimulus is removed. If so, it does not have to be prepared from the composition (X) according to the first embodiment. For example, when the polymer obtained by polymerizing the polymerizable compound (A) and the compound of the metal ion (B) are melt-kneaded and then molded to be produced from the composition (X). It is also possible to produce a molded product having the same chemical structure and physical properties as the above. Further, the molded product is not limited to the one produced from the polymerizable compound (A) and the metal ion (B). For example, when the resin matrix constituting the molded product has a chemical bond (hereinafter referred to as dynamic bond) that easily dissociates when a stimulus is applied and easily rebonds when the stimulus is removed, the molded product has a chemical bond. It can be a molded product according to the second embodiment. Examples of dynamic bonds are metal coordination bonds, electrostatic interactions, hydrogen bonds, donor acceptor interactions, host-guest interactions, π-π interactions, imine bonds, acyl bonds, disulfide bonds, deals alder bonds. , Esther bond, boronic acid ester bond and the like.

The coordination bond between the coordinating functional group and the metal ion (B) in the first embodiment is a kind of dynamic bond. When the resin matrix constituting the molded product has a dynamic bond, the molded product changes from the first state to the second state when a stimulus according to the type of dynamic bond is applied, and the stimulus is removed. In this case, the molded product can change from the second state to the first state. In order for the molded body to have a sufficiently high storage elastic modulus in the first state and the molded body to have a sufficiently low storage elastic modulus in the second state, the number density of dynamic bonds in the molded body is required. It is preferred that it is high and the dynamic bonds are dispersed throughout the part.

The glossiness of the molded product according to the second embodiment may be 10 GU or more and 1000 GU or less at an incident angle of 60 °. When the glossiness of the molded body is 10 GU or more and 1000 GU or less at an incident angle of 60 °, the scratches are particularly noticeable when the molded body is scratched, but as described above, the scratches are repaired even if the molded body is scratched. Because it is easy, the appearance of the molded product is easily maintained.

The blackness of the molded product produced from the composition (X) may be CIELAB and L ^* may be 0 or more and 20 or less. Even when the blackness of the molded body is CIELAB and L ^* is 0 or more and 20 or less, the scratches are particularly noticeable when the molded body is scratched, but as described above, the scratches are repaired even if the molded body is scratched. Because it is easy to be formed, the appearance of the molded product is easily maintained. In order to adjust the blackness of the molded product, the molded product may contain a black coloring material. The black colorant may be, for example, the same as that previously described for the first embodiment.

The glossiness and color that the molded product according to the second embodiment can have are not limited to the above, and the molded product may have an appropriate glossiness and an appropriate color.

The composite member according to the third embodiment of the present disclosure will be described.

The composite member includes a black member and a molded body that covers the black member. The molded product is a molded product produced from the composition (X) according to the first embodiment, or a molded product according to the second embodiment. The composite member is configured so that the observer can visually recognize the color of the black member through the molded body.

Specifically, for example, the molded product has light transmission. Further, in the composite member, the black member and the molded body may or may not be in direct contact with each other. When the black member and the molded body are not in direct contact with each other, at least one of the gap and the light-transmitting member is interposed between the black member and the molded body, whereby the observer However, it is preferable that the color of the black member can be visually recognized through the molded body.

According to the third embodiment, when the observer can visually recognize the color of the black member through the molded body, the scratches are particularly noticeable when the molded body is scratched, but as described above, the molded body is scratched. Since it is easy to repair even if it is attached, it is easy to maintain a good appearance of the composite member.

The molded product made from the composition (X) according to the first embodiment, the molded product according to the second embodiment, and the composite member according to the third embodiment can be applied to various uses. For example, they may be applied to products such as building materials, automotive parts, electrical product housings, space parts and the like. In this case, even if the product is scratched, it can be easily repaired. Building materials may include residential interior members such as flooring and water-related members.

Hereinafter, specific examples of the embodiments according to the present disclosure will be described. The embodiments according to the present disclosure are not limited to the following examples.

1. 1. Preparation of composition The composition was prepared by mixing the raw materials shown in Tables 1 and 2. When blending a metal ion compound (sodium acetate, zinc acetate or sodium methacrylate), first mix the metal ion compound with an unsaturated carboxylic acid (methacrylic acid and acrylic acid), and then add the remaining components. Formulated. The thermal radical polymerization initiator shown in Tables 1 and 2 is bis peroxydicarbonate (4-t-butyl 2-cyclohexane-1-yl).

The "molar ratio ((a2) :( a1): (B))" in Tables 1 and 2 indicates the unsaturated carboxylic acid ester and unsaturated carboxylic acid contained in the component (a) in the composition, and the metal. The molar ratio of ions.

2. Preparation of molded body By arranging two stainless steel plates at intervals and surrounding the gap between the stainless steel plates with silicon rubber, a plate-like space was formed between the stainless steel plates. The space was filled with the composition, and in this state, the composition was heated at 70 ° C. for 2 hours, and then further heated at 90 ° C. for 1 hour. As a result, the composition was cured to prepare a molded product having dimensions of 80 mm × 70 mm × 2 mm.

In Comparative Example 2 in which the unsaturated carboxylic acid was not blended, the sodium acetate was not completely dissolved and the molded product became remarkably non-uniform, so the following evaluation test was not performed.

3. 3. Measurement of storage elastic modulus The storage elastic modulus of the molded product was measured under the conditions of atmospheric pressure, atmospheric pressure, and humidity of 65%. In the measurement, a viscoelasticity measuring device (DMS6220, manufactured by Hitachi High-Technologies Corporation) is used as the measuring device, the measurement mode is bending (double-sided beam), the measurement temperature range is from 25 ° C to 200 ° C, and the temperature rise rate is 10 ° C. It was measured under the condition of / minute. As a result, the relationship curve between storage viscoelasticity and temperature was obtained. The results for Example 1 are shown in FIG. 1, the results for Example 2 are shown in A in FIG. 2, and the results for Example 3 are shown in B in FIG.

From this relational curve, the storage elastic modulus at 25 ° C. (standard state) and the storage elastic modulus at 160 ° C. were read. Moreover, the temperature at which the storage elastic modulus reaches 10 MPa at the time of raising the temperature was read. The results are shown in Tables 1 and 2. In Comparative Example 3, the storage elastic modulus decreased only to 44 MPa and did not reach 10 MPa even at 160 ° C.

4. Hardness measurement The pencil hardness of the molded product under standard conditions was measured based on JIS K5600. The results are shown in Tables 1 and 2.

5. Restorability 1
After scratching the surface of the molded product with a cutter knife to a length of 30 mm in the standard state, ^{press pressure of about 3.92 MPa (40 kgf / cm 2} ) for 10 minutes while heating the molded product to 200 ° C. with a hand press. added. Subsequently, the surface of the molded product was visually observed. As a result, the case where no scratches were found was evaluated as "A", and the case where no scratches were found was evaluated as "B". The results are shown in Tables 1 and 2.

6. Repairability 2
After scratching the surface of the molded product with a cutter knife to a length of 30 mm in the standard state, press pressure of ^{about 0.0196 MPa (0.2 kgf / cm 2) while heating the molded product to 180 ° C. with an iron.} Added for minutes. Subsequently, the surface of the molded product was visually observed. As a result, the case where no scratches were found was evaluated as "A", and the case where no scratches were found was evaluated as "B". The results are shown in Tables 1 and 2.

7. Restorability 3
The initial glossiness of the surface of the molded product was measured. As a result, the glossiness was 10 GU or more in each of the Examples and Comparative Examples.

Subsequently, sandpaper # 100 manufactured by Mitsuya Co., Ltd. was rubbed on the surface of the molded product while manually reciprocating 10 times, and then the glossiness of the surface was measured. As a result, the glossiness was less than 10 GU in each of the Examples and Comparative Examples.

Subsequently, the molded product was heated to 200 ° C. with a hand press, and ^{a press pressure of about 3.92 MPa (40 kgf / cm 2} ) was applied for 10 minutes, and then the glossiness of the surface was measured. As a result, the case where the glossiness was 10 GU or more was evaluated as "A", and the case where the glossiness was less than 10 GU was evaluated as "B". The results are shown in Tables 1 and 2.

8. Chemical resistance The molded product was immersed in acetone at 25 ° C. for 3 hours. The case where the weight loss rate of the molded product resulting from this is 10% by mass or less is "A", the case where it is more than 10% by mass and 20% by mass or less is "B", and the case where it is more than 20% by mass is "C". I evaluated it. The results are shown in Tables 1 and 2.

9. The water resistant molded product was immersed in hot water at 80 ° C. for 96 hours. When the weight increase rate of the molded product by this treatment is less than 5% by mass, it is evaluated as "A", when it is 5% by mass or more and less than 10% by mass, it is evaluated as "B", and when it is 10% by mass or more, it is evaluated as "C". did. The results are shown in Tables 1 and 2.

10. Glass transition temperature The dynamic viscoelasticity of the molded product was measured. Using a viscoelasticity measuring device (DMS6220, manufactured by Hitachi High-Technologies Corporation), the measurement mode is bending (double-sided beam), the measurement temperature range is from 25 ° C to 200 ° C, and the temperature rise rate is 10 ° C / min. did. The temperature at the peak position in the relationship curve between tan δ and temperature obtained by this was regarded as the glass transition temperature. The results are shown in Tables 1 and 2. In Comparative Example 1, no glass transition temperature was observed between 25 ° C. and 200 ° C., and it is judged that the glass transition temperature is less than 25 ° C.

11. Relationship between the ratio of metal ions and the glass transition temperature and IR peak Based on Example 3, the change in the glass transition temperature of the molded product when the ratio of sodium ions in the composition was changed was investigated. In measuring the glass transition temperature, differential scanning calorimetry (DSC) of the molded product was performed. A differential scanning calorimetry device (DSC3500, manufactured by Netch Co., Ltd.) was used as the measuring device, and the measuring conditions were from 30 ° C. to 230 ° C. and the temperature rising rate was 5 ° C./min. From the DSC curve obtained thereby, the glass transition temperature was specified.

The result is shown in FIG. The vertical axis of FIG. 3 indicates the glass transition temperature, and the numerical value on the horizontal axis indicates the ratio of sodium ions to unsaturated carboxylic acid (mol%).

As shown in FIG. 3, the glass transition temperature increased as the sodium ion ratio increased until the sodium ion ratio reached about 30 mol%. It is presumed that this is because the higher the proportion of sodium ions, the higher the number density of the coordination structures in the molded body, and the more rigid the molded body. As the proportion of sodium ions increased, the glass transition temperature became less likely to change. This is because the number of sodium ions increased in excess of the ratio for the sodium ions and the coordinating functional group to form a stable coordination structure, so that the number density of the coordination structure increased even if the sodium ions were increased. It is presumed that this is because it has disappeared.

Infrared spectroscopy (IR) of the molded product was also performed. The result is shown in FIG. In A, B, C and D in FIG. 4, the ratio of sodium ions to the total amount of substance of the unsaturated carboxylic acid ester and the unsaturated carboxylic acid in the composition is 0 mol%, 2 mol%, 4 mol% and The IR spectrum when it is 5 mol% is shown. According to this result, in the IR spectrum, the absorption peak corresponding to the ionic bond between the carboxylate group and the sodium ion at around ^{1580 cm-1 is the ratio of sodium ions until the ratio of sodium ions reaches about 30 mol%.} Increased as the value increased.

From these results, it can be determined that a crosslinked structure consisting of metal ions and coordinating functional groups is formed in the molded body, and the number density of the crosslinked structure depends on the proportion of metal ions.

As is clear from the above embodiments and examples, the polymerizable composition according to the first aspect of the present disclosure contains a polymerizable compound (A) and a metal ion (B). The polymerizable compound (A) contains the component (a) having a solubility parameter value range of 2.0 or less in a proportion of 50 mol% or more and 100 mol% or less. The component (a) contains at least an unsaturated carboxylic acid (a1).

According to the first aspect, a molded product can be prepared from the polymerizable composition, and the molded product can be easily repaired even if it is scratched and has a high hardness.

In the first aspect of the polymerizable composition according to the second aspect of the present disclosure, the component (a) further contains an unsaturated carboxylic acid ester (a2).

According to the second aspect, the unsaturated carboxylic acid ester (a2) can increase the hydrophobicity of the molded product, which makes it easier to impart water resistance to the molded product.

The polymerizable composition according to the third aspect of the present disclosure is the unsaturated carboxylic acid ester (a2) with respect to the sum of the unsaturated carboxylic acid (a1) and the unsaturated carboxylic acid ester (a2) in the second aspect. The ratio is 50 mol% or more and 99 mol% or less.

According to the third aspect, the molded product tends to have particularly high water resistance, and high storage viscoelasticity in the first state and low storage viscoelasticity in the second state are likely to be realized.

In the polymerizable composition according to the fourth aspect of the present disclosure, in the second or third aspect, the unsaturated carboxylic acid (a1) contains at least one of acrylic acid and methacrylic acid, and the unsaturated carboxylic acid. The ester (a2) contains at least one of an acrylic acid ester and a methacrylic acid ester.

According to the fourth aspect, a high storage elastic modulus in the first state is particularly likely to be realized.

In the polymerizable composition according to the fifth aspect of the present disclosure, in any one of the first to fourth aspects, at least a part of the unsaturated carboxylic acid (a1) is neutralized with the metal ion (B). ing.

According to the fifth aspect, a high storage elastic modulus in the first state is particularly likely to be realized.

In the polymerizable composition according to the sixth aspect of the present disclosure, in any one of the first to fifth aspects, the ratio of the metal ion (B) to the unsaturated carboxylic acid (a1) is 1 mol% or more and 100 mol. % Or less.

According to the sixth aspect, high storage viscoelasticity in the first state and low storage viscoelasticity in the second state are likely to be realized.

In the polymerizable composition according to the seventh aspect of the present disclosure, in any one of the first to sixth aspects, the metal ion (B) is selected from the group consisting of an alkali metal ion and an alkaline earth metal ion. Contains at least one of the following.

According to the seventh aspect, a high storage elastic modulus in the first state and a low storage elastic modulus in the second state are particularly likely to be realized.

The molded article according to the eighth aspect of the present disclosure includes a cured product of the polymerizable composition according to the aspect at any of the first to seventh positions.

According to the eighth aspect, the molded product can be easily repaired even if it is scratched and has a high hardness.

In the eighth aspect, the molded article according to the ninth aspect of the present disclosure changes from the first state to the second state when a stimulus is applied, and from the second state when the stimulus is removed. It changes to the first state, and the storage elastic modulus in the first state is 1 GPa or more, and the storage elastic modulus in the second state is 10 MPa or less.

According to the ninth aspect, in the first state, the molded body tends to have high hardness and strength, and in the second state, the molded body is particularly liable to be plastically deformed, so that even if a large and deep scratch is made, it is liable to be repaired.

The molded product according to the tenth aspect of the present disclosure contains a cured product of a polymerizable composition containing the polymerizable compound (A), and changes from the first state to the second state when a stimulus is applied. And, when the stimulus is removed, the state changes from the second state to the first state, the storage elastic modulus in the first state is 1 GPa or more, and the storage elastic modulus in the second state is 10 MPa or less. ..

According to the tenth aspect, the molded product can be easily repaired even if it is scratched and has a high hardness.

The molded article according to the eleventh aspect of the present disclosure includes at least one selected from the group consisting of heat, pressure, liquid, gas and light in the ninth or tenth aspect.

According to the eleventh aspect, the stimulus can be utilized to easily repair the molded product.

In the eleventh aspect, the molded article according to the twelfth aspect of the present disclosure is the second when the stimulus contains heat and the molded article in the first state is heated from 25 ° C. to raise the temperature. The temperature at which the above state is reached is in the range of 100 ° C. to 200 ° C.

According to the twelfth aspect, in the environment in which the molded product is used, the storage elastic modulus of the molded product is unlikely to be excessively lowered, and the molded product tends to maintain high hardness. Further, in heating the molded body to change it to the second state, it is not necessary to heat the molded body to an excessively high temperature, which facilitates the work of repairing the molded body.

The molded product according to the thirteenth aspect of the present disclosure has a glossiness of 10 GU or more and 1000 GU or less at an incident angle of 60 ° in any one of the eighth to twelfth aspects.

According to the thirteenth aspect, even if the molded body is scratched, it is easily repaired, so that even if the glossiness of the molded body is lowered due to the scratch, the glossiness is easily restored.

The molded product according to the fourteenth aspect of the present disclosure has an L ^* according to CIELAB of 0 or more and 20 or less in any one of the eighth to thirteenth aspects.

According to the fourteenth aspect, if the molded body is black, the scratches are particularly noticeable when the molded body is scratched, but even if the molded body is scratched, the scratches are easily repaired, so that the appearance of the molded body is good. Easy to keep in.

The composite member according to the fifteenth aspect of the present disclosure includes a black member and a molded body according to any one of the eighth to fourteenth aspects covering the member.

According to the fifteenth aspect, when the color of the black member is visually recognized through the molded body, the scratches are particularly noticeable when the molded body is scratched, but even if the molded body is scratched, it is repaired. Because it is easy to be formed, the appearance of the molded product is easily maintained.

Claims (15)

Containing a polymerizable compound (A) and a metal ion (B),
The polymerizable compound (A) contains the component (a) having a solubility parameter value range of 2.0 or less in a proportion of 50 mol% or more and 100 mol% or less.
The component (a) contains at least an unsaturated carboxylic acid (a1).
Polymerizable composition. The component (a) further contains an unsaturated carboxylic acid ester (a2).
The polymerizable composition according to claim 1. The ratio of the unsaturated carboxylic acid ester (a2) to the total of the unsaturated carboxylic acid (a1) and the unsaturated carboxylic acid ester (a2) is 50 mol% or more and 99 mol% or less.
The polymerizable composition according to claim 2. The unsaturated carboxylic acid (a1) contains at least one of acrylic acid and methacrylic acid, and the unsaturated carboxylic acid ester (a2) contains at least one of acrylic acid ester and methacrylic acid ester.
The polymerizable composition according to claim 2 or 3. At least a part of the unsaturated carboxylic acid (a1) is neutralized with the metal ion (B).
The polymerizable composition according to any one of claims 1 to 4. The ratio of the metal ion (B) to the unsaturated carboxylic acid (a1) is 1 mol% or more and 100 mol% or less.
The polymerizable composition according to any one of claims 1 to 5. The metal ion (B) contains at least one selected from the group consisting of alkali metal ions and alkaline earth metal ions.
The polymerizable composition according to any one of claims 1 to 6. A cured product of the polymerizable composition according to any one of claims 1 to 7.
Molded body. When a stimulus is given, it changes from the first state to the second state, and when the stimulus is removed, it changes from the second state to the first state.
The storage elastic modulus in the first state is 1 GPa or more, and
The storage elastic modulus in the second state is 10 MPa or less.
The molded product according to claim 8. Containing a cured product of a polymerizable composition containing the polymerizable compound (A),
When a stimulus is given, it changes from the first state to the second state, and when the stimulus is removed, it changes from the second state to the first state.
The storage elastic modulus in the first state is 1 GPa or more, and
The storage elastic modulus in the second state is 10 MPa or less.
Molded body. The stimulus comprises at least one selected from the group consisting of heat, pressure, liquid, gas and light.
The molded product according to claim 9 or 10. The stimulus involves heat
When the molded product in the first state is heated from 25 ° C. to raise the temperature, the temperature at which the second state is reached is in the range of 100 ° C. to 200 ° C.
The molded product according to claim 11. The glossiness at an incident angle of 60 ° is 10 GU or more and 1000 GU or less.
The molded product according to any one of claims 8 to 12. ^{L *} by CIELAB is 0 or more and 20 or less,
The molded product according to any one of claims 8 to 13. The molded product according to any one of claims 8 to 14, comprising a black member and a molded body covering the member.
Composite member.

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