Hollow resin particles, their manufacturing methods and applications

Abstract

This invention provides a hollow resin particle having a shell and a hollow portion surrounded by the shell, and possessing excellent dielectric properties unaffected by high-temperature environments. Furthermore, this invention provides a method for manufacturing such a hollow resin particle. Moreover, this invention provides uses for such a hollow resin particle. In an embodiment of this invention, the hollow resin particle has a shell and a hollow portion surrounded by the shell, and when subjected to a heating test under condition I (180°C and 1 hour), the dielectric loss tangent Df1 measured at a frequency of 10 GHz before the heating test and the dielectric loss tangent Df2 measured at a frequency of 10 GHz after the heating test under condition I satisfy the formula: Df2-Df1≤0.004.

Description

Technical Field

[0001] This invention relates to a hollow resin particle, its manufacturing method, and its uses. Prior Technology

[0002] To achieve high-speed information processing using electronic machines, efforts are being made to reduce the dielectric constant and dielectric loss tangent of the insulating layer of multilayer printed circuit boards. As part of this effort, research is underway to introduce voids into the resin layer by mixing hollow particles with shells and hollow portions surrounded by those shells in a thermosetting resin, thereby achieving a low dielectric constant and low dielectric loss tangent.

[0003] As for previous hollow resin particles, the report describes obtaining hollow particles by suspension polymerization of monomers, primarily composed of acrylic polyfunctional monomers such as trimethylolpropane tri(meth)acrylate and acrylic monofunctional monomers primarily composed of methyl acrylate, with a hydrophobic solvent (Patent Document 1). However, generally speaking, acrylic resins have high dielectric constants and dielectric loss tangents, and insufficient heat resistance. Therefore, the hollow particles described in Patent Document 1 are not suitable for achieving the purpose of lowering the dielectric constant and dielectric loss tangent of the resin layer.

[0004] As for previous hollow resin particles, it was reported that hollow resin particles were obtained by suspension polymerization of a polymerizable monomer containing more crosslinkable hydrocarbon monomers such as divinylbenzene together with a hydrophobic solvent (Patent Document 2). However, hollow resin particles containing more divinylbenzene have a higher dielectric loss tangent because more vinyl groups remain inside the particles. Previous technical documents Patent documents

[0005] Patent Document 1: International Publication No. 2022-107674 Patent Document 2: International Publication No. 2023-074651 Summary of the Invention

[0006] [The problem the invention aims to solve] Previously, hollow resin particles suffered from resin oxidation and deterioration under high-temperature environments, potentially leading to a deterioration in the dielectric properties of components containing these particles. In particular, the dielectric constant and dielectric loss tangent of the hollow resin particles deteriorated due to heat exposure during component processing, making it difficult to achieve low dielectric constants and low dielectric loss tangents in the components. Therefore, there is a need for hollow resin particles unaffected by high-temperature environments. This invention addresses these problems by providing a hollow resin particle having a shell and a hollow portion surrounded by the shell, exhibiting excellent dielectric properties unaffected by high-temperature environments. Furthermore, a method for manufacturing such hollow resin particles is provided. Finally, applications of such hollow resin particles are provided. [Technical means to solve the problem]

[0007] [1] In embodiments of the present invention, hollow resin particles have a shell portion and a hollow portion surrounded by the shell portion, and When a heating test is performed under condition I at 180°C for 1 hour, the dielectric loss tangent Df1 measured at a frequency of 10 GHz before the heating test and the dielectric loss tangent Df2 measured at a frequency of 10 GHz after the heating test under condition I satisfy equation (1). Df2-Df1≤0.004···(1) [2] The dielectric loss tangent Df1 of the hollow resin particles described in [1] above may not reach 0.002. [3] The relative permittivity of the hollow resin particles described in [1] or [2] above at a measurement frequency of 10 GHz may not reach 1.5. [4] Hollow resin particles as described in any of [1] to [3] above, wherein the shell portion may contain a polymer (P) obtained by reacting a composition (A) comprising at least one of a group consisting of a crosslinking monomer (a) and a compound (c) selected from a monofunctional monomer (b) and having an ether structure represented by formula (2). [Chemistry 1] [5] As described in [4] above, the hollow resin particles, wherein the crosslinking monomer (a) may be an aromatic crosslinking monomer. [6] As described in [5] above, when the total amount of the crosslinking monomer (a), the monofunctional monomer (b) and the compound (c) is set to 100 parts by weight, the aromatic crosslinking monomer may be 1 to 50 parts by weight. [7] Hollow resin particles as described in any of [4] to [6] above, wherein the monofunctional monomer (b) may be selected from at least one of the group consisting of styrene, α-methylstyrene, ethylvinylbenzene, vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, vinylbiphenyl, vinylnaphthalene, and vinylnaphthalene. [8] The hollow resin particles described in any of [4] to [7] above, wherein the shell portion may contain 0 to 10 parts by weight of the hydrocarbon resin (B) relative to 100 parts by weight of the total amount of the polymer (P) and the hydrocarbon resin (B). [9] The 5% heat weight reduction temperature of hollow resin particles described in any of [1] to [8] above when heated at 10°C / min in air atmosphere can be above 270°C.

[10] The volume average particle size of the hollow resin particles described in any of [1] to [9] above can be 0.1 μm to 30 μm.

[11] When the hollow resin particles described in any of [1] to

[10] above are subjected to a heating test at 260°C and 2 minutes under condition II, the dielectric loss tangent Df1 at a measurement frequency of 10 GHz before the heating test and the dielectric loss tangent Df3 at a measurement frequency of 10 GHz after the heating test under condition II satisfy equation (3). Df3-Df1≤0.004···(3)

[12] In embodiments of the present invention, hollow resin particles have a shell portion and a hollow portion surrounded by the shell portion, and When the heating test under condition II is carried out at 260°C for 2 minutes, the dielectric loss tangent Df1 measured at a frequency of 10 GHz before the heating test and the dielectric loss tangent Df3 measured at a frequency of 10 GHz after the heating test under condition II satisfy equation (3). Df3-Df1≤0.004···(3)

[13] The dielectric loss tangent Df1 of the hollow resin particles described in

[12] above may not reach 0.002.

[14] The hollow resin particles described in any of [1] to

[13] above can be used in resin compositions for semiconductor components.

[15] The resin composition for semiconductor components according to embodiments of the present invention comprises hollow resin particles as described in any one of [1] to

[13] above.

[16] In an embodiment of the present invention, the method for manufacturing hollow resin particles involves reacting a composition (A) comprising at least one of the group consisting of a crosslinking monomer (a), a monofunctional monomer (b), and a compound (c) having an ether structure represented by formula (2) in an aqueous medium in the presence of a non-reactive solvent. When the total amount of the above-mentioned crosslinking monomer (a), the above-mentioned monofunctional monomer (b), and the above-mentioned compound (c) is set to 100 parts by weight, the above-mentioned crosslinking monomer (a) is 1 part by weight to 50 parts by weight. [Chemistry 2] [Effects of the Invention]

[0008] According to embodiments of the present invention, a hollow resin particle having a shell and a hollow portion surrounded by the shell, and possessing excellent dielectric properties unaffected by high-temperature environments, can be provided. Furthermore, a method for manufacturing such a hollow resin particle can be provided. Moreover, uses for such a hollow resin particle can be provided. Simple Explanation of the Diagram

[0009] Figures 1(a) to (c) are schematic cross-sectional views illustrating the structure of the hollow section. Figure 2 is a SEM image of the cross-section of particle (1) obtained in Example 1. Figure 3 is a SEM image of the cross-section of particle (2) obtained in Example 2. Figure 4 is a SEM image of the cross-section of particle (3) obtained in Example 3. Figure 5 is a SEM image of the cross-section of particle (4) obtained in Example 4. Figure 6 is a SEM image of the cross-section of particle (5) obtained in Example 5. Figure 7 is a SEM image of the cross-section of the particle (6) obtained in Example 6. Figure 8 is a SEM image of the cross-section of the particle (7) obtained in Example 7. Figure 9 is a SEM image of a cross-section of the particle (C1) obtained in Comparative Example 1. Figure 10 is a SEM image of a cross-section of the particle (C2) obtained in Comparative Example 2. Implementation

[0010] The embodiments of the present invention will be described below, but the present invention is not limited to these embodiments.

[0011] In this specification, when the expression "(meth)acrylic acid" is used, it means "acrylic acid and / or methacrylic acid"; when the expression "(meth)acrylate" is used, it means "acrylate and / or methacrylate"; when the expression "(meth)allyl" is used, it means "allyl and / or methylallyl"; and when the expression "(meth)acryl" is used, it means "acryl and / or methacryl".

[0012] ≪≪1. Hollow Resin Particles≫≫ ≪1-1. Structure and Properties of Hollow Resin Particles≫ In an embodiment of the present invention, the hollow resin particles are hollow resin particles having a shell portion and a hollow portion surrounded by the shell portion. In an embodiment of the present invention, when the hollow resin particles are subjected to a heating test at 180°C and 1 hour under condition I, the dielectric loss tangent Df1 at a measurement frequency of 10 GHz before the heating test and the dielectric loss tangent Df2 at a measurement frequency of 10 GHz after the heating test under condition I satisfy the following formula (1). Df2-Df1≤0.004···(1)

[0013] The term "hollow" as used here refers to a state in which the interior is filled with substances other than resin, such as gas or liquid, which can further demonstrate the effects of the present invention. It is more preferably meant to refer to a state filled with gas.

[0014] The hollow portion may contain one hollow region, or it may contain multiple hollow regions or a porous structure. Preferably, the hollow portion contains a porous structure. Figure 1(a) is a schematic cross-sectional view of a hollow resin particle containing one hollow region. Figure 1(b) is a schematic cross-sectional view of a hollow resin particle containing multiple hollow regions. Figure 1(c) is a schematic cross-sectional view of a hollow resin particle containing a porous structure. When the hollow portion contains multiple hollow regions, as shown in Figure 1(b), the hollow portion has multiple independent pores. When the hollow portion is a porous structure, the hollow portion has interconnected pores like a three-dimensional mesh structure. When the hollow portion is a porous structure, for example, there may be a case where the hollow portion contains one hollow region (connected pore) and a mixed form containing multiple independent pores and one or more interconnected pores.

[0015] In the embodiment of the present invention, the dielectric loss tangent Df1 before the heating test and the dielectric loss tangent Df2 after the heating test under condition I satisfy the relationship of the above equation (1). Since the difference between Df2 and Df1 is sufficiently small, the increase in dielectric loss tangent caused by exposure to high temperatures is suppressed. Based on the above configuration, the deterioration of dielectric properties caused by high-temperature environments is reduced, and hollow resin particles with excellent dielectric properties unaffected by high-temperature environments can be realized. Therefore, resin compositions using hollow resin particles according to the embodiments of the present invention can exhibit excellent dielectric properties unaffected by high-temperature environments. Examples of excellent dielectric properties include, for example, low dielectric constant and low dielectric loss tangent.

[0016] The dielectric loss tangent Df1 before the heating test is preferably less than 0.002. Therefore, the hollow resin particles in the embodiments of the present invention possess further superior dielectric properties.

[0017] The lower limit of the difference between Df2 and Df1 represented by Df2-Df1 is, for example, -0.01 or more, preferably 0 or more. The difference between Df2 and Df1 is preferably 0.003 or less, more preferably 0.002 or less, further preferably 0.001 or less, and even more preferably 0.0005 or less.

[0018] In the embodiments of the present invention, when the hollow resin particles are subjected to a heating test under condition II at 260°C for 2 minutes, it is preferable that the dielectric loss tangent Df1 and the dielectric loss tangent Df3 at the measurement frequency of 10 GHz after the heating test under condition II satisfy the following formula (3). Df3-Df1≤0.004···(3)

[0019] Another aspect of the present invention provides hollow resin particles. It consists of a shell and hollow resin particles surrounded by the shell. When the heating test under condition II is performed, the dielectric loss tangent Df1 at the measurement frequency of 10 GHz before the heating test and the dielectric loss tangent Df3 at the measurement frequency of 10 GHz after the heating test under condition II satisfy equation (3).

[0020] These hollow resin particles suppress the increase in dielectric loss tangent even at higher temperatures. Based on the above configuration, hollow resin particles with excellent dielectric properties unaffected by high-temperature environments can be achieved. Therefore, resin compositions using the hollow resin particles of the embodiments of the present invention can exhibit excellent dielectric properties unaffected by high-temperature environments.

[0021] In this specification, "(before the heating test) dielectric loss tangent Df1" refers to the dielectric loss tangent of the hollow resin particles in their initial state before the heating test, neither under condition I nor under condition II. Therefore, equation (1) above represents the relationship between the change in dielectric loss tangent of the hollow resin particles caused by the heating test under condition I and the initial value, and equation (3) above represents the relationship between the change in dielectric loss tangent of the hollow resin particles caused by the heating test under condition II and the initial value. The dielectric loss tangent Df1 is preferably less than 0.002, and more preferably less than 0.0017.

[0022] The lower limit of the difference between Df3 and Df1 represented by Df3-Df1 is, for example, 0 or more. The difference between Df3 and Df1 is preferably 0.0035 or less, more preferably 0.003 or less, further preferably 0.0025 or less, and even more preferably 0.002 or less.

[0023] In embodiments of the present invention, the volume average particle size of the hollow resin particles is preferably 0.1 μm to 100 μm, more preferably 0.2 μm to 50.0 μm, further preferably 0.3 μm to 30.0 μm, and even more preferably 0.4 μm to 20.0 μm. In embodiments of the present invention, the volume average particle size of the hollow resin particles can be 0.1 μm to 30 μm. If the volume average particle size of the hollow resin particles in embodiments of the present invention is within the above range, the effects of the present invention can be further demonstrated. When the volume average particle size of the hollow resin particles in embodiments of the present invention is too small and deviates from the above range, the shell thickness becomes relatively thin, thus there is a risk that the hollow resin particles will not have sufficient strength. Furthermore, when the hollow resin particles are mixed with a thermosetting resin, there is a risk that the thermosetting resin may enter the interior of the hollow resin particles. In embodiments of the present invention, when the volume average particle size of the hollow resin particles is too large and deviates from the above range, there is a risk that the polymer generated by the polymerization of monomer components in suspension polymerization may not be able to separate from the solvent, thereby making it difficult to form a shell.

[0024] In embodiments of the present invention, the coefficient of variation (CV) of the particle size of the hollow resin particles is preferably 10% to 50%, more preferably 15% to 45%, further preferably 18% to 42%, and even more preferably 20% to 40%. If the coefficient of variation (CV) of the particle size of the hollow resin particles in embodiments of the present invention is within the above range, the effects of the present invention can be further demonstrated. When the coefficient of variation (CV) of the particle size of the hollow resin particles in embodiments of the present invention is too small and deviates from the above range, when the hollow resin particles are mixed with a thermosetting resin to form a resin composition, the hollow resin particles are not easily dispersed within the thermosetting resin. For example, when a resin layer is formed from the resin composition, there is a risk of uneven thickness. When the coefficient of variation (CV) of the particle size of the hollow resin particles in embodiments of the present invention is too large and deviates from the above range, due to the increase in the amount of coarse particles, for example, when a resin layer is formed from the resin composition, there is a risk of film formation difficulties or uneven thickness.

[0025] In embodiments of the present invention, the 5% heat weight reduction temperature of the hollow resin particles when heated at a rate of 10°C / min in a nitrogen atmosphere is preferably 300°C or higher, more preferably 320°C or higher, further preferably 340°C or higher, and even more preferably 360°C or higher. The upper limit of this 5% heat weight reduction temperature in a nitrogen atmosphere is actually preferably below 500°C. If the 5% heat weight reduction temperature of the hollow resin particles in embodiments of the present invention when heated at a rate of 10°C / min in a nitrogen atmosphere is within the above-mentioned range, then the hollow resin particles in embodiments of the present invention exhibit excellent heat resistance. In embodiments of the present invention, when the 5% heat weight reduction temperature of hollow resin particles heated at 10°C / min in a nitrogen atmosphere is too small and deviates from the above range, for example, when hollow resin particles are mixed with thermosetting resin to form a resin composition, the particles are deformed and lose the hollow portion due to the heating used for the curing reaction. Therefore, there is a risk that the dielectric properties that the hollow resin particles should exhibit in the resin composition, such as the effect of low dielectric constant and low dielectric loss tangent, will be reduced.

[0026] In embodiments of the present invention, the 5% heat weight reduction temperature of the hollow resin particles when heated at 10°C / min in air is preferably 270°C or higher, more preferably 280°C or higher, further preferably 290°C or higher, and even more preferably 300°C or higher. The upper limit of this 5% heat weight reduction temperature in air is preferably below 500°C. If the 5% heat weight reduction temperature of the hollow resin particles in embodiments of the present invention is within the above range when heated at 10°C / min in air, the hollow resin particles in embodiments of the present invention exhibit excellent heat resistance. In embodiments of the present invention, when the 5% heat weight reduction temperature of hollow resin particles heated at 10°C / min in an air atmosphere is too small and deviates from the above range, for example, when hollow resin particles are mixed with thermosetting resin, the particles are deformed and lose the hollow part due to the heating used for the curing reaction. Therefore, there is a risk that the dielectric properties that the hollow resin particles should exhibit in the resin composition, such as the effect of low dielectric constant and low dielectric loss tangent, will be reduced.

[0027] ≪1-2. Shell≫ The shell comprises a polymer (P), which is obtained, for example, by reacting a composition (A) comprising at least one of a group consisting of a crosslinking monomer (a) and a compound (c) having an ether structure represented by the following formula (2). The reaction is, for example, a polymerization reaction. The polymer (P) is preferably obtained by polymerizing a monomer component (M) comprising a crosslinking monomer (a) and a monofunctional monomer (b), or by polymerizing a monomer component (M) and a compound (c). By comprising a polymer (P) having this structure in the shell, the effects of the present invention can be further demonstrated. [Chemistry 3]

[0028] The polymer (P) can be a single type or two or more types.

[0029] Regarding the content ratio of polymer (P) in the shell, which can further demonstrate the effects of the present invention, it is preferably 60% to 100% by weight, more preferably 70% to 100% by weight, even more preferably 80% to 100% by weight, and even more preferably 90% to 100% by weight.

[0030] The shell portion may contain any suitable other components without impairing the effects of the present invention. For example, the shell portion may contain a hydrocarbon resin (B). The hydrocarbon resin (B) may be only one type or may be two or more types. By including a hydrocarbon resin (B) in the shell portion, it is easy to construct a particle structure having a shell portion and a hollow portion surrounded by the shell portion. Furthermore, by including a hydrocarbon resin (B) in the shell portion, the effects of the present invention can be further manifested. The shell portion may contain 0 to 10 parts by weight of hydrocarbon resin (B) relative to 100 parts by weight of the total amount of polymer (P) and hydrocarbon resin (B). In terms of further manifesting the effects of the present invention, the ratio of hydrocarbon resin (B) relative to 100 parts by weight of the total amount of polymer (P) and hydrocarbon resin (B) is preferably 1 to 10 parts by weight, more preferably 1 to 8 parts by weight, further preferably 2 to 8 parts by weight, particularly preferably 2 to 6 parts by weight, and most preferably 2 to 5 parts by weight. Alternatively, the hydrocarbon resin (B) may be 1 to 5 parts by weight. If the ratio of the hydrocarbon resin (B) is within the above range, the effects of the present invention can be further demonstrated. This allows for the creation of hollow resin particles with excellent dielectric properties unaffected by temperature conditions and high heat resistance.

[0031] The shell may also not contain hydrocarbon resin (B).

[0032] Regarding the ratio of the total amount of polymer (P) and hydrocarbon resin (B) in the shell, which can further demonstrate the effect of the present invention, it is preferably 60% to 100% by weight, more preferably 70% to 100% by weight, even more preferably 80% to 100% by weight, even more preferably 90% to 100% by weight, particularly preferably 95% to 100% by weight, and most preferably 98% to 100% by weight.

[0033] As the hydrocarbon resin (B), any suitable compound may be used without impairing the effects of the present invention. Examples of hydrocarbon resins (B) include: aliphatic / aromatic hydrocarbon resins, aromatic hydrocarbon resins, alicyclic hydrocarbon resins, and aliphatic hydrocarbon resins. The hydrocarbon resin (B) is preferably selected from at least one of the group consisting of aliphatic / aromatic hydrocarbon resins, aromatic hydrocarbon resins, and aliphatic hydrocarbon resins, more preferably from at least one of the group consisting of aliphatic / aromatic hydrocarbon resins and aromatic hydrocarbon resins, and even more preferably from an aliphatic / aromatic hydrocarbon resin. Based on the above, hollow resin particles with excellent dielectric properties unaffected by temperature environments can be realized, and furthermore, hollow resin particles with excellent heat resistance can be realized. Therefore, when a resin composition is prepared by mixing hollow resin particles with a thermosetting resin or other resin, even if the thermosetting resin containing the hollow resin particles is heated during molding or soldering, substantial changes are unlikely to occur in the hollow resin particles. Thus, the resin composition can further exhibit the desired dielectric properties. These hydrocarbon resins can be used alone or in combination of two or more.

[0034] Aliphatic / aromatic hydrocarbon resins refer to hydrocarbon resins obtained by copolymerizing aliphatic and aromatic hydrocarbons. Examples of aliphatic / aromatic hydrocarbon resins include resins obtained by polymerizing styrene, vinyltoluene, indene, and 1,3-pentadiene as main raw materials.

[0035] Aromatic hydrocarbon resins are resins obtained by polymerizing styrene, vinyltoluene, indene, etc., as main raw materials.

[0036] Alicyclic hydrocarbon resins are, for example, resins obtained by hydrogenating aliphatic / aromatic hydrocarbon resins or aromatic hydrocarbon resins.

[0037] Aliphatic hydrocarbon resins are hydrocarbon resins formed by polymerizing one or more aliphatic hydrocarbons with polymerizable unsaturated bonds.

[0038] The polymer (P) is obtained, for example, by polymerizing a composition (A) comprising at least one of the group consisting of a crosslinking monomer (a) and a compound (c) selected from a monofunctional monomer (b) and having an ether structure represented by formula (2). That is, the polymer (P) has a structural unit derived from a crosslinking monomer and at least one of the group consisting of a structural unit derived from a monofunctional monomer and an ether structure represented by formula (2).

[0039] The polymer (P) is preferably a polymer obtained by polymerizing a monomer component (M) comprising a crosslinking monomer (a) and a monofunctional monomer (b), or a polymer obtained by polymerizing the monomer component (M) with the aforementioned compound (c).

[0040] Examples of crosslinking monomers (a) include: polyfunctional (meth)acrylates such as ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and glycerol tri(meth)acrylate; polyfunctional acrylamide derivatives such as N,N'-methylenebis(meth)acrylamide and N,N'-ethyl bis(meth)acrylamide; polyfunctional allyl derivatives such as diallylamine and tetraallyloxyethane; and aromatic crosslinking monomers such as divinylbenzene, divinylnaphthalene, diallyl phthalate, and divinylbiphenyl. In terms of further demonstrating the effects of the present invention, the crosslinking monomer (a) is preferably an aromatic crosslinking monomer, and more preferably divinylbenzene. The crosslinking monomer (a) may be only one type or may be two or more types.

[0041] When composition (A) contains an aromatic crosslinking monomer, and the total amount of the crosslinking monomer (a), monofunctional monomer (b), and compound (c) is set to 100 parts by weight, the aromatic crosslinking monomer is preferably 1 to 50 parts by weight, more preferably 1 to 40 parts by weight, further preferably 1 to 35 parts by weight, even more preferably 1 to 30 parts by weight, and most preferably 1 to 26 parts by weight. Furthermore, the aromatic crosslinking monomer is preferably 3 to 50 parts by weight, more preferably 5 to 50 parts by weight, even more preferably 8 to 40 parts by weight, even more preferably 10 to 40 parts by weight, and most preferably 10 to 35 parts by weight. This allows for the creation of hollow resin particles with excellent dielectric properties unaffected by high-temperature environments. If the content ratio of the aromatic crosslinking monomer is too high and deviates from the above range, the dielectric properties of the hollow resin particles may deteriorate. If the content ratio of aromatic crosslinking monomers is too low and deviates from the above range, there is a risk that the particles will agglomerate during the manufacturing process and hollow resin particles cannot be fully obtained.

[0042] Examples of monofunctional monomers (b) include: alkyl methacrylates with 1 to 16 carbon atoms, such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, and cetyl methacrylate; aromatic monofunctional monomers such as styrene, α-methylstyrene, ethylvinylbenzene, vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, vinylbiphenyl, and vinylnaphthalene; dicarboxylic acid ester monomers such as dimethyl maleate, diethyl fumarate, and diethyl fumarate; maleic anhydride; N-vinylcarbazole; and (meth)acrylonitrile. In terms of further demonstrating the effects of the present invention, aromatic monofunctional monomers are preferred as monofunctional monomers (b). The monofunctional monomer (b) is preferably selected from at least one of the group consisting of styrene, α-methylstyrene, ethylvinylbenzene, vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, vinylbiphenyl, vinylnaphthalene, and vinylnaphthalene, and more preferably styrene or ethylvinylbenzene. The monofunctional monomer (b) may be only one type or may be two or more types.

[0043] When composition (A) contains an aromatic monofunctional monomer, and the total amount of the crosslinking monomer (a), the monofunctional monomer (b), and the compound (c) is set to 100 parts by weight, the aromatic monofunctional monomer is preferably 10 to 99 parts by weight, more preferably 20 to 99 parts by weight, further preferably 30 to 99 parts by weight, and even more preferably 40 to 99 parts by weight. Furthermore, the aromatic monofunctional monomer is preferably 20 to 95 parts by weight, more preferably 25 to 90 parts by weight, further preferably 30 to 90 parts by weight, even more preferably 35 to 85 parts by weight, and most preferably 40 to 85 parts by weight. This allows for the creation of hollow resin particles with excellent dielectric properties unaffected by high-temperature environments.

[0044] The combined content ratio of the crosslinking monomer (a) and the monofunctional monomer (b) in the monomer component (M) is, for example, 50% to 100% by weight, which can further enhance the effects of the present invention. It is more preferably 60% to 100% by weight, more preferably 70% to 100% by weight, even more preferably 80% to 100% by weight, particularly preferably 90% to 100% by weight, and most preferably 95% to 100% by weight.

[0045] In terms of the effectiveness of the invention, relative to the total amount of 100 parts by weight of crosslinking monomer (a) and monofunctional monomer (b), the content ratio of crosslinking monomer (a) is preferably 5 parts by weight to 85 parts by weight, more preferably 10 parts by weight to 70 parts by weight, further preferably 15 parts by weight to 60 parts by weight, further preferably 15 parts by weight to 50 parts by weight, even more preferably 20 parts by weight to 45 parts by weight, and most preferably 20 parts by weight to 40 parts by weight.

[0046] In terms of the effectiveness of the invention, relative to the total amount of 100 parts by weight of the crosslinking monomer (a) and the monofunctional monomer (b), the content ratio of the monofunctional monomer (b) is preferably 15 parts by weight to 95 parts by weight, more preferably 30 parts by weight to 90 parts by weight, further preferably 40 parts by weight to 85 parts by weight, further preferably 50 parts by weight to 85 parts by weight, even more preferably 55 parts by weight to 80 parts by weight, and most preferably 60 parts by weight to 80 parts by weight.

[0047] In addition to cross-linking monomers (a) and monofunctional monomers (b), the monomer component (M) may also contain other monomers (m). There may be only one other monomer (m) or more than two.

[0048] As other monomers (m), any suitable monomer may be used without impairing the effects of the present invention. Such other monomers (m) may, for example, be compounds having at least one of the group consisting of phosphate ester structures and free radical reactive groups, preferably compounds having phosphate ester structures and free radical reactive groups. In terms of further demonstrating the effects of the present invention, such compounds having at least one of the group consisting of phosphate ester structures and free radical reactive groups are preferably compounds represented by formula (4). [Chemistry 4]

[0049] In formula (4), R1 and R3 are straight-chain or branched alkyl groups with 1 to 30 carbon atoms, and R2 represents a methyl or hydrogen atom. In formula (4), m represents 1 to 300. In formula (4), n represents 1 to 3. In formula (4), a is 0 or 1, b is 0 to 300, and c is 0 or 1.

[0050] In formula (4), R1 is preferably a straight-chain or branched alkyl group having 1 to 20 carbon atoms, more preferably a straight-chain or branched alkyl group having 1 to 10 carbon atoms, further preferably a straight-chain or branched alkyl group having 1 to 8 carbon atoms, especially preferably a straight-chain or branched alkyl group having 1 to 6 carbon atoms, and most preferably a straight-chain or branched alkyl group having 1 to 4 carbon atoms.

[0051] In formula (4), R3 is preferably a straight-chain or branched alkyl group having 1 to 20 carbon atoms, more preferably a straight-chain or branched alkyl group having 1 to 10 carbon atoms, further preferably a straight-chain or branched alkyl group having 1 to 8 carbon atoms, especially preferably a straight-chain or branched alkyl group having 1 to 6 carbon atoms, and most preferably a straight-chain or branched alkyl group having 1 to 4 carbon atoms.

[0052] In formula (4), m is preferably 1~100, more preferably 1~50, even more preferably 1~40, and even more preferably 1~30.

[0053] In equation (4), b is preferably 0~100, more preferably 0~50, even more preferably 0~10, especially preferably 0~5, and most preferably 0 or 1.

[0054] As for such compounds having at least one of the group consisting of a phosphate ester structure and a free radical reactive group, those that are commercially available can be used. For example, from the point of view of compatibility, an example of such compounds is the trade name "KAYAMER (registered trademark) PM-21" (manufactured by Nippon Kayaku Co., Ltd.).

[0055] Regarding the proportion of at least one compound selected from the group consisting of phosphate ester structures and free radical reactive groups in the monomer component (M) to further demonstrate the effects of the present invention, it is preferably 0% to 10% by weight, more preferably 0.01% to 5% by weight, even more preferably 0.05% to 3% by weight, and even more preferably 0.1% to 1% by weight.

[0056] As compound (c), any suitable compound may be used as long as it has the ether structure and free radical reactive group represented by formula (2) above, without impairing the effects of the present invention. In terms of further demonstrating the effects of the present invention, polyphenylene ether is preferably exemplified as such compound (c). Polyphenylene ether is a reactive polyphenylene ether that reacts with the monomer component (M) using a polymerization initiator, and typically, it is a modified polyphenylene ether having a polymerizable double bond at at least one end. The modified polyphenylene ether preferably has polymerizable double bonds at both ends, and more preferably is a low molecular weight modified oligomer with difunctional groups based on polyphenylene ether. Here, "having difunctional groups" means having a functional group with a double bond, or having a functional group with a substituent having a double bond located at both ends of the oligomer. In terms of making it easier to produce hollow resin particles with excellent heat resistance, the number average molecular weight Mn of the above-mentioned oligomer is preferably 500 to 3500.

[0057] As a better example of such modified polyphenylene ether, the compound represented by the following formula (5) can be cited. [Chemistry 5]

[0058] In formula (5), n1 and n2 are integers from 0 to 300, with at least one of them being an integer greater than or equal to 1. L3 represents a divalent linkage. L3 is preferably selected from the group consisting of alkylene, alkenylene, -O-, -CO-, -CS-, -SO-, and -SO2-, more preferably alkylene, and even more preferably isopropylidene (-C(CH3)2-). Commercially available products representing the compound in formula (5) can be exemplified by, for example, the "Noryl (registered trademark)" series (Noryl (registered trademark) SA9000, etc.) (manufactured by SABIC). As shown above, the modified polyphenylene ether preferably has (meth)acrylic groups at both ends. That is, compound (c) can be a polyphenylene ether having (meth)acrylic groups at both ends.

[0059] As another preferred example of modified polyphenylene ether, the compound represented by the following formula (6) can be cited. [Chemistry 6]

[0060] In equation (6), n1 and n2 are integers from 0 to 300, provided that at least one of them is an integer greater than or equal to 1. Commercially available products representing the compounds represented by equation (6) can be exemplified by, for example, the "OPE-2St" series (manufactured by Mitsubishi Gas Chemical Co., Ltd.).

[0061] Other commercially available products of polyphenylene ether include, for example, the "Lupiace" series (manufactured by Mitsubishi Chemical Corporation) and the "Zylon" series (manufactured by Asahi Kasei Corporation).

[0062] The reaction of composition (A) can be carried out by any suitable reaction without impairing the effects of the present invention. Such a reaction is, for example, suspension polymerization.

[0063] In suspension polymerization, typically, an oil phase is added to an aqueous phase, and the polymerization reaction is carried out in suspension. Any suitable solvent may be included in the aqueous or oil phase without impairing the effects of the invention. Examples of such solvents include, for instance, aqueous media or non-reactive solvents as described below. There may be only one solvent, or there may be two or more.

[0064] The reaction of composition (A) can be carried out in the presence of hydrocarbon resin (B). For example, hydrocarbon resin (B) can be used when carrying out the polymerization reaction of composition (A) containing crosslinking monomer (a) and monofunctional monomer (b). Hydrocarbon resin (B) is as described above.

[0065] When reacting the composition (A), any suitable additive (C) that is not a crosslinking monomer (a), monofunctional monomer (b), compound (c), or hydrocarbon resin (B) may be used, without impairing the effects of the present invention. Additive (C) may be only one type or may be two or more types. The additive (C) referred to herein does not include solvents or dispersants such as aqueous media or non-reactive solvents as described below.

[0066] The content ratio of additive (C) relative to the total amount of crosslinking monomer (a), monofunctional monomer (b) and compound (c) is preferably 0% to 40% by weight, more preferably 0% to 30% by weight, further preferably 0% to 20% by weight, and even more preferably 0% to 10% by weight.

[0067] Examples of additives (C) include: non-crosslinked polymers, polymerization initiators, surfactants, and chain transfer agents.

[0068] By including a non-crosslinked polymer as an additive (C), the phase separation of the polymer (P) generated during the reaction and the solvent can be promoted, thereby promoting shell formation.

[0069] Examples of non-crosslinked polymers include at least one selected from the group consisting of polyolefins, styrene-based polymers, (meth)acrylic polymers, and styrene-(meth)acrylic polymers.

[0070] Examples of polyolefins include polyethylene, polypropylene, and polyalphaolefins. From the viewpoint of the solubility of the monomer component (M) and the compound (c), it is preferable to use long-chain alpha-olefin side-chain crystalline polyolefins, low molecular weight polyolefins or olefin oligomers manufactured by metallocene catalysts in the raw materials.

[0071] Examples of styrene-based polymers include polystyrene, styrene-acrylonitrile copolymers, and acrylonitrile-butadiene-styrene copolymers.

[0072] Examples of (meth)acrylic polymers include: poly(meth)acrylate, poly(meth)acrylate, poly(meth)acrylate, poly(meth)acrylate, poly(meth)acrylate, poly(meth)acrylate, etc.

[0073] Examples of styrene-(meth)acrylate polymers include: styrene-(meth)acrylate methyl acrylate copolymers, styrene-(meth)acrylate ethyl acrylate copolymers, styrene-(meth)acrylate butyl acrylate copolymers, and styrene-(meth)acrylate propyl acrylate copolymers.

[0074] From the viewpoint that the desired hollow resin particles can be produced more stably in suspension polymerization, a surfactant can be used as an additive (C). As a surfactant, in order to further demonstrate the effects of the present invention, it is preferable to select at least one of an amphoteric surfactant and an anionic surfactant, more preferably at least an amphoteric surfactant. Specifically, it is preferable to add at least one of an amphoteric surfactant and an anionic surfactant to the aqueous phase containing the aqueous medium, more preferably to add at least one amphoteric surfactant to the aqueous phase containing the aqueous medium (adding only an amphoteric surfactant, or adding both an amphoteric surfactant and an anionic surfactant).

[0075] As an amphoteric surfactant, any suitable amphoteric surfactant may be used without impairing the effects of the present invention. Such amphoteric surfactant may be a known amphoteric surfactant used in the manufacture of resin particles. Examples of amphoteric surfactants include: lauryl dimethylamine oxide, lauryl dimethylaminoacetic acid betaine, phosphate ester surfactants, and phosphite ester surfactants. There may be only one amphoteric surfactant or two or more.

[0076] As an anionic surfactant, any suitable anionic surfactant may be used without impairing the effects of the present invention. Examples of such anionic surfactants include: fatty acid salts, polysulfonates, polycarboxylate salts, alkyl sulfate salts, alkyl aryl sulfonates, alkyl naphthalene sulfonates, dialkyl sulfonates, dialkyl sulfosuccinates, alkyl phosphates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl aryl ether sulfates, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate sulfonate, glyceryl borate fatty acid esters, and polyoxyethylene glycerol fatty acid esters. Specifically, examples include: sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, ammonium polyoxyethylene lauryl ether sulfate, polyoxyethylene nonylphenyl ether sulfate salt, and sodium salts of β-naphthalene sulfonic acid formalin condensate. The anionic surfactant may be only one type or two or more types.

[0077] The amount of surfactant used relative to 100 parts by weight of aqueous medium is preferably in the range of 0.01 parts by weight to 0.3 parts by weight, and more preferably in the range of 0.02 parts by weight to 0.2 parts by weight.

[0078] Examples of chain transfer agents include: thiols, styrene dimers, terpenes, halogenated hydrocarbons, and α-methylstyrene. Examples of thiols include n-octanethiol, n-dodecanethiol, tridecanethiol, 2-hydroxyethylthiol, n-octadecylthiol (stearylthiol), alkyl dithiol, and trithiocyanate, with n-octanethiol and n-dodecanethiol being preferred. Examples of styrene dimers include α-methylstyrene dimers. Examples of terpenes include γ-terpinene and dipentene. Examples of halogenated hydrocarbons include halogenated hydrocarbons. Among these chain transfer agents, thiols, α-methylstyrene, and styrene dimers are preferred, more preferably thiols and α-methylstyrene, and even more preferably thiols. These chain transfer agents can be used alone or in combination of two or more.

[0079] Regarding the amount of chain transfer agent used, when the total amount of crosslinking monomer (a), monofunctional monomer (b), and compound (c) is set to 100 parts by weight, it is preferably 0.1 parts by weight to 10 parts by weight, more preferably 0.1 parts by weight to 5 parts by weight, further preferably 0.1 parts by weight to 3 parts by weight, and even more preferably 0.1 parts by weight to 1 part by weight.

[0080] When reacting the composition (A), any suitable dispersant (D) that is not a crosslinking monomer (a), a monofunctional monomer (b), a compound (c), or a hydrocarbon resin (B) may be used, without impairing the effects of the present invention. The dispersant (D) may be only one type or may be two or more types.

[0081] The dispersion stabilizer (D) is preferably 0.5 to 10 parts by weight relative to 100 parts by weight of the aqueous medium. The dispersion stabilizer (D) may be a single type or two or more types.

[0082] Examples of dispersing stabilizers (D) include: polyvinyl alcohol, polycarboxylic acids, cellulose derivatives (hydroxyethyl cellulose, carboxymethyl cellulose, etc.), polyvinylpyrrolidone, sodium tripolyphosphate, and other inorganic water-soluble polymers. Examples of dispersing stabilizers also include: phosphates such as calcium phosphate, magnesium phosphate, aluminum phosphate, and zinc phosphate; pyrophosphates such as calcium pyrophosphate, magnesium pyrophosphate, aluminum pyrophosphate, and zinc pyrophosphate; and water-insoluble inorganic compounds such as calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilate, calcium sulfate, barium sulfate, and colloidal silica. Among these, magnesium pyrophosphate is preferred in terms of being relatively easy to remove from hollow resin particles and not easily remaining on the surface of hollow resin particles.

[0083] ≪1-3. Relative permittivity and dielectric loss tangent of hollow resin particles≫ In electronic devices, where hollow resin particles are used for communication, the transmission loss of radio waves transmitted through the dielectric material due to thermal conversion is expressed as the product of the square root of the frequency and the dielectric loss tangent. In other words, the transmitted signal is easily converted into heat proportional to the frequency. Therefore, in order to suppress transmission loss, the higher the frequency band, the lower the dielectric properties required for the materials of communication components (semiconductor components).

[0084] In this embodiment of the invention, the relative permittivity of the hollow resin particles at a measurement frequency of 10 GHz is preferably 1.0 to 2.5, more preferably 1.0 to 2.3, further preferably 1.0 to 2.0, and even more preferably 1.0 to 1.5. Here, in this specification, when simply referred to as "relative permittivity of the hollow resin particles," it means the relative permittivity of the hollow resin particles before the heating test. The relative permittivity before the heating test is the relative permittivity of the hollow resin particles (i.e., the hollow resin particles in their initial state) under the condition of measuring the dielectric loss tangent Df1.

[0085] In embodiments of the present invention, the dielectric loss tangent of the hollow resin particles at a measurement frequency of 10 GHz is preferably 0~0.0016, more preferably 0~0.0015, further preferably 0~0.0014, and even more preferably 0~0.0013. Here, in this specification, when simply referred to as "dielectric loss tangent of hollow resin particles," it means the dielectric loss tangent Df1 of the hollow resin particles before the heating test. If the relative permittivity and dielectric loss tangent of the hollow resin particles in embodiments of the present invention are within the above ranges, the effects of the present invention can be further demonstrated.

[0086] In embodiments of the present invention, the hollow resin particles preferably have a relative permittivity of less than 2.0 and a dielectric loss tangent of less than 0.0017 at a measurement frequency of 10 GHz, and more preferably have a relative permittivity of less than 1.5 and a dielectric loss tangent of less than 0.0017 at a measurement frequency of 10 GHz.

[0087] In embodiments of the present invention, when the relative permittivity of the hollow resin particles exceeds 2.0, even if the hollow resin particles are mixed in, for example, a thermosetting resin, a sufficiently low permittivity effect cannot be obtained. This can lead to transmission losses and increased heat generation in the component when used in high-frequency bands. The aforementioned adverse effects are more likely to occur when the relative permittivity of the hollow resin particles exceeds 2.5.

[0088] In the embodiments of the present invention, the relative permittivity of hollow resin particles after heating at 180°C and for 1 hour under condition I is preferably 1.0 to 2.5, more preferably 1.0 to 2.3, further preferably 1.0 to 2.0, and even more preferably 1.0 to 1.5 at a measurement frequency of 10 GHz.

[0089] In embodiments of the present invention, the dielectric loss tangent Df2 of the hollow resin particles after the heating test under condition I described above, at a measurement frequency of 10 GHz, is preferably 0~0.005, more preferably 0~0.004, further preferably 0~0.003, and even more preferably 0~0.002. If the relative permittivity and dielectric loss tangent of the hollow resin particles after the heating test under condition I described above are within the above ranges, the effects of the present invention can be further demonstrated.

[0090] In embodiments of the present invention, the relative permittivity of hollow resin particles after heating at 260°C for 10 minutes under condition II is preferably 1.0 to 2.5, more preferably 1.0 to 2.3, and even more preferably 1.0 to 2.0 at a measurement frequency of 10 GHz.

[0091] In embodiments of the present invention, the dielectric loss tangent Df3 of the hollow resin particles after the heating test under condition II described above, at a measurement frequency of 10 GHz, is preferably 0 to 0.010, more preferably 0 to 0.006, further preferably 0 to 0.005, and even more preferably 0 to 0.004. If the relative permittivity and dielectric loss tangent of the hollow resin particles after the heating test under condition II described above in embodiments of the present invention are within the above ranges, the effects of the present invention can be further demonstrated.

[0092] The relative permittivity and dielectric loss tangent of the hollow resin particles in the embodiments of the present invention are not limited to the values ​​described above. For example, when the hollow resin particles in the embodiments of the present invention are used for purposes other than semiconductor components, the values ​​of the relative permittivity and dielectric loss tangent are not limited to the values ​​described above.

[0093] ≪1-4. Applications of Hollow Resin Particles≫ The hollow resin particles in the embodiments of the present invention can be used for various applications. In terms of making more effective use of the effects of the present invention, the hollow resin particles in the embodiments of the present invention are suitable for semiconductor components, and representatively, can be suitably used in resin compositions for semiconductor components. Furthermore, in addition to the above-mentioned use in resin compositions for semiconductor components, the hollow resin particles in the embodiments of the present invention can also be used, for example, in coating compositions, cosmetics, paper coating compositions, heat-insulating resin compositions, light-diffusing resin compositions, light-diffusing films, and other applications.

[0094] <Resin Compositions for Semiconductor Components> The hollow resin particles in the embodiments of the present invention can achieve low dielectric constant and low dielectric loss tangent, and exhibit excellent heat resistance, thus making them suitable for use in resin compositions for semiconductor components.

[0095] The resin composition for semiconductor components according to embodiments of the present invention comprises hollow resin particles according to embodiments of the present invention.

[0096] Semiconductor components refer to components that constitute semiconductors, such as semiconductor packages or semiconductor modules. In this specification, resin compositions for semiconductor components refer to resin compositions used in semiconductor components.

[0097] Semiconductor packaging refers to the use of IC chips as essential components, and the use of at least one component selected from molding resin, underfill material, molding underfill material, die bond material, prepreg for semiconductor packaging substrate, metal foil laminate for semiconductor packaging substrate, and printed circuit board for semiconductor packaging.

[0098] A semiconductor module is defined as a component that incorporates semiconductor packaging as an essential element, and is constructed using at least one of the following components: prepreg for printed circuit boards, metal foil laminate for printed circuit boards, additive material for printed circuit boards, solder resist, cover film, electromagnetic wave shielding film, and bonding sheet for printed circuit boards.

[0099] <Coating Composition> The hollow resin particles in the embodiments of the present invention can impart an excellent appearance to the coating film containing them, and are therefore suitable for use in coating compositions.

[0100] The coating composition of the embodiments of the present invention comprises hollow resin particles of the embodiments of the present invention.

[0101] The coating composition of the embodiments of the present invention preferably comprises at least one selected from adhesive resins and UV-curing resins. The adhesive resin may be only one type or may be two or more types. The UV-curing resin may be only one type or may be two or more types.

[0102] As the adhesive resin, any suitable adhesive resin may be used without impairing the effects of the present invention. Examples of such adhesive resins include: resins soluble in organic solvents or water, and emulsion-type aqueous resins that can be dispersed in water. Specifically, examples of adhesive resins include: acrylic resins, alkyd resins, polyester resins, polyurethane resins, chlorinated polyolefin resins, and amorphous polyolefin resins.

[0103] As the UV-curing resin, any suitable UV-curing resin may be used without impairing the effects of the present invention. Examples of such UV-curing resins include: polyfunctional (meth)acrylate resins, polyfunctional aminocarbamate acrylate resins, preferably polyfunctional (meth)acrylate resins, and more preferably polyfunctional (meth)acrylate resins having three or more (meth)acrylic groups in one molecule. As a polyfunctional (meth)acrylate resin having three or more (meth)acrylic groups in one molecule, examples include: trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, 1,2,4-cyclohexane tetra(meth)acrylate, pentaglycerol triacrylate, neopentyltetra(meth)acrylate, neopentyltetra(meth)acrylate, dinepentyltetra(meth)acrylate, dinepentyltetra(meth)acrylate, dinepentyltetra(meth)acrylate, dinepentyltetra(meth)acrylate, dinepentyltetra(meth)acrylate, trinepentyltetra(meth)acrylate, and trinepentyltetra(meth)acrylate.

[0104] When the coating composition of an embodiment of the present invention comprises at least one selected from adhesive resins and UV-curing resins, its content ratio can be any suitable ratio depending on the purpose. Typically, relative to the total amount of at least one selected from adhesive resins (converted to solids content in the case of emulsion-type waterborne resins) and UV-curing resins and hollow resin particles in an embodiment of the present invention, the hollow resin particles in an embodiment of the present invention are preferably 5% to 50% by weight, more preferably 10% to 50% by weight, and even more preferably 20% to 40% by weight.

[0105] When using UV-curable resins, it is preferable to use a photopolymerization initiator in conjunction with the resin. As the photopolymerization initiator, any suitable photopolymerization initiator may be used without impairing the effects of the present invention. Examples of such photopolymerization initiators include: acetophenones, benzoin derivatives, benzophenones, phosphine oxides, ketals, α-hydroxyalkyl phenyl ketones, α-aminealkyl phenyl ketones, anthraquinones, and 9-oxosulfuron-methyl. Classes, azo compounds, peroxides (as described in Japanese Patent Application Publication No. 2001-139663, etc.), 2,3-dialkyldione compounds, disulfide compounds, fluorinated amine compounds, aromatic strontium compounds, onium salts, borates, active halogen compounds, and α-acryloyl oxime esters.

[0106] The coating composition of embodiments of the present invention may contain a solvent. The solvent may be only one type, or it may be two or more types. When the coating composition of embodiments of the present invention contains a solvent, the content ratio can be any suitable ratio depending on the purpose.

[0107] As a solvent, any suitable solvent may be used without impairing the effects of the present invention. Preferably, such a solvent is one that can dissolve or disperse the adhesive resin or UV-curable resin. Examples of such solvents for oil-based coatings include: hydrocarbon solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; and ether solvents such as dialkylene, ethylene glycol diethyl ether, and ethylene glycol monobutyl ether. Examples of solvents for water-based coatings include: water and alcohols.

[0108] The coating composition of the embodiments of the present invention can also be diluted to adjust the viscosity as needed. Any suitable diluent can be used as the diluent, depending on the purpose. Examples of such diluents include the solvents described above. There may be only one diluent, or there may be two or more diluents.

[0109] The coating composition of the embodiments of the present invention may contain other components as needed, such as coating conditioner, flow conditioner, ultraviolet absorber, light stabilizer, hardening catalyst, extender pigment, coloring pigment, metallic pigment, mica powder pigment, and dye.

[0110] When forming a coating film using the coating composition of the embodiments of the present invention, any suitable coating method may be adopted as the coating method depending on the purpose. Examples of such coating methods include: spray coating, roller coating, brush coating, reverse roller coating, gravure coating, die coating, corner wheel coating, and spraying.

[0111] When forming a coating film using the coating composition of the embodiments of the present invention, any suitable forming method may be adopted depending on the purpose. For example, such a forming method may be described as follows: a method of forming a coating film by coating any coating surface of a substrate, drying the coating film, and then hardening the coating film as needed to form a coating film. Examples of substrates may include: metal, wood, glass, and plastics (PET (polyethylene terephthalate), PC (polycarbonate), acrylic resin, TAC (triacetal cellulose), etc.).

[0112] <Insulating Resin Composition> The hollow resin particles in the embodiments of the present invention can impart excellent thermal insulation properties to the coatings containing them, and are therefore suitable for use in thermal insulation resin compositions. Coatings containing the hollow resin particles in the embodiments of the present invention exhibit excellent reflectivity in the wavelength range from ultraviolet to near-infrared light.

[0113] The heat-insulating resin composition of the embodiments of the present invention comprises hollow resin particles of the embodiments of the present invention.

[0114] The heat-insulating resin composition of the embodiments of the present invention preferably comprises at least one selected from adhesive resins and UV-curing resins. Regarding adhesive resins and UV-curing resins, the above description of the coating composition can be referenced.

[0115] The heat-insulating resin composition of embodiments of the present invention may contain a solvent. Regarding the solvent, the above description of the coating composition can be referenced.

[0116] The heat-insulating resin composition of the embodiments of the present invention can be diluted to adjust the viscosity as needed. The above description of the coating composition can be used as a diluent.

[0117] The heat-insulating resin composition of the embodiments of the present invention may contain other components as needed, such as coating modifiers, flow modifiers, ultraviolet absorbers, light stabilizers, hardening catalysts, extender pigments, coloring pigments, metallic pigments, mica powder pigments, and dyes.

[0118] The above description of the coating composition can be used as a reference for coating methods and forming methods when forming a coating film using the heat-insulating resin composition according to the embodiments of the present invention.

[0119] <Light-diffusing resin composition> The hollow resin particles in the embodiments of the present invention can impart excellent light diffusivity to the coating containing them, and are therefore suitable for use in light-diffusing resin compositions.

[0120] The light-diffusing resin composition of the embodiments of the present invention comprises hollow resin particles of the embodiments of the present invention.

[0121] The light-diffusing resin composition of the embodiments of the present invention preferably comprises at least one selected from adhesive resins and UV-curing resins. Regarding adhesive resins and UV-curing resins, the above description of the coating composition can be referenced.

[0122] The light-diffusing resin composition of embodiments of the present invention may contain a solvent. Regarding the solvent, the above description of the coating composition can be referenced.

[0123] The light-diffusing resin composition of the embodiments of the present invention can be diluted to adjust the viscosity as needed. The above description of the coating composition can be used as a diluent.

[0124] The light-diffusing resin composition of the embodiments of the present invention may contain other components as needed, such as coating conditioners, flow conditioners, ultraviolet absorbers, light stabilizers, hardening catalysts, extender pigments, coloring pigments, metallic pigments, mica powder pigments, and dyes.

[0125] The above description of the coating composition can be used as a reference for coating methods and forming methods when forming a coating film using the light-diffusing resin composition according to the embodiments of the present invention.

[0126] <Light diffusion film> In the embodiments of the present invention, hollow resin particles can impart excellent light diffusion properties to films containing coatings, and therefore can also be suitably used in light diffusion films.

[0127] The light diffusion film of the embodiments of the present invention comprises hollow resin particles of the embodiments of the present invention.

[0128] The light diffusion film of the present invention comprises a light diffusion layer formed from the light diffusion resin composition of the present invention and a substrate. Furthermore, the light diffusion layer may or may not be the outermost layer of the light diffusion film. The light diffusion film of the present invention may include any other suitable layers depending on the purpose. Examples of such other layers include: a protective layer, a hard coating layer, a planarization layer, a high refractive index layer, an insulating layer, a conductive resin layer, a conductive metal microparticle layer, a conductive metal oxide microparticle layer, and a base coating layer.

[0129] Examples of substrates include: metal, wood, glass, plastic film, plastic sheet, plastic lens, plastic panel, cathode ray tube, fluorescent display tube, and liquid crystal display panel. Examples of plastics that constitute plastic film, plastic sheet, plastic lens, and plastic panel include: PET (polyethylene terephthalate), PC (polycarbonate), acrylic resin, and TAC (triacetin cellulose).

[0130] ≪≪2. Manufacturing Method of Hollow Resin Particles≫≫ The method for manufacturing hollow resin particles of the present invention involves reacting a composition (A) comprising at least one of the following groups: a crosslinking monomer (a), a monofunctional monomer (b), and a compound (c) having an ether structure represented by the following formula (2), in an aqueous medium in the presence of a non-reactive solvent. In this case, when the total amount of the crosslinking monomer (a), the monofunctional monomer (b), and the compound (c) is set to 100 parts by weight, the crosslinking monomer (a) is 1 to 50 parts by weight. [Chemistry 7]

[0131] According to the above manufacturing method, hollow resin particles of the embodiments of the present invention can be easily manufactured, for example.

[0132] The preferred method for manufacturing hollow resin particles in this invention involves a crosslinking monomer (a) comprising an aromatic crosslinking monomer. When the total amount of the crosslinking monomer (a), the monofunctional monomer (b), and the compound (c) is set to 100 parts by weight, the aromatic crosslinking monomer is preferably 1 to 50 parts by weight, more preferably 1 to 40 parts by weight, further preferably 1 to 35 parts by weight, even more preferably 1 to 30 parts by weight, and most preferably 1 to 26 parts by weight. Furthermore, the aromatic crosslinking monomer is preferably 3 to 50 parts by weight, more preferably 5 to 50 parts by weight, even more preferably 8 to 40 parts by weight, even more preferably 10 to 40 parts by weight, and most preferably 10 to 35 parts by weight.

[0133] Composition (A) may comprise a monofunctional monomer (b) and a compound (c).

[0134] For example, hollow resin particles according to embodiments of the present invention can be obtained by reacting a crosslinking monomer (a) and at least one of the group consisting of a monofunctional monomer (b) and a compound (c) in an aqueous medium in the presence of a non-reactive solvent. Typically, hollow resin particles according to embodiments of the present invention can be manufactured by subjecting a monomer component (M) comprising a crosslinking monomer (a) and a monofunctional monomer (b) to a suspension polymerization reaction, or by subjecting a monomer component (M) and a compound (c) to a suspension polymerization reaction.

[0135] Suspension polymerization is typically carried out using an aqueous phase containing an aqueous medium and an oil phase containing composition (A) and a non-reactive solvent. More preferably, suspension polymerization is carried out by adding an oil phase containing composition (A) and a non-reactive solvent to the aqueous phase containing the aqueous medium to disperse it and then heating it.

[0136] Regarding dispersion, any suitable dispersion method can be used as long as the oil phase can exist in the aqueous phase in droplet form, without impairing the effects of the present invention. Representative examples of such dispersion methods include those using a homogenizer or homogenizer, such as a Polytron Homogenizer, an ultrasonic homogenizer, or a high-pressure homogenizer.

[0137] As long as the polymerization temperature is suitable for suspension polymerization, any appropriate polymerization temperature can be used within the range that does not impair the effects of the present invention. A preferred polymerization temperature is 30°C to 90°C.

[0138] The polymerization time can be any suitable time as long as it is appropriate for suspension polymerization, without compromising the effects of the present invention. A preferred polymerization time is 1 hour to 48 hours.

[0139] It is preferable to perform a post-polymerization heating system for a suitable treatment to obtain hollow resin particles with a higher degree of completion.

[0140] Preferably, the temperature at which post-polymerization heating is performed is within the range that does not impair the effects of the present invention, and any suitable temperature can be used. A preferred temperature for such post-heating is 70°C to 120°C.

[0141] The subsequent heating time after polymerization is preferably within the range that does not impair the effects of the present invention, and any appropriate time can be used. The preferred duration for this subsequent heating is 1 hour to 24 hours.

[0142] Regarding the monomer components (M) and compounds (c), please refer directly to the descriptions in the sections 1-2 of ≪≪1. Hollow Resin Particles≫≫.

[0143] In addition to crosslinking monomers (a) and monofunctional monomers (b), the monomer component (M) may also contain other monomers (m). There may be only one type of other monomer (m), or there may be two or more types. For details regarding crosslinking monomers (a), monofunctional monomers (b), and other monomers (m), please refer to the explanations in ≪≪1. Hollow Resin Particles≫≫, ≪1-2. Shell Part≫.

[0144] In terms of further demonstrating the effects of the present invention, the manufacturing method of the present invention allows the composition (A) to be reacted in an aqueous medium in the presence of a hydrocarbon resin (B) and a non-reactive solvent. That is, the oil phase may contain the hydrocarbon resin (B).

[0145] In terms of further demonstrating the effects of the present invention, when the total amount of the crosslinking monomer (a), monofunctional monomer (b), compound (c), and hydrocarbon resin (B) is set to 100 parts by weight, the hydrocarbon resin (B) is preferably 1 to 10 parts by weight, more preferably 1 to 8 parts by weight, further preferably 2 to 8 parts by weight, even more preferably 2 to 6 parts by weight, and most preferably 2 to 5 parts by weight. Alternatively, the hydrocarbon resin (B) may be 1 to 5 parts by weight. This allows for the acquisition of hollow resin particles with excellent dielectric properties unaffected by high-temperature environments.

[0146] When composition (A) contains compound (c), the oil phase may not contain hydrocarbon resin (B).

[0147] Regarding hydrocarbon resins (B), the descriptions in ≪≪1. Hollow Resin Particles≫≫ and ≪1-2. Shells≫ can be directly referenced.

[0148] The non-reactive solvent is a solvent that does not chemically react with any of the monomer component (M), compound (c), and hydrocarbon resin (B), and is preferably an organic solvent. Typically, the non-reactive solvent acts as a cavitation agent to fill the voids in the particles. Examples of non-reactive solvents include: heptane, hexane, toluene, cyclohexane, methyl acetate, ethyl acetate, methyl ethyl ketone, chloroform, and carbon tetrachloride. For ease of removal from the hollow resin particles, the boiling point of the non-reactive solvent is preferably below 100°C.

[0149] The non-reactive solvent used as a cavitation agent can be a single solvent or a mixture of solvents.

[0150] The amount of non-reactive solvent added is preferably 20 to 250 parts by weight relative to the total amount of monomer component (M) and compound (c) of 100 parts by weight.

[0151] Examples of aqueous media include water and mixtures of water and lower alcohols (methanol, ethanol, etc.).

[0152] The amount of aqueous medium used can be any appropriate amount without impairing the effects of the present invention. Typically, the amount of aqueous medium used is the appropriate amount for the reaction to proceed in a suspension polymerization reaction in which the oil phase is added to the aqueous phase and suspended in the aqueous phase, relative to 100 parts by weight of the monomer component (M), compound (c), hydrocarbon resin (B), and non-reactive solvent, preferably 100 parts by weight to 5000 parts by weight, and more preferably 150 parts by weight to 2000 parts by weight.

[0153] During the reaction of composition (A), any suitable additive (C) that is not a monomer component (M), compound (c), or hydrocarbon resin (B) may be added without impairing the effects of the present invention. Additive (C) may be only one type or may be two or more types. The additive (C) referred to herein does not include solvents such as aqueous media or non-reactive solvents, or dispersants and stabilizers.

[0154] The content ratio of additive (C) relative to the total amount of monomer component (M), compound (c) and hydrocarbon resin (B) is preferably 0% to 40% by weight, more preferably 0% to 30% by weight, further preferably 0% to 20% by weight, and even more preferably 0% to 10% by weight.

[0155] Examples of additives (C) include: non-crosslinked polymers, polymerization initiators, and surfactants.

[0156] For non-crosslinked polymers, the descriptions in ≪≪1. Hollow Resin Particles≫≫ and ≪1-2. Shells≫ can be directly referenced.

[0157] As a polymerization initiator, any suitable polymerization initiator may be used without impairing the effects of the present invention. Examples of such polymerization initiators include: lauryl peroxide, benzoyl peroxide, o-chlorobenzoyl peroxide, o-methoxybenzoyl peroxide, 3,5,5-trimethylhexyl peroxide, tributyl peroxide, di- and tributyl peroxide, and other organic peroxides; azo compounds such as 2,2'-azobisisobutyronitrile, 1,1'-azobiscyclohexanenitrile, and 2,2'-azobis(2,4-dimethylpentanonitrile).

[0158] The content of the polymerization initiator relative to the total amount of monomer component (M) and compound (c) is preferably in the range of 0.1% to 5% by weight. There may be only one polymerization initiator or two or more.

[0159] The polymerization initiator can be contained in the oil phase, the aqueous phase, or used separately from both phases. As a representative embodiment, the polymerization initiator is contained in the oil phase.

[0160] Regarding surfactants, please refer directly to the descriptions in Section 1-2, "Shell Part," of Section 1. Hollow Resin Particles.

[0161] When reacting the composition (A), any suitable dispersant (D) may be used without impairing the effects of the present invention.

[0162] The dispersant stabilizer may be contained in the oil phase, the aqueous phase, or used separately from both phases. As a representative embodiment, the dispersant stabilizer is contained in the aqueous phase.

[0163] The dispersant stabilizer (D) is equivalent to 100 parts by weight of the aqueous medium contained in the aqueous phase, preferably 0.5 parts by weight to 10 parts by weight.

[0164] The dispersant stabilizer (D) may be only one type or two or more types.

[0165] As a specific example of a dispersing stabilizer (D), the description in the items ≪≪1. Hollow Resin Particles≫≫ and ≪1-2. Shells≫ can be directly cited. [Example]

[0166] The present invention will be specifically described below with reference to specific embodiments, but the present invention is not limited to these embodiments.

[0167] <Determination of volume average particle size and coefficient of variation (CV) of particle size> The volume-average particle size was determined using the Coulter method as follows. The volume average particle size was measured using a Coulter Multisizer 4e (a measuring device manufactured by Beckman Coulter Inc.). The measurement was performed using an pore size calibrated according to the Beckman Coulter Multisizer 4e user guide. The pore size used for the measurement was appropriately selected based on the assumed volume average particle size of the particles being measured. For example, a pore size of 10 μm was selected when the assumed volume average particle size was 0.2 μm to 6 μm; a pore size of 50 μm was selected when the assumed volume average particle size was 1.0 μm to 32 μm; and a pore size of 100 μm was selected when the assumed volume average particle size was 2.0 μm to 60 μm. If the measured volume average particle size differed from the assumed volume average particle size, the pore size was changed, and the measurement was performed again. As the sample for testing, a dispersion was prepared by dispersing 0.1 g of particles in 10 mL of a 0.1% by weight nonionic surfactant aqueous solution using a touch mixer (manufactured by Yamato Scientific Co., Ltd., "TOUCHMIXER MT-31") and an ultrasonic cleaner (manufactured by VELVO-CLEAR Co., Ltd., "ULTRASONIC CLEANER VS-150"). During the test, the mixture was slowly stirred in a beaker until no bubbles were present, and the test was stopped when 100,000 particles were measured. Furthermore, the volume average particle size was set as the arithmetic mean of the particle size distribution based on the volume of 100,000 particles. The coefficient of variation (CV) of particle size is calculated using the following formula. The coefficient of variation (CV) of particle size (%) = (standard deviation of particle size distribution based on volume ÷ volume mean particle size) × 100 (%)

[0168] <Determination of 5% heat weight reduction temperature when heated at a rate of 10°C / min in air or nitrogen atmosphere> The 5% reduction in thermal mass temperature was measured using a differential thermal gravimetric analyzer (manufactured by Hitachi High-Tech Science Co., Ltd., "NEXTA STA200RV"). The sampling method and temperature conditions were as follows. The sample was prepared by seamlessly filling the bottom of a platinum measuring vessel with 10.5 ± 0.5 mg of the sample. Using alumina as a reference, the 5% thermogravimetric decrease (TGA) temperature was determined under conditions of an air or nitrogen flow rate of 200 mL / min. The TG / DTA curve was obtained by heating the sample from 30°C to 800°C at a heating rate of 10°C / min. Using the instrument's built-in analysis software, the temperature at which the 5% weight loss occurred was calculated from the obtained curve and set as the 5% TGA temperature.

[0169] <Observation of the presence and shape of hollow parts within particles> The presence or absence of hollow parts in particles and their shape are observed by observing particle cross-sections. The dried particles were mixed with the photocurable resin "D-800" (manufactured by NEC Corporation), and cured by irradiation with ultraviolet light. The cured material was then cut with pliers, and the cross-section was smoothly machined using a cutting machine. The sample was then coated using a sputtering apparatus (manufactured by NEC Corporation, "AUTO FINE COATER JFC-1300"). Subsequently, the cross-section of the sample was photographed using the secondary electron detector of a scanning electron microscope (manufactured by Hitachi High-Tech Co., Ltd., "SU1510"). At this time, the magnification was set to 3000x, 4000x, or 5000x for imaging.

[0170] <Dielectric properties of hollow resin particles before heating test> The dielectric properties of the hollow resin particles were measured using a dielectric constant measuring device (ADMS01Nc series) manufactured by AET Corporation. The measurements were conducted at a frequency of 10 GHz, an ambient temperature of 23°C, and a relative humidity of 51 ± 1%. Based on the perturbation theory of resonators, the relative permittivity and dielectric loss tangent (Df1) of the hollow resin particles before the heating test were calculated.

[0171] <Dielectric properties of hollow resin particles after heating test under condition I> First, a specified amount of particles is placed in a constant humidity oven at a temperature of 180°C for 1 hour to conduct the heating test under condition I. After the particles were cooled following the heating test, their dielectric properties were measured under the same conditions and methods as those described above for <Dielectric Properties of Hollow Resin Particles Before Heating Test>. The relative permittivity and dielectric loss tangent (Df2) of the hollow resin particles after the heating test under condition I were calculated.

[0172] <Dielectric properties of hollow resin particles after heating test under condition II> First, a specified amount of particles is placed in a constant humidity oven at a temperature of 260°C for 2 minutes to conduct a heating test. After the particles were cooled following the heating test, their dielectric properties were measured under the same conditions and methods as those described above for <Dielectric Properties of Hollow Resin Particles Before Heating Test>. The relative permittivity and dielectric loss tangent (Df3) of the hollow resin particles after the heating test under Condition II were calculated.

[0173] [Example 1] A mixture of 87.1 g of styrene (manufactured by Denka Co., Ltd.), 39.0 g of divinylbenzene (DVB) 810 (Nippon Steel Chemical Materials Co., Ltd., 81% content, 19% ethylvinylbenzene (EVB)), 130 g of heptane, 3.9 g of PETROTAC 90 (aliphatic / aromatic hydrocarbon resin, manufactured by Tosoh Co., Ltd.), 2.6 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (ADVN, trade name "V-65", manufactured by Fujifilm and Wako Pure Chemical Co., Ltd.) as a polymerization initiator, and 0.52 g of "KAYAMER (registered trademark) PM-21" (manufactured by Nippon Kayaku Co., Ltd.) as another monomer was prepared to form an oil phase. An oil phase was added to 1111 g of a 2.0 wt% aqueous dispersion of magnesium pyrophosphate as the aqueous phase. The dispersion was carried out using a Polytron Homogenizer (Central Scientific Trading Co., Ltd., "PT10-35") at 7,000 rpm for 5 minutes. Emulsification was then performed using a high-pressure emulsifier (Yoshida Machinery Co., Ltd., "NVL-AS200") at a processing pressure of 20 MPa to prepare a suspension. The obtained suspension was then polymerized by heating at 65°C for 5 hours, followed by a final reaction treatment at 80°C for 3 hours to complete the polymerization reaction and obtain a slurry. By adding hydrochloric acid to the obtained slurry to decompose magnesium pyrophosphate, the solid components are separated by filtration for dehydration, and after repeated washing with water for purification, the slurry is heated and dried to obtain particles as dry powder (1). The obtained particles (1) had a volume average particle size of 4.1 μm and a coefficient of variation (CV) of 32.2%. A cross-sectional photograph of the obtained particles (1) is shown in Figure 2. It was confirmed that the obtained particles (1) were hollow resin particles containing a porous structure surrounded by a shell. The formulation amount and various measurement results are shown in Table 1.

[0174] [Example 2] The amount of styrene (manufactured by Denka Corporation) was set to 74.1 g, and the amount of divinylbenzene (DVB) 810 (Nippon Steel Chemical Materials Co., Ltd., 81% content, 19% ethylvinylbenzene (EVB)) was set to 52.0 g. Otherwise, the process was carried out in the same manner as in Example 1 to obtain particles (2). The obtained particles (2) had a volume average particle size of 4.4 μm and a coefficient of variation (CV) of 24.6%. A cross-sectional photograph of the obtained particles (2) is shown in Figure 3. It was confirmed that the obtained particles (2) were hollow resin particles containing a porous structure surrounded by a shell. The formulation amount and various measurement results are shown in Table 1.

[0175] [Example 3] An oil phase was prepared by mixing 39.0 g of reactive low molecular weight polyphenylene ether (trade name "Noryl (registered trademark) SA9000-111 resin", manufactured by SABIC Corporation), 52.0 g of styrene (manufactured by Denka Corporation), 39.0 g of divinylbenzene (DVB) 810 (Nippon Steel Chemical Materials Co., Ltd., 81% content, 19% ethylvinylbenzene (EVB)), 1.3 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (ADVN, trade name "V-65", manufactured by Fujifilm and Wako Pure Chemical Co., Ltd.), 0.52 g of "KAYAMER (registered trademark) PM-21" (manufactured by Nippon Kayaku Co., Ltd.), and 0.65 g of octyl mercaptan (1-octane mercaptan, manufactured by Tokyo Chemical Industry Co., Ltd.), which is a chain transfer agent. An oil phase was added to 1111 g of a 2.0 wt% magnesium pyrophosphate aqueous dispersion as the aqueous phase. The dispersion was carried out using a Polytron Homogenizer (Central Scientific Trading Co., Ltd., "PT10-35") at 7,000 rpm for 5 minutes. Emulsification was then performed using a high-pressure emulsifier (Yoshida Machinery Co., Ltd., "NVL-AS200") at a processing pressure of 20 MPa to prepare a suspension. The obtained suspension was then heated at 60°C for 5 hours, followed by stirring at 90°C for 2 hours to complete the polymerization reaction and obtain a slurry. By adding hydrochloric acid to the obtained slurry to decompose magnesium pyrophosphate, the solid components are separated by filtration for dehydration, and after repeated washing with water for purification, the slurry is heated and dried to obtain particles as dry powder (3). The volume-average particle size of the obtained particles (3) was 4.4 μm, and the coefficient of variation (CV) was 34.1%. A cross-sectional photograph of the obtained particles (3) is shown in Figure 4. It was confirmed that the obtained particles (3) were hollow resin particles containing a porous structure surrounded by a shell. The formulation amount and various measurement results are shown in Table 1.

[0176] [Example 4] The amount of styrene (manufactured by Denka Corporation) was set to 52.0 g, and the amount of divinylbenzene (DVB) 810 (Nippon Steel Chemical Materials Co., Ltd., 81% content, 19% ethylvinylbenzene (EVB)) was set to 78.0 g. PETROTAC90 (aliphatic / aromatic hydrocarbon resin, manufactured by Tosoh Corporation) was not used. Otherwise, the process was carried out in the same manner as in Example 1 to obtain particles (4). The volume-average particle size of the obtained particles (4) was 3.9 μm, and the coefficient of variation (CV) was 28.9%. A cross-sectional photograph of the obtained particles (4) is shown in Figure 5. It was confirmed that the obtained particles (4) were hollow resin particles containing a porous structure surrounded by a shell. The formulation amount and various measurement results are shown in Table 1.

[0177] [Example 5] Using 3.9 g of VYBARTM260 (paraffin, manufactured by Nucera Solutions) instead of 3.9 g of PETROTAC90 (aliphatic / aromatic hydrocarbon resin, manufactured by Tosoh Corporation), the same procedure as in Example 1 was followed to obtain particles (5). The obtained particles (5) had a volume average particle size of 4.0 μm and a coefficient of variation (CV) of 27.5%. A cross-sectional photograph of the obtained particles (5) is shown in Figure 6. It was confirmed that the obtained particles (5) were hollow resin particles with a porous structure surrounded by a shell. The formulation amount and various measurement results are shown in Table 1.

[0178] [Example 6] The oil phase was prepared in the same manner as in Example 5. It was added to 1111 g of a 2.0 wt% magnesium pyrophosphate aqueous dispersion (which served as the aqueous phase). An emulsification process was performed using a Polytron Homogenizer (manufactured by Central Scientific Trading Co., Ltd., "PT10-35") at 7,000 rpm for 5 minutes to prepare a suspension. The obtained suspension was then polymerized by heating at 65°C for 5 hours. The remaining reaction was carried out by heating at 80°C for 2 hours to complete the polymerization reaction and obtain a slurry. By adding hydrochloric acid to the obtained slurry to decompose magnesium pyrophosphate, the solid components are separated by filtration for dehydration, and after repeated washing with water for purification, the slurry is heated and dried to obtain particles as dry powder (6). The volume average particle size of the obtained particles (6) was 9.1 μm, and the coefficient of variation was 42.5%. A cross-sectional photograph of the obtained particles (6) is shown in Figure 7. It was confirmed that the obtained particles (6) were hollow resin particles containing a porous structure surrounded by a shell. The formulation amount and various measurement results are shown in Table 1.

[0179] [Example 7] The oil phase was prepared in the same manner as in Example 3. It was added to 1111 g of a 2.0 wt% magnesium pyrophosphate aqueous dispersion (which served as the aqueous phase). An emulsification process was performed using a Polytron Homogenizer (manufactured by Central Scientific Trading Co., Ltd., "PT10-35") at 7,000 rpm for 5 minutes to prepare a suspension. The obtained suspension was then polymerized by heating at 60°C for 5 hours. The remaining reaction was carried out by heating at 80°C for 2 hours to complete the polymerization reaction and obtain a slurry. By adding hydrochloric acid to the obtained slurry to decompose magnesium pyrophosphate, the solid components are separated by filtration for dehydration, and after repeated washing with water for purification, the slurry is heated and dried to obtain particles as dry powder (7). The volume average particle size of the obtained particles (7) was 11.3 μm, and the coefficient of variation was 40.4%. A cross-sectional photograph of the obtained particles (7) is shown in Figure 8. It was confirmed that the obtained particles (7) were hollow resin particles with a porous structure surrounded by a shell. The dosage and various measurement results are shown in Table 1.

[0180] [Comparative Example 1] An oil phase was prepared by mixing 65.0 g of methyl methacrylate, 65.0 g of ethylene glycol dimethacrylate, 130 g of cyclohexane, 1.3 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (ADVN, trade name "V-65", manufactured by Fujifilm and Wako Pure Chemical Industries Co., Ltd.) as a polymerization initiator, and 0.52 g of "KAYAMER (registered trademark) PM-21" (manufactured by Nippon Kayaku Co., Ltd.) as another monomer. An oil phase was added to 1111 g of a 2.0 wt% magnesium pyrophosphate aqueous dispersion as the aqueous phase, and the mixture was dispersed and emulsified using a Polytron Homogenizer (manufactured by Central Scientific Trading Co., Ltd., "PT10-35") at 7,000 rpm for 5 minutes to prepare a suspension. The obtained suspension was then polymerized by heating at 55°C for 5 hours, followed by a final reaction treatment at 80°C for 2 hours to complete the polymerization reaction and obtain a slurry. By adding hydrochloric acid to the obtained slurry to decompose magnesium pyrophosphate, the solid components are separated by filtration for dehydration, and after repeated washing with water for purification, the slurry is heated and dried to obtain particles (Cl) as dried powder. The obtained particles (C1) had a volume average particle size of 7.6 μm and a coefficient of variation (CV) of 26.8%. A cross-sectional photograph of the obtained particles (C1) is shown in Figure 9. It was confirmed that the obtained particles (C1) are hollow resin particles containing a porous structure surrounded by a shell. The formulation amount and various measurement results are shown in Table 1.

[0181] [Comparative Example 2] Particles (C2) were obtained by using styrene (manufactured by Denka Co., Ltd.) and setting the amount of divinylbenzene (DVB) 810 (Nippon Steel Chemical Materials Co., Ltd., 81% content, 19% ethylvinylbenzene (EVB)) to 130.0 g. Otherwise, the process was carried out in the same manner as in Example 1. The obtained particles (C2) had a volume average particle size of 4.3 μm and a coefficient of variation (CV) of 28.9%. A cross-sectional photograph of the obtained particles (C2) is shown in Figure 10. It was confirmed that the obtained particles (C2) are hollow resin particles containing a porous structure surrounded by a shell. The formulation amount and various measurement results are shown in Table 1.

[0182] [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 oil phase Composition (A) Monomer (M) Monofunctional monomer (b) styrene 87.1 74.1 52.0 52.0 87.1 87.1 52.0 - - Ethylvinylbenzene 7.4 9.9 7.4 14.8 7.4 7.4 7.4 - 24.7 Methyl methacrylate - - - - - - - 65.0 - Crosslinking monomer (a) Divinylbenzene 31.6 42.1 31.6 63.2 31.6 31.6 31.6 - 105.3 Ethylene glycol dimethacrylate - - - - - - - 65.0 - Other monomers (m) KAYAMER PM-21 0.52 0.52 0.52 0.52 0.52 0.52 0.52 0.52 0.52 Compound (c) Reactive polyphenylene ether - - 39.0 - - - 39.0 - - Hydrocarbon resins (B) PETROTAC 90 3.9 3.9 - - - - - - 3.9 VYVAR 260 - - - - 3.9 3.9 - - - non-reactive solvents heptane 130 130 130 130 130 130 130 - 130 Cyclohexane - - - - - - - 130 - Additive (C) Polymerization initiator ADVN 2.6 2.6 1.3 2.6 2.6 2.6 1.3 1.3 2.6 Chain transfer agent Octylthiol - - 0.65 - - - 0.65 - - Aqueous phase Dispersant stabilizer (D) Magnesium pyrophosphate 2.0wt% aqueous dispersion 1111 1111 1111 1111 1111 1111 1111 1111 1111 Particle properties Volume average particle size (μm) 4.1 4.4 4.4 3.9 4.0 9.1 11.3 7.6 4.3 Coefficient of variation (CV) of particle size (%) 32.2 24.6 34.1 28.9 27.5 42.5 40.4 26.8 28.9 5% reduction in thermal weight at temperature (air atmosphere) (°C) 305.8 308.3 329.1 311.4 275.5 292.6 328.3 258.5 329.4 5% reduction in thermal weight at temperature (nitrogen atmosphere) (°C) 368.2 371.8 386.1 377.1 349.4 365.8 383.5 239.4 410.3 Particle internal structure Internal porous material Internal porous material Internal porous material Internal porous material Internal porous material Internal porous material Internal porous material Internal porous material Internal porous material Dielectric properties of particles before heating test Relative permittivity 1.46 1.42 1.48 1.46 1.46 1.48 1.49 1.39 1.46 Df1: Dielectric loss tangent 0.00108 0.00139 0.00091 0.00120 0.00120 0.00142 0.00112 0.00718 0.00206 Dielectric properties of particles after heating test under condition I Relative permittivity 1.43 1.51 1.46 1.42 1.44 1.49 1.48 1.51 1.57 Df2: Dielectric loss tangent 0.00158 0.00181 0.00110 0.00223 0.00172 0.00182 0.00135 0.01123 0.00879 Df2-Df1 0.00050 0.00042 0.00019 0.00103 0.00052 0.00040 0.00023 0.00405 0.00673 Dielectric properties of particles after heating test under condition II Relative permittivity 1.52 1.48 1.47 1.48 1.49 1.49 1.51 1.45 1.52 Df3: Dielectric loss tangent 0.00230 0.00347 0.00178 0.00301 0.00280 0.00372 0.00168 0.01210 0.00953 Df3-Df1 0.00122 0.00208 0.00087 0.00181 0.00160 0.00230 0.00056 0.00492 0.00747

[0183] According to the results in Table 1, the particles obtained in Examples 1 to 7 are hollow resin particles with excellent dielectric properties that are not affected by high-temperature environments.

[0184] <Performance Evaluation: Evaluation of the relative permittivity and dielectric loss tangent of the film with added particles> A film containing particles (1) obtained in Example 1, a film containing particles (3) obtained in Example 3, and a film containing particles (C1) obtained in Comparative Example 1 were prepared in the following manner, and the relative permittivity and dielectric loss tangent of the films were evaluated. The obtained particles (0.425 g), ethyl acetate (8.3 g), and solvent-soluble polyimide KPI-MX300F (manufactured by Kurabo Corporation, "MAZERUSTAR KK-250") were degassed and stirred using a planetary stirrer (manufactured by Kurabo Corporation, "MAZERUSTAR KK-250") to prepare an evaluation mixture. The evaluation mixture was coated onto a 5 mm thick glass plate using a dressing apparatus set to a wet thickness of 250 μm. Ethyl acetate was removed by heating at 60°C for 30 minutes, at 90°C for 10 minutes, at 150°C for 30 minutes, and at 200°C for 30 minutes. The plate was then cooled to room temperature to obtain a film containing the particles. The relative permittivity and dielectric loss tangent of the obtained films were evaluated using the cavity resonance method (measurement frequency: 10 GHz). The measurement results were set as the relative ratio (%) with the measurement value of the particle-free film being 100%. The results are shown in Table 2.

[0185] [Table 2] A membrane containing particles (1) of Example 1 A membrane containing particles (3) of Example 3 A membrane containing particles (C1) of Comparative Example 1 A membrane that does not contain particles (reference) Relative permittivity (%) 79.9 81.2 94.2 100 Dielectric loss tangent (%) 72.9 73.6 79.3 100

[0186] According to the results in Table 2, it can be seen that the hollow resin particles provided by the present invention, compared with the particles (C1) of Comparative Example 1, have the effect of further reducing the relative permittivity and dielectric loss tangent of the substrate, which is effective for achieving the purpose of reducing the dielectric constant and dielectric loss tangent of semiconductor materials. [Industrial Applicability]

[0187] Hollow resin particles obtained by means of the embodiments of the present invention and the manufacturing method of the embodiments of the present invention can be used in semiconductor materials, etc.

Claims

1. A hollow resin particle having a shell and a hollow portion surrounded by the shell, wherein, under a heating test at 180°C and 1 hour, the dielectric loss tangent Df1 at a measured frequency of 10 GHz before the heating test and the dielectric loss tangent Df2 at a measured frequency of 10 GHz after the heating test under condition I satisfy formula (1), Df2-Df1≤0.004・・・(1), wherein the shell comprises a polymer (P), which is obtained by reacting a composition (A) comprising at least one of a crosslinking monomer (a) and a compound (c) selected from a monofunctional monomer (b) and a compound having an ether structure represented by formula (2), wherein the composition (A) comprises the monofunctional monomer (b) and the monofunctional monomer (b) comprises styrene, [Chemical 1].

2. As in request item 1, the hollow resin particles, wherein the dielectric loss tangent Df1 does not reach 0.

002.

3. As in request item 1, the relative permittivity of the hollow resin particles at a measured frequency of 10 GHz does not reach 1.

5.

4. Hollow resin particles as claimed in claim 1, wherein the crosslinking monomer (a) is an aromatic crosslinking monomer.

5. In the hollow resin particles of claim 4, when the total amount of the crosslinking monomer (a), the monofunctional monomer (b), and the compound (c) is set to 100 parts by weight, the aromatic crosslinking monomer is 1 to 50 parts by weight.

6. The hollow resin particles of claim 1, wherein the shell portion further comprises or does not comprise hydrocarbon resin (B), and when the shell portion comprises hydrocarbon resin (B), the content of hydrocarbon resin (B) is 1 to 10 parts by weight relative to 100 parts by weight of the aggregate of the polymer (P) and the hydrocarbon resin (B).

7. The hollow resin particles as claimed in claim 1, wherein the 5% heat weight reduction temperature when the hollow resin particles are heated in an air atmosphere at a rate of 10°C / min is 270°C or higher.

8. The hollow resin particles in Request 1 have a volume average particle size of 0.1 μm to 30 μm.

9. A hollow resin particle having a shell and a hollow portion surrounded by the shell, wherein, under a heating test at 260°C for 2 minutes, the dielectric loss tangent Df1 at a measured frequency of 10 GHz before the heating test and the dielectric loss tangent Df3 at a measured frequency of 10 GHz after the heating test under condition II satisfy formula (3), Df3-Df1≤0.004・・・(3), wherein the shell comprises a polymer (P), which is obtained by reacting a composition (A) comprising at least one of a crosslinking monomer (a) and a compound (c) selected from a group consisting of a monofunctional monomer (b) and an ether structure represented by formula (2), wherein the composition (A) comprises the monofunctional monomer (b) and the monofunctional monomer (b) comprises styrene, [Chemical 2].

10. Hollow resin particles as claimed in claim 9, wherein the dielectric loss tangent Df1 does not reach 0.

002.

11. Hollow resin particles as claimed in any of claims 1 to 10, used in resin compositions for semiconductor components.

12. A resin composition for semiconductor components comprising hollow resin particles as claimed in claim 11.

13. A method for manufacturing hollow resin particles, wherein a composition (A) comprising at least one of a group consisting of a crosslinking monomer (a) and a compound (c) having an ether structure represented by formula (2) is reacted in an aqueous medium in the presence of a non-reactive solvent, wherein the composition (A) comprises the monofunctional monomer (b), the monofunctional monomer (b) comprises styrene, and when the total amount of the crosslinking monomer (a), the monofunctional monomer (b) and the compound (c) is set to 100 parts by weight, the crosslinking monomer (a) is 1 to 50 parts by weight, [Chemical 3].

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