Hollow resin particles and their manufacturing methods, resin compositions for semiconductor components, coating compositions, heat-insulating resin compositions, light-diffusing resin compositions, and light-diffusing films.

Abstract

This invention provides hollow resin particles, which exhibit excellent heat resistance due to the presence of hollow portions within the particles. Furthermore, this invention provides a simple method for manufacturing such hollow resin particles. And furthermore, this invention provides uses for such hollow resin particles. In the embodiments of the present invention, the hollow resin particles are those with hollow portions inside the particles, having an ether structure represented by formula (1), and an average particle size of 0.1 μm to 100 μm.

Description

Technical Field

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

[0002] Resin particles utilize their characteristics for various applications, such as imparting light scattering properties to transparent resins, providing matte and scratch-resistant properties to coatings and inks, and imparting slip properties to cosmetics to prevent film adhesion.

[0003] To impart various properties, research is currently underway to control the particle shape of resin particles. For example, research is being conducted on introducing hollow resin particles with hollow sections inside the particles.

[0004] Patent Document 1 shows that hollow resin particles are suitable for imparting opacity to coating agents such as paints or paper coating compositions. Patent Document 1 also shows that hollow resin particles are lightweight due to their hollow interior, and because of the diffuse reflection of light due to the hollow portion, they exhibit excellent optical properties such as opacity, whiteness, and gloss, and also possess heat insulation effects. Patent Document 1 specifically describes obtaining styrene-based hollow resin particles by suspension polymerization of divinylbenzene with saturated hydrocarbons having 8 to 18 carbon atoms.

[0005] Patent Document 2 shows that hollow resin particles are used in numerous fields such as thermal recording materials (e.g., thermal recording paper or thermal transfer receiving paper), pesticides, pharmaceuticals, fragrances, liquid crystals, and adhesives. Patent Document 2 describes a method for obtaining acrylic hollow resin particles by suspending and polymerizing a monomer whose main component is an acrylic polyfunctional monomer, represented by trimethylolpropane tri(meth)acrylate or dipentaerythritol hexaacrylate, with a hydrophobic solvent.

[0006] Patent Document 3 shows that hollow particles with a single-phase structure, formed by a shell composed of free radical reactive monofunctional monomers and crosslinking monomers, are suitable for reducing dielectric constant and reducing dielectric loss tangent in the insulating layer of multilayer printed circuit boards. Patent Document 3 also describes styrene-based hollow resin particles obtained by suspension polymerization of divinylbenzene with saturated hydrocarbons having 8 to 18 carbon atoms (more specifically, hexadecane).

[0007] Patent Document 4 shows that spherical porous resin powder (porous particles) has the effect of preventing makeup from smudging due to sebum or sweat secreted by the skin and maintaining a refreshing feeling. In Patent Document 4, as porous particles, acrylic porous particles containing methyl methacrylate or trimethylolpropane tri(meth)acrylate are described.

[0008] Patent Document 5 shows that porous resin particles are lightweight and have excellent dispersibility, and therefore can be used in cosmetics, light diffusing agents, matting agents, diagnostic reagents, porosipheral agents, absorbents, lightweighting agents, thermal insulation materials, thermal insulation coatings, white pigments, inkjet acceptors, and slow-release agents. Patent Document 5 specifically describes acrylic porous particles containing methyl methacrylate, etc.

[0009] Patent Document 6 demonstrates that porous hollow polymer particles (hollow porous particles) exhibit excellent fragrance release properties, light diffusion properties, liquid absorption properties, body feel, solvent resistance, and mechanical strength. Patent Document 6 specifically describes a method for obtaining acrylic hollow porous particles by suspension polymerization of monomers whose main component is an acrylic monomer represented by methyl methacrylate or trimethylolpropane tri(meth)acrylate with a hydrophobic solvent.

[0010] Patent Document 7 shows that porous hollow polymer particles (hollow porous particles) have excellent mechanical strength and can be effectively used as pore-forming agents. Patent Document 7 specifically describes a method for obtaining acrylic hollow porous particles by suspension polymerization of monomers whose main component is an acrylic monomer represented by methyl methacrylate or trimethylolpropane tri(meth)acrylate with a hydrophobic solvent.

[0011] Patent Document 8 describes engineering plastic particles that exhibit higher heat resistance and solvent resistance compared to particles containing ethylene-based polymers (general polymers) made from acrylic resins, styrene, etc. Patent Document 8 specifically describes particles containing polyamide, polyphenylene ether, polyetherimide, polyarylate, polyamideimide, and epoxy resin.

[0012] Recently, there has been a demand for resin particles with high heat resistance in various applications.

[0013] The hollow particles, porous particles, and hollow porous particles described in Patent Documents 1 to 7 include acrylic resins and ethylene-based polymers (general polymers) made from styrene and other raw materials, which have insufficient heat resistance.

[0014] Although the particles described in Patent Document 8 have excellent heat resistance, no measures have been taken to control the particle structure, such as porous, hollow, or hollow porous particles. [Previous Technical Documents] [Patent Literature]

[0015] Patent Document 1: Japanese Patent Application Publication No. 2002-080503 Patent Document 2: Japanese Patent No. 6513273 Patent Document 3: Japanese Patent No. 4171489 Patent Document 4: Japanese Patent Application Publication No. 2003-081738 Patent Document 5: Japanese Patent Application Publication No. 2014-111728 Patent Document 6: Japanese Patent Application Publication No. 2009-120806 Patent Document 7: Japanese Patent No. 4445495 Patent Document 8: Japanese Patent No. 5387796 Summary of the Invention

[0016] [The problem the invention aims to solve] This invention was made to solve the aforementioned prior problems, and its main objective is to provide a hollow resin particle that exhibits excellent heat resistance due to the presence of hollow portions within the particle. Furthermore, this invention provides a simple method for manufacturing such hollow resin particles. Finally, it provides an application for this hollow resin particle. [Technical means to solve the problem]

[0017] In embodiments of the present invention, the hollow resin particles are those having hollow portions within the particles. Having the ether structure represented by formula (1), The average particle size is 0.1 μm to 100 μm. [Chemistry 1]

[0018] In one embodiment, the hollow portion includes a hollow region.

[0019] In one embodiment, the hollow portion comprises a plurality of hollow regions.

[0020] In one embodiment, the hollow portion is a porous structure.

[0021] In one embodiment, the hollow resin particle of the present invention includes a shell portion and the aforementioned hollow portion surrounded by the shell portion.

[0022] In one embodiment, the 5% heat weight reduction temperature of the hollow resin particles when heated at 10°C / min in a nitrogen atmosphere is 300°C or higher.

[0023] In one embodiment, hollow resin particles are used in a resin composition for semiconductor components.

[0024] In one embodiment, hollow resin particles are used in a coating composition according to an embodiment of the present invention.

[0025] In one embodiment, hollow resin particles are used in an insulating resin composition.

[0026] In one embodiment, hollow resin particles are used in a light-diffusing resin composition.

[0027] In one embodiment, hollow resin particles are used in a light diffusion film.

[0028] The resin composition for semiconductor components according to embodiments of the present invention comprises hollow resin particles according to embodiments of the present invention.

[0029] The coating composition of the embodiments of the present invention comprises hollow resin particles of the embodiments of the present invention.

[0030] The heat-insulating resin composition of the embodiments of the present invention comprises hollow resin particles of the embodiments of the present invention.

[0031] The light-diffusing resin composition of the embodiments of the present invention comprises hollow resin particles of the embodiments of the present invention.

[0032] The light diffusion film of the embodiments of the present invention comprises hollow resin particles of the embodiments of the present invention.

[0033] The manufacturing method of the embodiments of the present invention is the manufacturing method of hollow resin particles according to the embodiments of the present invention. The reaction is carried out in an aqueous medium in the presence of a non-reactive solvent by reacting 20 to 100 parts by weight of a compound (A) having the ether structure represented by formula (1) and 80 to 0 parts by weight of a monomer (B) reacting with the compound (A) (the total amount of the compound (A) and the monomer (B) is 100 parts by weight). [Chemistry 2] [Effects of the Invention]

[0034] According to embodiments of the present invention, a hollow resin particle is provided, which exhibits excellent heat resistance due to the presence of hollow portions within the particle. Furthermore, a simple method for manufacturing such a hollow resin particle is provided. Finally, an application of such a hollow resin particle is provided. Simple Explanation of the Diagram

[0035] Figures 1(a) to (d) are schematic cross-sectional views illustrating the structure of the hollow section. Figure 2 is a cross-sectional photograph of the hollow resin particles (1) obtained in Example 1. Figure 3 is a cross-sectional photograph of the hollow resin particles (2) obtained in Example 2. Figure 4 is a cross-sectional photograph of the hollow resin particles (3) obtained in Example 3. Figure 5 is a cross-sectional photograph of the hollow resin particles (4) obtained in Example 4. Figure 6 is a cross-sectional photograph of the hollow resin particles (5) obtained in Example 5. Figure 7 is a cross-sectional photograph of the hollow resin particles (6) obtained in Example 6. Figure 8 is a cross-sectional photograph of the hollow resin particles (7) obtained in Example 7. Figure 9 is a cross-sectional photograph of the hollow resin particles (8) obtained in Example 8. Figure 10 is a cross-sectional photograph of the hollow resin particles (9) obtained in Example 9. Figure 11 is a cross-sectional photograph of the hollow resin particles (10) obtained in Example 10. Figure 12 is a TEM image of the hollow resin particles (11) obtained in Example 11. Figure 13 is a TEM image of the hollow resin particles (12) obtained in Example 12. Figure 14 is a cross-sectional photograph of the resin particles (13) with a porous structure obtained in Example 13. Figure 15 is a cross-sectional photograph of the hollow resin particles (14) obtained in Example 14. Figure 16 is a cross-sectional photograph of the hollow resin particles (15) obtained in Example 15. Figure 17 is a cross-sectional photograph of the hollow resin particles (16) obtained in Example 16. Figure 18 is a cross-sectional photograph of the hollow resin particles (17) obtained in Example 17. Figure 19 is a cross-sectional photograph of the particle (C1) obtained in Comparative Example 1. Figure 20 shows the ultraviolet-visible-near-infrared spectrophotometric reflectance spectrum of the hollow resin particles (1) obtained in Example 1. Implementation

[0036] The embodiments of the present invention will be described below, but the present invention is not limited to these embodiments.

[0037] 《1. Hollow Resin Particles》 1-1. Structure and Properties of Hollow Resin Particles The hollow resin particles in the embodiments of the present invention are hollow resin particles having a hollow portion inside. The term "hollow" here means that the interior is filled with a substance other than resin, such as gas or liquid. In order to further demonstrate the effects of the present invention, it is preferred that the interior is filled with gas.

[0038] In embodiments of the present invention, if the hollow resin particles have a hollow portion inside the particles, they may have a structure in which the hollow portion inside the particles is open to the outside of the particles in a portion of the particle surface, or they may have a structure including a shell and a hollow portion surrounded by the shell.

[0039] The hollow portion may contain a single hollow region as shown in the schematic cross-sectional view of Figure 1(a), or it may contain multiple hollow regions as shown in the schematic cross-sectional view of Figure 1(b).

[0040] The hollow portion can contain a porous structure as shown in the schematic cross-sectional views of Figure 1(c) and (d). In the case where the hollow portion is a porous structure, the hollow portion can contain a single hollow region (continuous pore) or a plurality of hollow regions (independent pore).

[0041] When the hollow part is a porous structure, it can have a structure in which the hollow part inside the particle is open to the outside of the particle in a part of the particle surface, as shown in Figure 1(c), or it can have a structure including a shell and a hollow part surrounded by the shell, as shown in Figure 1(d).

[0042] In embodiments of the present invention, the average particle size of the hollow resin particles is preferably 0.1 μm to 100 μm, more preferably 0.1 μm to 80 μm, further preferably 0.2 μm to 50 μm, and even more preferably 0.3 μm to 20 μm. If the average particle size of the hollow resin particles is within the above range, the effects of the present invention can be further demonstrated. In embodiments of the present invention, when the average particle size of the hollow resin particles is outside the above range and too small, the thickness of the resin layer constituting the hollow portion will become relatively thin, and therefore the hollow resin particles may not have sufficient strength. In embodiments of the present invention, when the average particle size of the hollow resin particles is outside the above range and too large, phase separation of the polymer and solvent generated by the polymerization of monomer components in suspension polymerization may become difficult to occur, thereby potentially making the formation of the hollow portion difficult.

[0043] 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 the aforementioned 5% heat weight reduction temperature is preferably 500°C or lower. If the 5% heat weight reduction temperature of the hollow resin particles when heated at a rate of 10°C / min in a nitrogen atmosphere in embodiments of the present invention is within the above range, the hollow resin particles of the present invention exhibit excellent heat resistance. If the 5% heat weight reduction temperature of the hollow resin particles when heated at a rate of 10°C / min in a nitrogen atmosphere in embodiments of the present invention is outside the above range and too low, the heat resistance may become insufficient.

[0044] Regarding the hollow resin particles in the embodiments of the present invention, the moisture content of the hollow resin particles after standing at 40°C and 95%RH for 96 hours is preferably 0.50% by weight or less, more preferably 0.45% by weight or less, further preferably 0.40% by weight or less, and even more preferably 0.35% by weight or less. The lower the moisture content, the better, preferably 0% by weight or more. If the moisture content of the hollow resin particles after standing at 40°C and 95%RH for 96 hours is within the above range, the effects of the present invention can be further demonstrated. If the moisture content of the hollow resin particles after standing at 40°C and 95%RH for 96 hours is outside the above range and is too high, the water absorption rate of the hollow resin particles may become high.

[0045] In embodiments of the present invention, the hollow resin particles have an ether structure represented by formula (1). Specifically, in embodiments of the present invention, the resin portion of the hollow resin particles has an ether structure represented by formula (1). [Chemistry 3]

[0046] In embodiments of the present invention, the hollow resin particles preferably comprise a polymer (P) having an ether structure represented by formula (1). By comprising such a polymer (P), the hollow resin particles in embodiments of the present invention can further exhibit the effects of the present invention.

[0047] The polymer (P) can be a single type or two or more types.

[0048] As an embodiment of the present invention, the content ratio of polymer (P) in the hollow resin particles is preferably 60% to 100% by weight, more preferably 70% to 100% by weight, and even more preferably 80% to 100% by weight, and even more preferably 90% to 100% by weight, in order to further demonstrate the effects of the present invention.

[0049] In embodiments of the present invention, the hollow resin particles may contain any other suitable components without compromising the effects of the present invention.

[0050] <Polymer (P)> As a polymer (P), if it has an ether structure represented by formula (1), any suitable polymer can be used without impairing the effects of the present invention. In terms of further demonstrating the effects of the present invention, such a polymer (P) is preferably exemplified by a polymer obtained by reacting a compound (A) having an ether structure represented by formula (1) with a monomer (B) that reacts with the compound (A).

[0051] The compound (A) having the ether structure represented by formula (1) may be only one type or more than two types.

[0052] The monomer (B) that reacts with the compound having the ether structure represented by formula (1) may be only one or more.

[0053] Regarding the ratio of compound (A) to monomer (B), when the total amount of compound (A) and monomer (B) is set to 100 parts by weight, the preferred ratio by weight (compound (A): monomer (B)) is (20 parts by weight to 100 parts by weight): (80 parts by weight to 0 parts by weight).

[0054] As one of the preferred embodiments described above, it is more preferably (50 parts by weight to 90 parts by weight): (50 parts by weight to 10 parts by weight), further preferably (55 parts by weight to 80 parts by weight): (45 parts by weight to 20 parts by weight), and even more preferably (60 parts by weight to 70 parts by weight): (40 parts by weight to 30 parts by weight).

[0055] As another embodiment of the above preferred ratio, it is more preferably (20 parts by weight to 80 parts by weight): (80 parts by weight to 20 parts by weight), further preferably (30 parts by weight to 70 parts by weight): (70 parts by weight to 30 parts by weight), and even more preferably (40 parts by weight to 60 parts by weight): (60 parts by weight to 40 parts by weight).

[0056] If the content of compound (A) is too low and outside the above range, the heat resistance may become insufficient.

[0057] As compound (A), if it has the ether structure represented by formula (1), any suitable compound may be used within the scope of not impairing the effects of the present invention. In terms of further demonstrating the effects of the present invention, such compound (A) is preferably polyphenylene ether. Commercially available polyphenylene ethers include, for example, those under the trade names "NORYL" (manufactured by SABIC Corporation), "Lupiace" (manufactured by Mitsubishi Chemical Corporation), "Zylon" (manufactured by Asahi Kasei Corporation), and "OPE-2St" (manufactured by Mitsubishi Gas Chemical Corporation).

[0058] In terms of compatibility with the following non-reactive solvents and the ease with which hollow resin particles with excellent heat resistance can be prepared, polyphenylene ether is preferably an oligomer, and preferably has a number average molecular weight (Mn) of 500 to 3500.

[0059] Examples of monomers (B) include crosslinking monomers and monofunctional monomers. From the perspective of further demonstrating the effects of the present invention, monomers that react with the terminal groups of compound (A) are preferred.

[0060] Examples of crosslinking monomers 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'-ethylenebis(meth)acrylamide; polyfunctional allyl derivatives such as diallylamine and tetraallyloxyethane; and aromatic crosslinking monomers such as divinylbenzene, divinylnaphthalene, and diallyl phthalate. From the perspective of further demonstrating the effects of the present invention, the crosslinking monomer is preferably an aromatic crosslinking monomer, and more preferably divinylbenzene. There may be only one type of crosslinking monomer, or there may be two or more types.

[0061] Examples of monofunctional monomers include: methyl methacrylate, ethyl methacrylate, butyl methacrylate, cetyl methacrylate, and other alkyl methacrylates (1-16 carbon atoms); 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 maleate, dimethyl fumarate, and diethyl fumarate; maleic anhydride; N-vinylcarbazole; and (meth)acrylonitrile. From the perspective of further demonstrating the effects of the present invention, the monofunctional monomer is preferably an aromatic monofunctional monomer, and more preferably styrene or ethylvinylbenzene. There may be only one monofunctional monomer, or there may be two or more monofunctional monomers.

[0062] Polymers (P) can be formed, in a typical sense, by the reaction of a compound (A) and a monomer (B).

[0063] The reaction between compound (A) and monomer (B) can be carried out by any suitable reaction without impairing the effects of the present invention. Such a reaction is preferably a suspension polymerization reaction.

[0064] In suspension polymerization, typically, an oil phase is added to an aqueous phase to suspend it and carry out the polymerization reaction. The aqueous or oil phase may contain any suitable solvent without impairing the effects of the invention. Examples of such solvents include aqueous media or non-reactive solvents as described below. There may be only one solvent or two or more.

[0065] When reacting compound (A) with monomer (B), any suitable additive (C) other than either compound (A) or monomer (B) may be used, without impairing the effects of the present invention. Additive (C) may be only one type or two or more types. The term "additive" as used herein does not include solvents such as aqueous media or non-reactive solvents as described below.

[0066] The content ratio of additive (C) relative to the total amount of compound (A) and monomer (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.

[0067] As additive (C), any suitable additive may be used without impairing the effects of the present invention. Examples of such additive (C) include non-crosslinked polymers, dispersing stabilizers, surfactants, and polymerization initiators.

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

[0069] As a non-crosslinked polymer, examples 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 solubility in monomer compositions, it is preferable to use crystalline polyolefins with side chains of long-chain alpha-olefins as raw materials, low molecular weight polyolefins or olefin oligomers manufactured by metallocene catalysts.

[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] 1-2. Specific Dielectric Constant of Hollow Resin Particles In embodiments of the present invention, the specific dielectric constant of the hollow resin particles is preferably 1.0 to 2.5, more preferably 1.0 to 2.4, and even more preferably 1.0 to 2.3. If the specific dielectric constant 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. In embodiments of the present invention, when the specific dielectric constant of the hollow resin particles exceeds 2.5, even if the hollow resin particles are mixed in, for example, a thermosetting resin, a sufficiently low dielectric constant cannot be obtained.

[0075] The specific permittivity of the hollow resin particles in the embodiments of the present invention can be calculated, for example, by referring to "Dielectric Constant of Mixed Systems" (Applied Physics, Vol. 27, No. 8 (1958)). When the specific permittivity of the mixture of the dispersion medium and hollow resin particles is set as ε, the specific permittivity of the substrate (e.g., a resin composition such as polyimide or epoxy resin) used as the dispersion medium is set as ε1, the specific permittivity of the hollow resin particles is set as ε2, and the volume fraction of the hollow resin particles in the mixture is set as ϕ, the following formula holds. That is, if ε, ε1, and ϕ are obtained experimentally, the specific permittivity ε2 of the hollow resin particles can be calculated. [Number 1]

[0076] Furthermore, the volume fraction ϕ of the hollow resin particles in the mixture of the dispersion medium and the hollow resin particles can be calculated as follows. [Number 2]

[0077] The density of the hollow resin particles can be determined experimentally using a specific gravity bottle (KOTEC Co., Ltd., TQC 50 mL specific gravity bottle) and the product name "ARUFON (trademark) UP-1080" (manufactured by Dong-A Synthetic Co., Ltd., density 1.05 g / cm3), which is a liquid polymer. Specifically, hollow resin particles and ARUFON UP-1080 are mixed and defoamed using a planetary stirrer (KURABO Co., Ltd., "MAZERUSTAR KK-250") to prepare an evaluation mixture, with the ratio of hollow resin particles being 10% by weight. The evaluation mixture is then filled into a 50 mL specific gravity bottle, and the weight of the filled specific gravity bottle is calculated by subtracting the weight of the empty specific gravity bottle from the weight of the bottle filled with the mixture. Based on this value, the density of the hollow resin particles can be calculated using the following formula. [Number 3]

[0078] 1-3. Applications of Hollow Resin Particles Hollow resin particles, as embodiments of the present invention, can be used in a variety of applications requiring heat resistance. Examples of such applications include coating compositions, cosmetics, paper coating compositions, heat insulation compositions, light diffusing compositions, light diffusing films, and semiconductor components (e.g., semiconductor packages or semiconductor modules).

[0079] <Resin Compositions for Semiconductor Components> The hollow resin particles in the embodiments of the present invention exhibit excellent heat resistance and can achieve low dielectric constant and low dielectric loss tangent, thus making them suitable for resin compositions for semiconductor components.

[0080] The resin composition for semiconductor components according to embodiments of the present invention comprises hollow resin particles according to embodiments of the present invention.

[0081] The term "semiconductor component" refers to a component that constitutes a semiconductor, such as a semiconductor package or semiconductor module. In this specification, the term "resin composition for semiconductor components" refers to a resin composition used in semiconductor components.

[0082] The term "semiconductor packaging" refers to a product that uses an IC chip as an essential component and is constructed using at least one of the following components: molding resin, underfill material, molding underfill material, die bond material, prepreg for semiconductor packaging substrate, metal foil laminate for semiconductor packaging substrate, and additive material for printed circuit board for semiconductor packaging.

[0083] The term "semiconductor module" refers to a device that uses semiconductor packaging as an essential component and is constructed using at least one of the following components: prepreg for printed circuit boards, metal foil laminate for printed circuit boards, add-in material for printed circuit boards, solder resist, cover film, electromagnetic wave shielding film, and bonding pad for printed circuit boards.

[0084] <Coating Composition> In embodiments of the present invention, hollow resin particles can impart an excellent appearance to coatings containing them, and are therefore applicable to coating compositions.

[0085] The coating composition of the embodiments of the present invention comprises hollow resin particles of the embodiments of the present invention.

[0086] 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.

[0087] 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 dispersible in water. Specifically, examples of adhesive resins include: acrylic resins, alkyd resins, polyester resins, polyurethane resins, chlorinated polyolefin resins, and amorphous polyolefin resins.

[0088] As a UV-curable resin, any suitable UV-curable resin can be used within the scope of not impairing the effects of the present invention. Examples of such UV-curable 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-cyclohexanetetra(meth)acrylate, pentaglycerol triacrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol triacrylate, and tripentaerythritol hexaacrylate.

[0089] 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 content ratio depending on the purpose. Typically, relative to the total amount of hollow resin particles selected from at least one selected from adhesive resins (in the case of emulsion-type waterborne resins, converted to solids content) and UV-curing resins 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.

[0090] When using UV-curable resins, it is preferable to use a photopolymerization initiator in conjunction with the resin. Any suitable photopolymerization initiator can be used without impairing the effects of the present invention. Examples of such photopolymerization initiators include: acetophenones, benzoin derivatives, benzophenones, phosphine oxides, ketals, α-hydroxyalkylphenyl ketones, α-aminoalkylphenyl ketones, anthraquinones, and 9-oxosulfuron. 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-acetylgoxime esters.

[0091] The coating composition of embodiments of the present invention may also 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.

[0092] As a solvent, any suitable solvent may be used within the scope of not impairing the effects of the present invention. Preferably, such a solvent is one capable of dissolving or dispersing the adhesive resin or UV-curing 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. For water-based coatings, examples include water and alcohols.

[0093] The coating composition of the embodiments of the present invention can also be diluted as needed to adjust the viscosity. Any suitable diluent can be used as needed. Examples of such diluents include the solvents described above. There may be only one diluent, or there may be two or more diluents.

[0094] The coating composition of the embodiments of the present invention may also 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.

[0095] When forming a coating film using the coating composition of the embodiments of the present invention, any suitable coating method may be adopted as needed. Examples of such coating methods include: spray coating, roller coating, brush coating, reverse roller coating, gravure coating, die coating, corner wheel coating, and spraying.

[0096] When forming a coating film using the coating composition of the embodiments of the present invention, any suitable forming method may be adopted as needed. For example, such a forming method may be described as follows: applying the coating to any surface of a substrate to form a coating film, drying the coating film, and then, if necessary, hardening the coating film to form a coating film. Examples of substrates may include: metal, wood, glass, and plastics (PET (polyethylene terephthalate), PC (polycarbonate), acrylic resin, TAC (triacetyl cellulose), etc.).

[0097] <Insulating Resin Composition> The hollow resin particles in embodiments of the present invention can impart excellent thermal insulation properties to coatings containing them, and are therefore applicable to thermal insulation resin compositions. Coatings containing the hollow resin particles in embodiments of the present invention exhibit excellent reflectivity in the wavelength range from ultraviolet to near-infrared light.

[0098] The heat-insulating resin composition of the embodiments of the present invention comprises hollow resin particles of the embodiments of the present invention.

[0099] The 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.

[0100] The heat-insulating resin composition of the embodiments of the present invention may also contain a solvent. Regarding the solvent, the above description of the coating composition can be referenced.

[0101] The insulating resin composition of the embodiments of the present invention can be diluted as needed to adjust the viscosity. The above description of the coating composition can be used as a diluent.

[0102] The heat-insulating resin composition of the embodiments of the present invention may include 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.

[0103] The above description of the coating composition can be used as a reference for the application method and formation method when forming a coating film using the heat-insulating resin composition according to the embodiments of the present invention.

[0104] <Light-diffusing resin composition> In embodiments of the present invention, hollow resin particles can impart excellent light diffusivity to coatings containing them, and are therefore suitable for light-diffusing resin compositions.

[0105] The light-diffusing resin composition of the embodiments of the present invention comprises hollow resin particles of the embodiments of the present invention.

[0106] 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.

[0107] The light-diffusing resin composition of embodiments of the present invention may also contain a solvent. Regarding solvents, the above description of the coating composition can be referenced.

[0108] The light-diffusing resin composition of the embodiments of the present invention can be diluted as needed to adjust the viscosity. The above description of the coating composition can be used as a diluent.

[0109] The light-diffusing 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.

[0110] The above description of the coating composition can be used as a reference for the coating method and the formation method when forming a coating film using the light-diffusing resin composition according to the embodiments of the present invention.

[0111] <Light diffusion film> In the embodiments of the present invention, hollow resin particles can impart excellent light diffusion properties to films containing such coatings, and therefore can also be applied to light diffusion films.

[0112] The light diffusion film of the embodiments of the present invention comprises hollow resin particles of the embodiments of the present invention.

[0113] 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 be the outermost layer of the light diffusion film, or it may not be the outermost layer. The light diffusion film of the present invention may also include any other suitable layers as needed. 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.

[0114] 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).

[0115] 2. Manufacturing Method of Hollow Resin Particles The method for manufacturing hollow resin particles in an embodiment of the present invention involves reacting 20 to 100 parts by weight of a compound (A) having an ether structure represented by formula (1) and 80 to 0 parts by weight of a monomer (B) reacting with the compound (A) (the total amount of the compound (A) and the monomer (B) is 100 parts by weight) in an aqueous medium in the presence of a non-reactive solvent. [Chemistry 4]

[0116] The hollow resin particles of the embodiments of the present invention can be easily manufactured by the above manufacturing method.

[0117] Hollow resin particles, as described in this invention, can be obtained by reacting compound (A) and monomer (B) in an aqueous medium in the presence of a non-reactive solvent. Typically, the hollow resin particles of this invention can be manufactured by feeding compound (A) and monomer (B) into a suspension polymerization reaction.

[0118] As for suspension polymerization, it is typically a suspension polymerization using an aqueous phase containing an aqueous medium and an oil phase containing compound (A), monomer (B) and a non-reactive solvent. Preferably, an oil phase containing compound (A), monomer (B) and a non-reactive solvent is added to the aqueous phase containing the aqueous medium, and the mixture is dispersed and heated to carry out suspension polymerization.

[0119] If the dispersion allows the oil phase to exist in the aqueous phase as droplets, then any suitable dispersion method can be used without compromising the effects of the present invention. A representative example of such a dispersion method is the use of a homogenizer or homogenizer, such as a Polytron homogenizer, an ultrasonic homogenizer, or a high-pressure homogenizer.

[0120] If 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 80°C.

[0121] If the polymerization time is suitable for suspension polymerization, any appropriate polymerization time can be used without compromising the effects of the present invention. A preferred polymerization time is 1 hour to 48 hours.

[0122] A suitable treatment is to perform a post-polymerization heating system to obtain hollow resin particles with high finish.

[0123] The temperature at which subsequent heating is preferably performed after polymerization can be any suitable temperature within the range that does not impair the effects of the present invention. This subsequent heating temperature is preferably 70°C to 120°C.

[0124] The subsequent heating after polymerization can be performed for any appropriate time without compromising the effects of the invention. This subsequent heating time is preferably 1 hour to 24 hours.

[0125] As for compounds (A) and monomers (B), the descriptions in the section on <Polymers (P)> of "1-1. Structure and Properties of Hollow Resin Particles" in "1. Hollow Resin Particles" can be directly quoted.

[0126] As for the ratio of compound (A) to monomer (B), the description in the section "Polymer (P)" of "1-1. Structure and Properties of Hollow Resin Particles" in "1. Hollow Resin Particles" can be directly quoted.

[0127] Examples of aqueous media include water and mixtures of water with lower alcohols (methanol, ethanol, etc.).

[0128] The amount of aqueous medium used can be any appropriate amount without impairing the effects of the present invention. This amount of aqueous medium is representative of suspension polymerization reactions in which an oil phase is added to an aqueous phase to suspend it. The appropriate amount for this reaction is, relative to the total weight of compound (A), monomer (B), and non-reactive solvent, 100 parts by weight, preferably 100 to 5000 parts by weight, and more preferably 150 to 2000 parts by weight.

[0129] The non-reactive solvent is a solvent in which neither the compound (A) having the ether structure represented by formula (1) nor the monomer (B) reacting with compound (A) undergoes a chemical reaction, preferably an organic solvent. The non-reactive solvent typically functions as a cavitation agent providing space for the particles. Examples of non-reactive solvents include: heptane, hexane, cyclohexane, methyl acetate, ethyl acetate, methyl ethyl ketone, chloroform, and carbon tetrachloride. For ease of removal from hollow resin particles, the boiling point of the non-reactive solvent is preferably below 100°C.

[0130] The non-reactive solvent used as a cavitation agent can be a single solvent or a mixture of solvents.

[0131] As for the amount of non-reactive solvent added, it is preferably 20 to 250 parts by weight relative to 100 parts by weight of the total amount of compound (A) and monomer (B).

[0132] When reacting compound (A) with monomer (B), any suitable additive (C) that is not equivalent to either compound (A) or monomer (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 term "additive" here does not include solvents such as aqueous media or non-reactive solvents.

[0133] As for the content ratio of additive (C), relative to the total amount of compound (A) and monomer (B), it 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.

[0134] As additive (C), any suitable additive may be used without impairing the effects of the present invention. Examples of such additive (C) include: non-crosslinked polymers, dispersing stabilizers, surfactants, and polymerization initiators.

[0135] For non-crosslinked polymers, you can directly refer to the description in the section "Polymers (P)" of "1-1. Structure and Properties of Hollow Resin Particles" in "1. Hollow Resin Particles".

[0136] Examples of dispersing stabilizers include polyvinyl alcohol, polycarboxylic acids, cellulose derivatives (hydroxyethyl cellulose, carboxymethyl cellulose, etc.), and polyvinylpyrrolidone. Additionally, inorganic water-soluble polymers such as sodium tripolyphosphate can also be used. Furthermore, water-insoluble inorganic compounds such as calcium phosphate, magnesium phosphate, aluminum phosphate, and zinc phosphate can also be used; pyrophosphates such as calcium pyrophosphate, magnesium pyrophosphate, aluminum pyrophosphate, and zinc pyrophosphate can also be used; and water-poorly soluble inorganic compounds such as calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilate, calcium sulfate, barium sulfate, and colloidal silica can also be used. Considering that magnesium pyrophosphate is easier to remove from hollow resin particles and less likely to remain on the surface of hollow resin particles, it is preferable to use magnesium pyrophosphate.

[0137] Regarding the amount of dispersant stabilizer added, it is preferably 0.5 to 10 parts by weight relative to 100 parts by weight of the aqueous medium. There may be only one type of dispersant stabilizer or two or more types.

[0138] Examples of surfactants include anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants.

[0139] Examples of anionic surfactants include: non-reactive anionic surfactants such as alkyl sulfate salts, alkyl phosphate salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfonates, alkyl diphenyl ether sulfonates, dialkyl sulfosuccinates, monoalkyl sulfosuccinates, and polyoxyethylene alkylphenyl ether phosphates; and reactive anionic surfactants such as polyoxyethylene-1-(allyloxymethyl)alkyl ether sulfate ammonium salt, polyoxyethylene alkylpropylene phenyl ether sulfate ammonium salt, and polyoxyethylene alkylalkenyl ether ammonium sulfate. Furthermore, surfactants are not limited to salt structures; for example, alkyl sulfates or alkyl phosphates can also be used. Specifically, lauryl sulfate or lauryl phosphate can be cited as examples.

[0140] Examples of cationic surfactants include alkyl trimethylammonium salts, alkyl triethylammonium salts, dialkyl dimethylammonium salts, dialkyl diethylammonium salts, N-polyoxyalkyl-N,N,N-trialkylammonium salts, and other cationic surfactants.

[0141] Examples of amphoteric surfactants include lauryl dimethylamine oxide, phosphate salts, and phosphite-based surfactants.

[0142] Nonionic surfactants include, for example: polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polysorbitan fatty acid esters, polyoxyethylene alkylamines, glycerol fatty acid esters, ethylene-oxypropylene block polymers, etc.

[0143] Regarding the amount of surfactant added, it is preferably 0.01% to 5% by weight relative to the total amount of compound (A), monomer (B), and non-reactive solvent. There may be only one type of surfactant or two or more types.

[0144] Furthermore, if the surfactant content ratio is increased, it is easier to construct a porous structure as shown in Figure 1(c), where the hollow portion inside the particle is open to the outside in a portion of the particle surface, or a structure as shown in Figure 1(d), which includes a shell and a hollow portion surrounded by the shell, wherein the hollow portion is a porous structure. Therefore, by controlling the surfactant content ratio, the structure of the hollow resin particles in the embodiments of the present invention can be controlled.

[0145] As polymerization initiators, any suitable polymerization initiator may be used within the scope that does not impair 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 (2-ethylhexanoate), di-tert-butyl peroxide, and other organic peroxides; and azo compounds such as 2,2'-azobisisobutyronitrile, 1,1'-azobiscyclohexanenitrile, and 2,2'-azobis(2,4-dimethylpentanonitrile).

[0146] The preferred ratio of the polymerization initiator to the total amount of compound (A) and monomer (B) is 0.1% to 5% by weight. The polymerization initiator may be a single type or two or more types. [Example]

[0147] The present invention will be specifically described below with reference to specific embodiments, but the present invention is not limited to these embodiments. Furthermore, unless otherwise specified, "parts" means "parts by weight" and "%" means "% by weight".

[0148] <Determination of Volume Average Particle Size (Examples 1-10, 13, Comparative Example 1)> The volume-average particle size was determined using the Coulter method as shown below. The volume-average particle size was measured using a Coulter Multisizer 3 (a measuring device manufactured by Beckman Coulter, Inc.). The measurement was performed using the aperture calibrated according to the user manual for the Multisizer 3 issued by Beckman Coulter, Inc. Furthermore, the pore size used for measurement should be appropriately selected based on the size of the particles being measured. For particles with an assumed volume average diameter of 1 μm to 10 μm, a pore size of 50 μm is selected; for particles with an assumed volume average diameter greater than 10 μm and less than 30 μm, a pore size of 100 μm is selected; for particles with an assumed volume average diameter greater than 30 μm and less than 90 μm, a pore size of 280 μm is selected; and for particles with an assumed volume average diameter greater than 90 μm and less than 150 μm, a pore size of 400 μm is selected. If the measured volume average diameter differs from the assumed volume average diameter, a pore size of suitable size is used, and the measurement is performed again. Current and Gain are appropriately set based on the selected pore size. For example, when selecting an aperture with a size of 50 μm, the Current (aperture current) is set to -800 and the Gain is set to 4; when selecting an aperture with a size of 100 μm, the Current (aperture current) is set to -1600 and the Gain is set to 2; when selecting apertures with sizes of 280 μm and 400 μm, the Current (aperture current) is set to -3200 and the Gain is set to 1. As the sample for the assay, 0.1 g of particles were dispersed in 10 ml of a 0.1 wt% nonionic surfactant aqueous solution using a touch mixer (Yamato Scientific Inc., "TOUCH MIXER MT-31") and an ultrasonic cleaner (VELVO-CLEAR Inc., "ULTRASONIC CLEANER VS-150") to prepare a dispersion. During the assay, the mixture was stirred slowly to the point where no air bubbles entered the beaker, and the assay ended when 100,000 particles were measured. Furthermore, the volume average particle size was calculated as the arithmetic mean of the volume-based particle size distribution of 100,000 particles.

[0149] <Determination of Average Particle Size (Examples 11, 12)> The Z-average particle diameter of the hollow resin particles or particles is measured by dynamic light scattering method, and the measured Z-average particle diameter is used as the average particle diameter of the obtained hollow resin particles or particles. That is, first, the obtained slurry-like hollow resin particles or particles are diluted with ion-exchanged water, laser light is irradiated onto the aqueous dispersion adjusted to 0.1% by weight, and the intensity of the scattered light scattered from the hollow resin particles or particles is measured with time variation in microsecond units. Subsequently, the scattering intensity distribution caused by the detected hollow resin particles or particles is applied to a normal distribution, and the Z-average particle diameter of the hollow resin particles or particles is obtained by the cumulative analysis method for calculating the average particle diameter. The measurement of the Z-average particle diameter can be easily carried out by a commercially available particle diameter measuring device. In the following Examples and Comparative Examples, the Z-average particle diameter was measured using a particle diameter measuring device (manufactured by Malvern Instruments Ltd., "Zetasizer Nano ZS"). Usually, commercially available particle diameter measuring devices are equipped with data analysis software, and the data analysis software automatically analyzes the measurement data, whereby the Z-average particle diameter can be calculated.

[0150] <Cross-sectional observation> A cured product is obtained by mixing the dried particles with a photocurable resin D-800 (manufactured by JEOL Ltd.) and irradiating ultraviolet light. Thereafter, the cured product is cut with pliers, the cross-sectional portion is processed smoothly using a cutter, and a sample is coated using a sputtering device "Auto-Fine Coater JFC-1300" manufactured by JEOL Ltd. Next, the cross-section of the sample is photographed using a secondary electron detector of a scanning electron microscope "SU1510" manufactured by Hitachi High-Technologies Corporation.

[0151] <TEM measurement: Observation of the presence or absence of hollow and the shape of the hollow resin particles or particles> For the hollow resin particles or particles as dry powder, surface treatment (10 Pa, 5 mA, 10 seconds) is performed using a coating device "Osmium Film Coater Neoc-Pro" manufactured by Meiwa Fosis Co., Ltd. Next, the hollow resin particles or particles are observed by TEM (transmission electron microscope, "H-7600" manufactured by Hitachi High-Technologies Corporation) to confirm the presence or absence of hollow and the shape of the hollow resin particles or particles. At this time, the acceleration voltage is set to 80 kV and the magnification is set to 5000 times or 10,000 times for photographing.

[0152] <Measurement of the 5% thermogravimetric reduction temperature when heating at 10 °C per minute in a nitrogen atmosphere> The 5% thermogravimetric reduction temperature was measured using a differential thermal-thermogravimetric simultaneous measurement device (TG / DTA6200, AST-2) manufactured by Seiko Nanotech Co., Ltd. The sampling method and temperature conditions are as follows. A sample of 10.5 ± 0.5 mg was filled seamlessly into the bottom of a platinum measuring vessel as the test sample. The 5% thermogravimetric decrease (TW) temperature was determined using alumina as a reference material at a nitrogen flow rate of 230 mL / min. The TG / DTA curve was obtained by heating the sample from 30°C to 500°C at a rate of 10°C / min. Based on the obtained curve, the temperature at which the weight decreased by 5% was calculated using the analytical software provided with the apparatus and was taken as the 5% TW temperature.

[0153] [Example 1] An oil phase was prepared by mixing a difunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Co., Ltd.) having the ether structure represented by formula (1), 2.5 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical Materials Co., Ltd., 81% content, 19% ethylvinylbenzene (EVB)), 5.0 g of heptane, 0.05 g of 2,2'-azobis(2,4-dimethylpentanonitrile) (trade name "V-65", manufactured by Fujifilm and Wako Pure Chemical Co., Ltd.) as a polymerization initiator, and 0.004 g of lauryl phosphate. An oil phase was added to 32 g of a 2% by weight aqueous dispersion of magnesium pyrophosphate as the aqueous phase, and a suspension was prepared using a Polytron homogenizer "PT10-35" (manufactured by Central Scientific Trading Co., Ltd.). The resulting suspension was heated at 50°C for 24 hours to carry out the reaction. Hydrochloric acid was added to the resulting slurry to decompose the magnesium pyrophosphate. The solid components were separated by filtration and dehydration. After repeated washing with water for purification, the slurry was dried at 60°C to obtain particles (1). A cross-sectional photograph of the obtained particle (1) is shown in Figure 2. It is confirmed that the obtained particle (1) is a mixture of hollow resin particles containing a hollow region surrounded by a shell and hollow resin particles containing a porous structure surrounded by a shell. The average particle size of the obtained particles (1) is 16.3 μm. The resulting particles (1) had a 5% decrease in thermal weight at a temperature of 306°C when heated at 10°C / min in a nitrogen atmosphere. The allocation quantities are shown in Table 1.

[0154] [Example 2] The difunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Co., Ltd.) having the ether structure represented by formula (1) was set at 3.0 g, and divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical Materials Co., Ltd., 81% content, 19% ethylvinylbenzene (EVB)) was set at 2.0 g. Otherwise, the same procedure as in Example 1 was performed to obtain particles (2). A cross-sectional photograph of the obtained particle (2) is shown in Figure 3. It is confirmed that the obtained particle (2) is a hollow resin particle surrounded by a shell and containing a hollow region. The average particle size of the obtained particles (2) is 15.2 μm. The resulting particles (2) had a 5% reduction in thermal weight at a temperature of 320°C when heated at 10°C / min in a nitrogen atmosphere. The allocation quantities are shown in Table 1.

[0155] [Example 3] The difunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Co., Ltd.) having the ether structure represented by formula (1) was set at 3.5 g, and divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical Materials Co., Ltd., 81% content, 19% ethylvinylbenzene (EVB)) was set at 1.5 g. Otherwise, the same procedure as in Example 1 was performed to obtain particles (3). A cross-sectional photograph of the obtained particle (3) is shown in Figure 4. It is confirmed that the obtained particle (3) is a hollow resin particle surrounded by a shell and containing a hollow region. The average particle size of the obtained particles (3) is 13.9 μm. The resulting particles (3) had a 5% decrease in thermal weight at a temperature of 309°C when heated at 10°C / min in a nitrogen atmosphere. The allocation quantities are shown in Table 1.

[0156] [Example 4] Using 2.5 g of reactive low molecular weight polyphenylene ether (trade name "Noryl (registered trademark) SA9000-111 resin", manufactured by SABIC Corporation) as a compound having the ether structure represented by formula (1), instead of 2.5 g of difunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Corporation) as a compound having the ether structure represented by formula (1), the same procedure as in Example 1 was performed to obtain particles (4). A cross-sectional photograph of the obtained particle (4) is shown in Figure 5. It is confirmed that the obtained particle (4) is a hollow resin particle with a porous structure surrounded by a shell. The average particle size of the obtained particles (4) was 16.5 μm. The resulting particles (4) had a 5% reduction in thermal weight at a temperature of 373°C when heated at 10°C / min in a nitrogen atmosphere. The allocation quantities are shown in Table 1.

[0157] [Example 5] Using 3.0 g of reactive low molecular weight polyphenylene ether (trade name "Noryl (registered trademark) SA9000-111 resin", manufactured by SABIC Corporation) which is a compound having the ether structure represented by formula (1), instead of 3.0 g of difunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Corporation) which is a compound having the ether structure represented by formula (1), the same procedure as in Example 2 was performed to obtain particles (5). A cross-sectional photograph of the obtained particle (5) is shown in Figure 6. It is confirmed that the obtained particle (5) is a hollow resin particle with a porous structure surrounded by a shell. The average particle size of the obtained particles (5) is 15.6 μm. The resulting particles (5) had a 5% reduction in thermal weight at a temperature of 420°C when heated at 10°C / min in a nitrogen atmosphere. The allocation quantities are shown in Table 1.

[0158] [Example 6] No lauryl phosphate 0.004 g was added to the oil phase. Instead of the 32 g of magnesium pyrophosphate 2% aqueous dispersion as the aqueous phase, 30 g of 1.5% aqueous solution of polyvinyl alcohol (GH-14L) was used. Otherwise, the process was the same as in Example 1 to obtain particles (6). A cross-sectional photograph of the obtained particle (6) is shown in Figure 7. It is confirmed that the obtained particle (6) is a mixture of hollow resin particles containing a hollow region surrounded by a shell and hollow resin particles containing a porous structure surrounded by a shell. The average particle size of the obtained particles (6) was 20.7 μm. The resulting particles (6) had a 5% decrease in thermal weight at a temperature of 302°C when heated at 10°C / min in a nitrogen atmosphere. The allocation quantities are shown in Table 1.

[0159] [Example 7] No lauryl phosphate 0.004 g was added to the oil phase. Instead of the 32 g of magnesium pyrophosphate 2% aqueous dispersion as the aqueous phase, 30 g of 1.5% aqueous solution of polyvinyl alcohol (GH-14L) was used. Otherwise, the process was the same as in Example 2 to obtain particles (7). A cross-sectional photograph of the obtained particle (7) is shown in Figure 8. It is confirmed that the obtained particle (7) is a hollow resin particle surrounded by a shell and containing a hollow region. The average particle size of the obtained particles (7) is 18.3 μm. The resulting particles (7) had a 5% reduction in thermal weight at a temperature of 315°C when heated at 10°C / min in a nitrogen atmosphere. The allocation quantities are shown in Table 1.

[0160] [Example 8] No lauryl phosphate 0.004 g was added to the oil phase. Instead of the 32 g of magnesium pyrophosphate 2% aqueous dispersion as the aqueous phase, 30 g of 1.5% aqueous solution of polyvinyl alcohol (GH-14L) was used. Otherwise, the process was the same as in Example 5 to obtain particles (8). A cross-sectional photograph of the obtained particle (8) is shown in Figure 9. It is confirmed that the obtained particle (8) is a hollow resin particle with a porous structure surrounded by a shell. The average particle size of the obtained particles (8) was 19.4 μm. The resulting particles (8) had a 5% decrease in thermal weight at a temperature of 411°C when heated at 10°C / min in a nitrogen atmosphere. The allocation quantities are shown in Table 1.

[0161] [Example 9] Using 1.8 g of reactive low molecular weight polyphenylene ether (trade name "Noryl (registered trademark) SA9000-111 resin", manufactured by SABIC Corporation) as a compound having the ether structure represented by formula (1), 1.2 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical Materials Co., Ltd., 81% content, 19% ethyl vinylbenzene (EVB)), 5.0 g of heptane, and 2.0 g of toluene as a compound having the ether structure represented by formula (1), instead of 2.5 g of difunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Co., Ltd.), 2.5 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical Materials Co., Ltd., 81% content, 19% ethyl vinylbenzene (EVB)), and 5.0 g of heptane, the same procedure as in Example 1 was performed to obtain particles (9). A cross-sectional photograph of the obtained particle (9) is shown in Figure 10. It is confirmed that the obtained particle (9) is a hollow resin particle with a porous structure surrounded by a shell. The average particle size of the obtained particles (9) is 15.1 μm. The resulting particles (9) had a 5% reduction in thermal weight at a temperature of 415°C when heated at 10°C / min in a nitrogen atmosphere. The allocation quantities are shown in Table 1.

[0162] [Example 10] Using 4.0 g of reactive low molecular weight polyphenylene ether (trade name "Noryl (registered trademark) SA9000-111 resin", manufactured by SABIC Corporation) as a compound having the ether structure represented by formula (1), 1.0 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical Materials Co., Ltd., 81% content, 19% ethyl vinylbenzene (EVB)), 4.0 g of heptane, and 1.0 g of cyclohexane instead of 2.5 g of difunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a compound having the ether structure represented by formula (1), 2.5 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical Materials Co., Ltd.), and 5.0 g of heptane, the same procedure as in Example 1 was performed to obtain particles (10). A cross-sectional photograph of the obtained particle (10) is shown in Figure 11. It is confirmed that the obtained particle (10) is a hollow resin particle with a porous structure surrounded by a shell. The average particle size of the obtained particles (10) is 13.1 μm. The resulting particles (10) had a 5% reduction in thermal weight at a temperature of 428°C when heated at 10°C / min in a nitrogen atmosphere. The allocation quantities are shown in Table 1.

[0163] [Example 11] An oil phase was prepared by mixing 1.5 g of a difunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Co., Ltd.) having the ether structure represented by formula (1), 1.5 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical Materials Co., Ltd., 81% content, 19% ethylvinylbenzene (EVB)), 3.0 g of heptane, and 0.09 g of PEROYL L (manufactured by Nippon Oil Co., Ltd.) as a polymerization initiator. Next, 34 g of ion-exchanged water was mixed with 0.0128 g of RAPISOL A-80 (Nippon Oil Co., Ltd.) to prepare an aqueous phase. An oil phase was added to the aqueous phase, and a suspension was prepared using an ultrasonic homogenizer (BRANSON Corporation, "SONIFIER450", conditions: duty cycle = 50%, output control = 5, processing time 3 minutes). The resulting suspension was reacted by heating at 70°C for 4 hours. The resulting slurry was heated at 100°C for 24 hours to obtain dried particles (11). The TEM image of the obtained particle (11) is shown in Figure 12. It is confirmed that the obtained particle (11) is a hollow resin particle with a porous structure surrounded by a shell. The average particle size of the obtained particles (11) is 320 nm. The resulting particles (11) had a 5% reduction in thermal weight at a temperature of 315°C when heated at 10°C / min in a nitrogen atmosphere. The allocation quantities are shown in Table 1.

[0164] [Example 12] An oil phase was prepared by mixing 1.08 g of reactive low molecular weight polyphenylene ether (trade name "Noryl (registered trademark) SA9000-111 resin", manufactured by SABIC Corporation, which is a compound having the ether structure represented by formula (1), 0.72 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical Materials Co., Ltd., 81% of the product, 19% of which is ethyl vinylbenzene (EVB)), 3.0 g of heptane, 1.2 g of toluene, and 0.03 g of PEROYL L (manufactured by Nippon Oil Co., Ltd.) as a polymerization initiator. Next, 34 g of ion-exchanged water was mixed with 0.0085 g of RAPISOL A-80 (Nippon Oil Co., Ltd.) to prepare an aqueous phase. An oil phase was added to the aqueous phase, and a suspension was prepared using an ultrasonic homogenizer (BRANSON Corporation, "SONIFIER450", conditions: duty cycle = 50%, output control = 5, processing time 3 minutes). The resulting suspension was reacted by heating at 70°C for 4 hours. The resulting slurry was heated at 100°C for 24 hours to obtain dried particles (12). The TEM image of the obtained particle (12) is shown in Figure 13. It is confirmed that the obtained particle (12) is a hollow resin particle with a porous structure surrounded by a shell. The average particle size of the obtained particles (12) is 379 nm. The resulting particles (12) had a 5% reduction in thermal weight at a temperature of 399°C when heated at 10°C / min in a nitrogen atmosphere. The allocation quantities are shown in Table 1.

[0165] [Example 13] 0.15 g of sodium lauryl sulfate was added to the aqueous phase in place of 0.004 g of lauryl phosphate, and the process was otherwise carried out in the same manner as in Example 5 to obtain particles (13). A cross-sectional photograph of the obtained particle (13) is shown in Figure 14. It is confirmed that the obtained particle (13) is a resin particle containing a porous structure. The average particle size of the obtained particles (13) was 5.4 μm. The resulting particles (13) had a 5% reduction in thermal weight at a temperature of 415°C when heated at 10°C / min in a nitrogen atmosphere. The allocation quantities are shown in Table 1.

[0166] [Example 14] 2.0 g of a difunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Co., Ltd.) having the ether structure represented by formula (1) and 3.0 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical Materials Co., Ltd., 81% content, 19% ethylvinylbenzene (EVB)) were obtained, and the same procedure as in Example 1 was performed to obtain particles (14). A cross-sectional photograph of the obtained particle (14) is shown in Figure 15. It is confirmed that the obtained particle (14) is a hollow resin particle with a porous structure surrounded by a shell. The average particle size of the obtained particles (14) was 14.4 μm. The resulting particles (14) had a 5% decrease in thermal weight at a temperature of 312°C when heated at 10°C / min in a nitrogen atmosphere. The allocation quantities are shown in Table 1.

[0167] [Example 15] Using 2.0 g of reactive low molecular weight polyphenylene ether (trade name "Noryl (registered trademark) SA9000-111 resin", manufactured by SABIC Corporation) and 3.0 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical Materials Co., Ltd., 81% content, 19% ethylvinylbenzene (EVB)), which is a compound having the ether structure represented by formula (1), instead of 2.5 g of difunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 2.5 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical Materials Co., Ltd., 81% content, 19% ethylvinylbenzene (EVB)), which is a compound having the ether structure represented by formula (1), the same procedure as in Example 1 was performed to obtain particles (15). A cross-sectional photograph of the obtained particle (15) is shown in Figure 16. It is confirmed that the obtained particle (15) is a hollow resin particle with a porous structure surrounded by a shell. The average particle size of the obtained particles (15) was 12.7 μm. The resulting particles (15) had a 5% decrease in thermal weight at a temperature of 366°C when heated at 10°C / min in a nitrogen atmosphere. The allocation quantities are shown in Table 1.

[0168] [Example 16] Using 1.5 g of reactive low molecular weight polyphenylene ether (trade name "Noryl (registered trademark) SA9000-111 resin", manufactured by SABIC Corporation) and 3.5 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical Materials Co., Ltd., 81% content, 19% ethylvinylbenzene (EVB)), which is a compound having the ether structure represented by formula (1), instead of 2.5 g of difunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 2.5 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical Materials Co., Ltd., 81% content, 19% ethylvinylbenzene (EVB)), which is a compound having the ether structure represented by formula (1), the same procedure as in Example 1 was performed to obtain particles (16). A cross-sectional photograph of the obtained particle (16) is shown in Figure 17. The obtained particle (16) is a hollow resin particle with a porous structure surrounded by a shell. The average particle size of the obtained particles (16) was 10.9 μm. The resulting particles (16) had a 5% decrease in thermal weight at a temperature of 371°C when heated at 10°C / min in a nitrogen atmosphere. The allocation quantities are shown in Table 1.

[0169] [Example 17] Using 1.0 g of reactive low molecular weight polyphenylene ether (trade name "Noryl (registered trademark) SA9000-111 resin", manufactured by SABIC Corporation) and 4.0 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical Materials Co., Ltd., 81% content, 19% ethylvinylbenzene (EVB)), which is a compound having the ether structure represented by formula (1), instead of 2.5 g of difunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 2.5 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical Materials Co., Ltd., 81% content, 19% ethylvinylbenzene (EVB)), which is a compound having the ether structure represented by formula (1), the same procedure as in Example 1 was performed to obtain particles (17). A cross-sectional photograph of the obtained particle (17) is shown in Figure 18. It is confirmed that the obtained particle (17) is a hollow resin particle with a porous structure surrounded by a shell. The average particle size of the obtained particles (17) was 11.3 μm. The resulting particles (17) had a 5% decrease in thermal weight at a temperature of 382°C when heated at 10°C / min in a nitrogen atmosphere. The allocation quantities are shown in Table 1.

[0170] [Comparative Example 1] An oil phase was prepared by mixing 2.5 g of methyl methacrylate, 2.5 g of ethylene glycol dimethacrylate, 5 g of cyclohexane, 0.05 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (trade name "V-65", manufactured by Fujifilm and Koh Genuine Pharmaceutical Co., Ltd.) as a polymerization initiator, and 0.004 g of lauryl phosphate. An oil phase was added to 32 g of a 2% by weight aqueous dispersion of magnesium pyrophosphate as the aqueous phase, and a suspension was prepared using a Polytron PT10-35 homogenizer (manufactured by Central Scientific Trading Co., Ltd.). The resulting suspension was reacted by heating at 50°C for 24 hours. Hydrochloric acid was added to the resulting slurry to decompose the magnesium pyrophosphate. The solid components were separated by filtration and dehydration. After repeated washing with water for purification, the slurry was dried at 60°C to obtain particles (Cl) as a dried powder. A cross-sectional photograph of the obtained particle (C1) is shown in Figure 19. It is confirmed that the obtained particle (C1) is a hollow resin particle surrounded by a shell and containing a hollow region. The average particle size of the obtained particles (C1) was 8.3 μm. The resulting particles (C1) showed a 5% decrease in thermal weight at a temperature of 245°C when heated at a rate of 10°C / min under a nitrogen atmosphere. The allocation quantities are shown in Table 1.

[0171] [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Oil phase (parts by weight) (A) OPE-2St 1200 2.5 3.0 3.5 - - 2.5 3.0 - - SA9000-111 - - - 2.5 3.0 - - 3.0 1.8 (B) DVB810 (DVB: 81%, EVB: 19%) 2.5 2.0 1.5 2.5 2.0 2.5 2.0 2.0 1.2 Methyl methacrylate - - - - - - - - - Ethylene glycol dimethacrylate - - - - - - - - - (A):(B) (weight ratio) 50:50 60:40 70:30 50:50 60:40 50:50 60:40 60:40 60:40 heptane 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Toluene - - - - - - - - 2.0 Cyclohexane - - - - - - - - - V-65 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 PEROYL L - - - - - - - - - Lauryl phosphoric acid 0.004 0.004 0.004 0.004 0.004 - - - 0.004 Aqueous phase (parts by weight) Magnesium pyrophosphate 2% by weight aqueous dispersion 32 32 32 32 32 - - - 32 1.5% by weight aqueous solution of polyvinyl alcohol - - - - - 30 30 30 - Ion-exchanged water - - - - - - - - - A-80 - - - - - - - - - Sodium lauryl sulfate - - - - - - - - - Average particle size (μm) 16.3 15.2 13.9 16.5 15.6 20.7 18.3 19.4 15.1 5% reduction in heat weight at temperature (°C) 306 320 309 373 420 302 315 411 415 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Comparative Example 1 Oil phase (parts by weight) (A) OPE-2St 1200 - 1.5 - - 2.0 - - - - SA9000-111 4.0 - 1.08 3.0 - 2.0 1.5 1.0 - (B) DVB810 (DVB: 81%, EVB: 19%) 1.0 1.5 0.72 2.0 3.0 3.0 3.5 4.0 - Methyl methacrylate - - - - - - - - 2.5 Ethylene glycol dimethacrylate - - - - - - - - 2.5 (A):(B) (weight ratio) 80:20 50:50 60:40 60:40 40:50 40:50 30:70 20:80 - heptane 4.0 3.0 3.0 5.0 5.0 5.0 5.0 5.0 - Toluene - - 1.2 - - - - - - Cyclohexane 1.0 - - - - - - - 5.0 V-65 0.05 - - 0.05 0.05 0.05 0.05 0.05 0.05 PEROYL L - 0.09 0.03 - - - - - - Lauryl phosphoric acid 0.004 - - - 0.004 0.004 0.004 0.004 0.004 Aqueous phase (parts by weight) Magnesium pyrophosphate 2% by weight aqueous dispersion 32 - - 32 32 32 32 32 32 1.5% by weight aqueous solution of polyvinyl alcohol - - - - - - - - - Ion-exchanged water - 34 34 - - - - - - A-80 - 0.0128 0.0085 - - - - - - Sodium lauryl sulfate - - - 0.15 - - - - - Average particle size (μm) 13.1 0.320 0.379 5.4 14.4 12.7 10.9 11.3 8.3 5% reduction in heat weight at temperature (°C) 428 315 399 415 312 366 371 382 245

[0172] <Performance Evaluation 1: Evaluation of Specific Permittivity and Dielectric Loss Tangent 1> 0.4 g of the particles obtained in each example and comparative example were mixed with 10 g of ultra-high heat resistant polyimide varnish (trade name "SPIXAREA HR (registered trademark) 002", manufactured by SOMAR Co., Ltd.) and defoamed using a planetary agitator defoamer (manufactured by KURABO Co., Ltd., "MAZERUSTAR KK-250") to prepare an evaluation mixture. The evaluation mixture was applied to a 5 mm thick glass plate using a coating apparatus set to a wet thickness of 250 μm. The solvent was removed by heating at 120°C for 10 minutes, 180°C for 180 minutes, and 270°C for 60 minutes, followed by cooling to room temperature to obtain a film sample containing the individual particles. The specific permittivity and dielectric loss tangent of the obtained film were evaluated using the cavity resonance method (measurement frequency: 5.8 GHz). The results are shown in Table 2.

[0173] [Table 2] A membrane containing particles (2) of Example 2 A membrane containing particles (5) of Example 5 Membrane without particles (refer to) Specific permittivity 2.64 2.68 3.45 Dielectric loss tangent 0.0290 0.0290 0.0321

[0174] Based on the results in Table 2, it can be confirmed that the hollow resin particles provided by the present invention have the effect of reducing the specific dielectric constant and dielectric loss tangent of the substrate, thus proving effective for the purpose of achieving low dielectric constant and low dielectric loss tangent in semiconductor materials.

[0175] <Performance Evaluation 2: Evaluation of Specific Permittivity and Dielectric Loss Tangent 2> Using a planetary agitator (manufactured by KURABO Co., Ltd., "MAZERUSTAR KK-250"), 0.425 g of particles obtained in the examples and comparative examples, 12.1 g of ethyl acetate, and 1.7 g of solvent-soluble polyimide KPI-MX300F (manufactured by Kawamura Sangyo Co., Ltd.) were defoamed and a mixture for evaluation was prepared. The evaluation mixture was applied to 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 min, 90°C for 10 min, 150°C for 30 min, and 200°C for 30 min. The plate was then cooled to room temperature to obtain a film sample containing all particles. The specific permittivity and dielectric loss tangent of the obtained film were evaluated using the cavity resonance method (measurement frequency: 5.8 GHz). The results are shown in Table 3.

[0176] [Table 3] A membrane containing particles (2) of Example 2 A membrane containing particles (5) of Example 5 A membrane containing particles (C1) of Comparative Example 1 Membrane without particles (refer to) Specific permittivity 1.90 2.01 2.25 2.46 Dielectric loss tangent 0.0060 0.0057 0.0105 0.0093

[0177] Based on the results in Table 3, it can be confirmed that the hollow resin particles provided by the present invention have the effect of reducing the specific dielectric constant and dielectric loss tangent of the substrate, thus proving effective for the purpose of achieving low dielectric constant and low dielectric loss tangent in semiconductor materials.

[0178] <Performance Evaluation 3: Moisture Content Evaluation> The particles obtained in each embodiment and comparative example were subjected to moisture absorption treatment under the following conditions. The particles obtained in each embodiment and comparative example were placed in a constant temperature and humidity bath at 40±1℃ and 95% relative humidity for 96 hours, then removed and cooled for 30 minutes at 20±1℃ and 65±5% relative humidity. After cooling, the moisture content was measured. The moisture content was measured using 0.1 g of particles obtained in each example and comparative example as samples, placed in a "CA-200" Karl von Sobel moisture analyzer and a "VA-236S" moisture vaporization apparatus manufactured by Mitsubishi Chemical ANALYTECH Co., Ltd. The anolyte and catholyte used in the measurement were "AQUAMICRON (registered trademark) AX" and "AQUAMICRON (registered trademark) CXU," respectively, manufactured by Mitsubishi Chemical Co., Ltd. The measurement (vaporization) temperature was 250°C. Nitrogen gas was used as the carrier gas. The carrier gas flow rate was 150 mL / min. The sample was tested three times. The moisture content of the air at the sample sampling point was measured twice, and the average value was used as a blank value. The moisture content (weight %) of the sample was calculated by subtracting the blank value from each measurement result and dividing by the sample weight. The moisture content (weight %) of the sample was calculated using the following formula. Moisture content (wt%) = [Measured moisture content (μg) - Blank moisture content (μg)] ÷ 1,000,000 ÷ Sample weight (g) × 100 As the final result, the average of the three measurements was taken as the moisture content (by weight %) of the sample. The results are shown in Table 4.

[0179] [Table 4] Particles in Example 1 (1) Example 2: Particles (2) Particles in Example 3 (3) Particles in Example 4 (4) Particles in Example 5 (5) Particles in Example 9 (9) Particles in Example 10 (10) Comparative Example 1 particle (C1) Moisture content (weight%) 0.29 0.35 0.42 0.24 0.18 0.49 0.31 3.18

[0180] According to the results in Table 4, the hollow resin particles provided by the present invention have a lower moisture content after moisture absorption treatment compared with the previous hollow resin particles, which is also suitable for achieving the purpose of low dielectric and low dielectric loss tangent in semiconductor materials.

[0181] <Performance Evaluation 4: Thermal Insulation Evaluation> 10 g of commercially available water-based paint (manufactured by ASAHIPEN Co., Ltd., trade name "Water-based Multipurpose Colored Paint") was mixed with 2.5 g of particles (1) obtained in Example 1, and the mixture was defoamed and stirred using a planetary agitator (manufactured by KURABO Co., Ltd., "MAZERUSTAR KK-250") to produce an evaluation paint. The evaluation coating was applied to the black side of the opacity test paper using a coating applicator set to a wet thickness of 250 μm, and then allowed to dry completely at room temperature to obtain a light reflectance evaluation sample plate. The reflectance of the light reflectance evaluation sample plate to ultraviolet, visible, and near-infrared light was evaluated in the following order. The reflectance was measured using a UV-Vis-NIR spectrophotometer (Shimadzu Corporation, Solid Spec3700). The reflectance characteristics (%) of the coated surface of the sample plate used for light reflectance evaluation were measured in the ultraviolet to near-infrared light (wavelength 300 nm to 2500 nm). Furthermore, a 60 mmΦ integrating sphere was used for the measurement, and a SPECTRALON standard white plate was used. The results are shown in Figure 20. As shown in Figure 20, it can be seen that it has a reflectivity of over 40% in almost all wavelengths from ultraviolet to near-infrared light.

[0182] <Performance Evaluation 5: Coating Appearance Evaluation> Two parts by weight of the particles (1) obtained in Example 1 and 20 parts by weight of commercially available acrylic water-based gloss coating (manufactured by KanpeHapio Co., Ltd., trade name "Super Hit") were mixed for 3 minutes using a stirring and defoaming device and then defoamed for 1 minute to obtain a coating composition. The obtained coating composition was applied to an ABS resin (acrylonitrile-butadiene-styrene resin) board using a coating device with a doctor blade having a gap of 75 μm, and then dried to obtain a coating film. Furthermore, a 50 μm matte coating was prepared by blow-coating the obtained coating composition onto an acrylic resin plate with a thickness of 3 mm. No lumps (protrusions) were found in the obtained coating, which exhibited good matte properties.

[0183] <Performance Evaluation 6: Light Diffusion Evaluation> Using a stirring and defoaming device, 7.5 parts by weight of particles (1) obtained in Example 1, 30 parts by weight of acrylic resin (manufactured by DIC Corporation, trade name "Acrydic A811"), 10 parts by weight of crosslinking agent (manufactured by DIC Corporation, trade name "VM-D"), and 50 parts by weight of butyl acetate as solvent were mixed for 3 minutes and defoamed for 1 minute to obtain a light-diffusing resin composition. Using a coating apparatus with a doctor blade having a gap of 50 μm, the obtained light-diffusing resin composition was coated onto a PET film with a thickness of 125 μm, and then dried at 70°C for 10 minutes to obtain a light-diffusing film. The total light transmittance and haze of the light diffusion film were measured using a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., trade name "NDH 2000") in accordance with JIS K 7361-1:1997 and JIS K 7136:2000, respectively. The higher the diffuseness of light passing through the light diffusion film (transmitted light), the higher the haze value. The results showed that the haze was 40.2% and the total light transmittance was 81.5%, confirming that the obtained light diffusion film has excellent light diffusion properties. [Industrial Applicability]

[0184] The hollow resin particles of the embodiments of the present invention, and the hollow resin particles obtained by the manufacturing method of the embodiments of the present invention, can be used in various applications requiring heat resistance. For example, the hollow resin particles of the embodiments of the present invention, and the hollow resin particles obtained by the manufacturing method of the embodiments of the present invention, can be applied to applications such as resin compositions for semiconductor components, coating compositions, heat insulation compositions, light diffusing compositions, and light diffusing films.

Claims

1. A hollow resin particle having a hollow portion within the particle, having an average particle size of 0.1 μm to 100 μm, wherein the hollow resin particle contains 60% to 100% by weight of a polymer (P) having an ether structure represented by formula (1), wherein the polymer (P) is obtained by reacting a monomer (B) with a compound (A), wherein the monomer (B) comprises an aromatic crosslinking monomer and an aromatic monofunctional monomer, and the compound (A) is a polyphenylene ether having a terminal group that reacts with the monomer (B) and an ether structure represented by formula (1), [Chemical 1].

2. The hollow resin particles as claimed in claim 1, wherein the hollow portion is any of the following: comprising a single hollow region, comprising a plurality of hollow regions, and comprising a porous structure.

3. The hollow resin particle as claimed in claim 1 includes a shell and the aforementioned hollow portion surrounded by the shell.

4. The hollow resin particles as claimed in claim 1, wherein the aforementioned aromatic crosslinking monomer system is selected from at least one of the group consisting of divinylbenzene, divinylnaphthalene, and diallyl phthalate.

5. The hollow resin particles as claimed in claim 1, wherein the aforementioned aromatic monofunctional monoparticles are selected from at least one of the group consisting of styrene, α-methylstyrene, ethyl vinylbenzene, vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, vinyl biphenyl, and vinyl naphthalene.

6. Hollow resin particles as claimed in claim 1, wherein the compound (A) is a difunctional polyphenylene ether oligomer with a number average molecular weight of 500 to 3500.

7. The hollow resin particles as claimed in claim 1, wherein the 5% heat weight reduction temperature of the hollow resin particles when heated at 10°C / min in a nitrogen atmosphere is 300°C or higher.

8. Hollow resin particles as claimed in claim 1, used in resin compositions for semiconductor components.

9. Hollow resin particles as claimed in claim 1, used in coating compositions.

10. Hollow resin particles as claimed in claim 1, used in thermal insulation resin compositions.

11. Hollow resin particles as claimed in claim 1, used in light-diffusing resin compositions.

12. Hollow resin particles as requested in item 1, used in a light diffusion film.

13. A resin composition for semiconductor components comprising hollow resin particles as claimed in any one of claims 1 to 7.

14. A coating composition comprising hollow resin particles as claimed in any one of claims 1 to 7.

15. A heat-insulating resin composition comprising hollow resin particles as claimed in any one of claims 1 to 7.

16. A light-diffusing resin composition comprising hollow resin particles as claimed in any one of claims 1 to 7.

17. A light diffusion film comprising hollow resin particles as claimed in any one of claims 1 to 7.

18. A method for manufacturing hollow resin particles, which is a method for manufacturing hollow resin particles as claimed in any one of claims 1 to 12, wherein 80 to 20 parts by weight of monomer (B) and 20 to 80 parts by weight of compound (A) (the total amount of compound (A) and monomer (B) is 100 parts by weight) are reacted in an aqueous medium in the presence of a non-reactive solvent, wherein the monomer (B) comprises an aromatic crosslinking monomer and an aromatic monofunctional monomer, and the compound (A) is a polyphenylene ether having a terminal group that reacts with the monomer (B) and an ether structure represented by formula (1), [Chemical 2].

19. The method for manufacturing hollow resin particles as claimed in claim 18, wherein the aforementioned aromatic crosslinking monomer system is selected from at least one of the group consisting of divinylbenzene, divinylnaphthalene, and diallyl phthalate.

20. The method for manufacturing hollow resin particles as claimed in claim 18, wherein the aforementioned aromatic monofunctional monoparticle is selected from at least one of the group consisting of styrene, α-methylstyrene, ethyl vinylbenzene, vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, vinyl biphenyl, and vinyl naphthalene.

21. The method for manufacturing hollow resin particles as claimed in claim 18, wherein the compound (A) is a difunctional polyphenylene ether oligomer with a number average molecular weight of 500 to 3500.

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