Hollow resin particles, methods for producing the same, and their applications

Abstract

To provide: a hollow resin particle that has a shell portion and a hollow portion surrounded by the shell portion and that can achieve reductions in dielectricity and dielectric loss tangent and can exhibit excellent heat resistance; a method of producing such a hollow resin particle in a simple manner; and a use of such a hollow resin particle.SOLUTION: A hollow resin particle according to an embodiment of the present invention includes a shell portion and a hollow portion surrounded by the shell portion, wherein the shell portion has an ether structure represented by formula (1).SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to hollow resin particles, a method for producing the same, and uses thereof.

Background Art

[0002] In order to increase the speed of information processing using electronic devices, attempts have been made to reduce the dielectric constant and the dielectric loss tangent of the insulating layer of a multilayer printed circuit board. As part of this, studies have been made to introduce air spaces into the resin layer to reduce the dielectric constant and the dielectric loss tangent by mixing hollow particles having a shell portion and a hollow portion surrounded by the shell portion into a thermosetting resin.

[0003] For hollow resin particles used in such applications, for example, even when heated during molding of the thermosetting resin in which the hollow resin particles are mixed or when using solder, high heat resistance is required so that no substantial change occurs in the hollow resin particles.

[0004] In addition, when moisture is present in the hollow resin particles, the moisture evaporates during heating as described above and becomes outgas, which may impair the reliability of the insulating layer. Therefore, hollow resin particles used in such applications are required to have a low water absorption rate.

[0005] It has been reported that acrylic hollow resin particles can be obtained by suspension polymerization of a monomer mainly composed of an acrylic polyfunctional monomer such as trimethylolpropane tri(meth)acrylate or dipentaerythritol hexaacrylate together with a hydrophobic solvent (Patent Document 1).

[0006] It has been reported that hollow resin particles in which the hollow surrounded by a shell is composed of a plurality of hollow regions can be obtained by suspension polymerization of a monomer mainly composed of an acrylic polyfunctional monomer such as trimethylolpropane tri(meth)acrylate and an acrylic monofunctional monomer such as methyl methacrylate together with a hydrophobic solvent (Patent Document 2).

[0007] It has been reported that styrene-based hollow resin particles can be obtained by suspension polymerization of divinylbenzene together with saturated hydrocarbons having 8 to 18 carbon atoms (more specifically, hexadecane) as hollow resin particles (Patent Document 3).

[0008] It has been reported that by incorporating hollow resin particles obtained by polymerizing polyfunctional monomers and monofunctional monomers into a resin, an organic insulating material with excellent insulating properties, low dielectric constant, and low dielectric loss tangent can be obtained. Specific monomers used include styrene, methyl methacrylate, divinylbenzene, and trimethylolpropane tri(meth)acrylate (Patent Document 4).

[0009] As hollow resin particles, styrene-based hollow resin particles have been reported in which the shell consists of either a polymer or copolymer of a crosslinkable monomer, or a copolymer of the crosslinkable monomer and a monofunctional monomer, and has a single-phase structure. Typically, these are obtained by suspension polymerization of divinylbenzene with saturated hydrocarbons having 8 to 18 carbon atoms (more specifically, hexadecane). Resin compositions containing these hollow resin particles and a thermosetting resin have been reported to be suitable for the manufacture of multilayer printed circuit boards used in electronic devices and the like (Patent Document 5).

[0010] Generally, acrylic resins are known to have high dielectric constant and dielectric loss tangent values, insufficient heat resistance, and high water absorption. For these reasons, the acrylic hollow resin particles described in Patent Documents 1 and 2 are unsuitable for purposes such as reducing the dielectric constant and dielectric loss tangent of the resin layer, providing high heat resistance to the resin layer, and suppressing water absorption of the resin layer.

[0011] The styrene-based hollow resin particles described in Patent Document 3 are made of a material (crosslinkable polystyrene) with lower dielectric constant and dielectric loss tangent compared to acrylic-based hollow resin particles. Therefore, they can be said to be effective particles for the purpose of lowering the dielectric and dielectric loss tangent of the resin layer. However, because saturated hydrocarbons with 8 to 18 carbon atoms (specifically, hexadecane) are used in their manufacture, it is difficult to remove the solvent from the hollow portion by distillation, etc., and saturated hydrocarbons with 8 to 18 carbon atoms remain in the resulting styrene-based hollow resin particles, making it difficult to obtain styrene-based hollow resin particles in which the hollow portion has been completely replaced with air. Furthermore, in order to obtain styrene-based hollow resin particles in which the hollow portion has been completely replaced with air, the manufacturing cost is increased due to the solvent removal as described above. In addition, the styrene-based hollow resin particles described in Patent Document 3 have insufficient heat resistance.

[0012] The hollow resin particles described in Patent Document 4 use a combination of styrene-based monomers and acrylic-based monomers with high dielectric constant and dielectric loss tangent values, resulting in insufficient reduction of dielectric constant and dielectric loss tangent in the resin layer. Furthermore, Patent Document 4 provides a guideline for heat resistance, which is the 10% weight loss temperature measured by TG-DTA under nitrogen atmosphere and heating conditions of 10°C / min, but the heat resistance is insufficient.

[0013] The hollow resin particles described in Patent Document 5, like the styrene-based hollow resin particles described in Patent Document 3, use saturated hydrocarbons with 8 to 18 carbon atoms (more specifically, hexadecane) in their production. As a result, it is difficult to remove the solvent from the hollow portion by distillation, and saturated hydrocarbons with 8 to 18 carbon atoms remain in the resulting styrene-based hollow resin particles, making it difficult to obtain styrene-based hollow resin particles in which the hollow portion has been completely replaced with air. Furthermore, obtaining styrene-based hollow resin particles in which the hollow portion has been completely replaced with air incurs manufacturing costs due to the solvent removal process described above. In addition, the styrene-based hollow resin particles described in Patent Document 5 have insufficient heat resistance. [Prior art documents] [Patent Documents]

[0014] [Patent Document 1] Patent No. 6513273 [Patent Document 2] Patent No. 4445495 [Patent Document 3] Japanese Patent Publication No. 2002-080503 [Patent Document 4] Japanese Patent Publication No. 2000-313818 [Patent Document 5] Patent No. 4171489 [Overview of the Initiative] [Problems that the invention aims to solve]

[0015] The present invention was made to solve the above-mentioned conventional problems, and its main objective is to provide hollow resin particles having a shell portion and a hollow portion surrounded by the shell portion, which can achieve low dielectric strength and low dielectric loss tangent, and exhibit excellent heat resistance. Furthermore, it is also to provide a simple method for manufacturing such hollow resin particles. Moreover, it is also to provide applications for such hollow resin particles. [Means for solving the problem]

[0016] The hollow resin particles according to the embodiments of the present invention are A hollow resin particle having a shell portion and a hollow portion surrounded by the shell portion, The shell portion has an ether structure represented by formula (1). [ka]

[0017] In one embodiment, the hollow resin particles according to the embodiment of the present invention have an average particle diameter of 0.1 μm to 50.0 μm.

[0018] In one embodiment, the hollow portion consists of a single hollow region.

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

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

[0021] In one embodiment, the 5% thermogravimetric weight loss temperature when the hollow resin particles are heated at 10 °C / min in a nitrogen atmosphere is 300 °C or higher.

[0022] In one embodiment, the hollow resin particles according to the embodiment of the present invention are used in a resin composition for semiconductor members.

[0023] In one embodiment, the hollow resin particles according to the embodiment of the present invention are used in a paint composition.

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

[0025] In one embodiment, the hollow resin particles according to the embodiment of the present invention are used in a light-diffusing resin composition.

[0026] In one embodiment, the hollow resin particles according to the embodiment of the present invention are used in a light-diffusing film.

[0027] The resin composition for semiconductor members according to the embodiment of the present invention contains the hollow resin particles according to the embodiment of the present invention.

[0028] The paint composition according to the embodiment of the present invention contains the hollow resin particles according to the embodiment of the present invention.

[0029] The heat-insulating resin composition according to the embodiment of the present invention contains the hollow resin particles according to the embodiment of the present invention.

[0030] The light-diffusing resin composition according to the embodiment of the present invention contains the hollow resin particles according to the embodiment of the present invention.

[0031] The light-diffusing film according to an embodiment of the present invention includes hollow resin particles according to an embodiment of the present invention.

[0032] The manufacturing method according to an embodiment of the present invention is: A method for producing hollow resin particles according to an embodiment of the present invention, 20 to 80 parts by weight of compound (A) having an ether structure represented by formula (1) and 80 to 20 parts by weight of monomer (B) that reacts with compound (A) (total amount of compound (A) and monomer (B) being 100 parts by weight) are reacted in an aqueous medium in the presence of a non-reactive solvent. [ka] [Effects of the Invention]

[0033] According to embodiments of the present invention, it is possible to provide hollow resin particles having a shell portion and a hollow portion surrounded by the shell portion, which can achieve low dielectric strength, low dielectric loss tangent, and excellent heat resistance. Furthermore, it is possible to provide a simple method for manufacturing such hollow resin particles. Moreover, it is possible to provide applications for such hollow resin particles. [Brief explanation of the drawing]

[0034] [Figure 1] This is a schematic cross-sectional view illustrating the structure of the hollow section. [Figure 2] This is a cross-sectional photograph of the hollow resin particles (1) obtained in Example 1. [Figure 3] This is a cross-sectional photograph of the hollow resin particles (2) obtained in Example 2. [Figure 4] This is a cross-sectional photograph of the hollow resin particles (3) obtained in Example 3. [Figure 5] This is a cross-sectional photograph of the hollow resin particles (4) obtained in Example 4. [Figure 6] This is a cross-sectional photograph of the hollow resin particles (5) obtained in Example 5. [Figure 7]This is a cross-sectional photograph of the hollow resin particles (6) obtained in Example 6. [Figure 8] This is a cross-sectional photograph of the hollow resin particles (7) obtained in Example 7. [Figure 9] This is a TEM image of the hollow resin particles (8) obtained in Example 8. [Figure 10] This is a TEM image of the hollow resin particles (9) obtained in Example 9. [Figure 11] This is a cross-sectional photograph of the hollow resin particles (10) obtained in Example 10. [Figure 12] This is a cross-sectional photograph of the hollow resin particles (11) obtained in Example 11. [Figure 13] This is a cross-sectional photograph of the particle (C1) obtained in Comparative Example 1. [Figure 14] This is a TEM image of the particle (C2) obtained in Comparative Example 2. [Figure 15] This is a UV-Vis-Near-Infrared spectral reflectance diagram of the hollow resin particles (1) obtained in Example 1. [Modes for carrying out the invention]

[0035] The following describes embodiments of the present invention, but the present invention is not limited to these embodiments.

[0036] ≪≪1. Hollow resin particles≫≫ ≪1-1. Structure and properties of hollow resin particles≫ The hollow resin particles according to the embodiment of the present invention are hollow resin particles having a shell portion and a hollow portion surrounded by the shell portion. Here, "hollow" means a state in which the inside is filled with a substance other than resin, such as a gas or liquid, and preferably means a state in which it is filled with gas, in order to better exhibit the effects of the present invention.

[0037] The shell portion and the hollow portion enclosed by the shell portion may consist of one hollow region, as shown in the schematic cross-sectional view of Figure 1(a), or may consist of multiple hollow regions, as shown in the schematic cross-sectional view of Figure 1(b).

[0038] The shell portion and the hollow portion enclosed by the shell portion may have a porous structure, as shown in the schematic cross-sectional view in Figure 1(c). When the hollow portion has a porous structure, it may consist of a single hollow region (continuous pore), multiple hollow regions (independent pores), or a mixture of these.

[0039] The average particle diameter of the hollow resin particles according to the embodiments of the present invention is preferably 0.1 μm to 50.0 μm, more preferably 0.1 μm to 40.0 μm, even more preferably 0.2 μm to 30.0 μm, and particularly preferably 0.3 μm to 20.0 μm. The effects of the present invention can be more fully realized when the average particle diameter of the hollow resin particles is within the above range. If the average particle diameter of the hollow resin particles according to the embodiments of the present invention is too small and outside the above range, the thickness of the shell portion will be relatively thin, which may result in hollow resin particles that do not have sufficient strength. If the average particle diameter of the hollow resin particles according to the embodiments of the present invention is too large and outside the above range, it may become difficult for the polymer and solvent to separate during suspension polymerization, which may make it difficult to form the shell portion.

[0040] The hollow resin particles according to the embodiments of the present invention have a 5% thermoweight loss temperature of 300°C or higher, more preferably 320°C or higher, even more preferably 340°C or higher, and particularly preferably 360°C or higher when heated at a rate of 10°C / min in a nitrogen atmosphere. In practice, the upper limit of the 5% thermoweight loss temperature is preferably 500°C or lower. If the 5% thermoweight loss temperature of the hollow resin particles according to the embodiments of the present invention, when heated at a rate of 10°C / min in a nitrogen atmosphere, falls within the above range, the hollow resin particles according to the embodiments of the present invention can exhibit excellent heat resistance. If the 5% thermoweight loss temperature of the hollow resin particles according to the embodiments of the present invention, when heated at a rate of 10°C / min in a nitrogen atmosphere, falls too low and falls outside the above range, for example, when the hollow resin particles are mixed with a thermosetting resin, the particles may deform due to heating for the curing reaction, and the hollow portion may be lost, which may reduce the low dielectric effect and the low dielectric loss tangent effect.

[0041] The hollow resin particles according to the embodiments of the present invention have a moisture content of preferably 0.50% by weight or less, more preferably 0.45% by weight or less, even more preferably 0.40% by weight or less, and particularly preferably 0.35% by weight or less, after being left standing for 96 hours in an atmosphere of 40°C and 95% RH. The lower the moisture content, the better, preferably 0% by weight or more. If the moisture content of the hollow resin particles after being left standing for 96 hours in an atmosphere of 40°C and 95% RH falls within the above range, the effects of the present invention can be more fully realized. If the moisture content of the hollow resin particles after being left standing for 96 hours in an atmosphere of 40°C and 95% RH falls outside the above range and is too high, the water absorption rate of the hollow resin particles may increase.

[0042] ≪1-2. Shell Section≫ The shell portion has an ether structure represented by formula (1). [ka]

[0043] The shell portion preferably contains a polymer (P) having an ether structure represented by formula (1). By including such a polymer (P) in the shell portion, the effects of the present invention can be more fully realized.

[0044] The polymer (P) may be of one type or two or more types.

[0045] The content ratio of polymer (P) in the shell portion is preferably 60% to 100% by weight, more preferably 70% to 100% by weight, even more preferably 80% to 100% by weight, and particularly preferably 90% to 100% by weight, in order to better exhibit the effects of the present invention.

[0046] The shell portion may contain any other suitable components, as long as they do not impair the effects of the present invention.

[0047] <Polymer (P)> As the polymer (P), any suitable polymer can be used as long as it has an ether structure represented by formula (1), provided that it does not impair the effects of the present invention. In terms of being able to better express the effects of the present invention, such a polymer (P) is preferably a polymer obtained by the reaction of a compound (A) having an ether structure represented by formula (1) with a monomer (B) that reacts with compound (A).

[0048] The compound (A) having the ether structure represented by formula (1) may be one type or two or more types.

[0049] The monomer (B) that reacts with the compound having an ether structure represented by formula (1) may be one type or two or more types.

[0050] The ratio of compound (A) to monomer (B) is, when the total amount of compound (A) and monomer (B) is 100 parts by weight, preferably (20 to 80 parts by weight):(80 to 20 parts by weight).

[0051] One embodiment of the above preferred ratio is more preferably (50 to 80 parts by weight):(50 to 20 parts by weight), even more preferably (55 to 75 parts by weight):(45 to 25 parts by weight), and particularly preferably (60 to 70 parts by weight):(40 to 30 parts by weight).

[0052] Another embodiment of the above preferred ratio is more preferably (30 to 70 parts by weight):(70 to 30 parts by weight), even more preferably (35 to 65 parts by weight):(65 to 35 parts by weight), and particularly preferably (40 to 60 parts by weight):(60 to 40 parts by weight).

[0053] If the content of compound (A) is too low and outside the above range, the heat resistance may be insufficient. If the content of compound (A) is too high and outside the above range, it may become difficult to form the shell portion and the hollow portion surrounded by the shell portion.

[0054] As compound (A), any suitable compound can be used as long as it has an ether structure represented by formula (1), provided that it does not impair the effects of the present invention. In terms of being able to better express the effects of the present invention, polyphenylene ether is a preferred example of such compound (A). Examples of commercially available polyphenylene ethers include the trade names "Noryl" (manufactured by SABIC Corporation), "Yupiace" (manufactured by Mitsubishi Chemical Corporation), "Xylon" (manufactured by Asahi Kasei Corporation), and "OPE-2St" (manufactured by Mitsubishi Gas Chemical Corporation).

[0055] From the standpoint of compatibility with the non-reactive solvents described later, and the ability to more easily produce hollow resin particles with excellent heat resistance, the polyphenylene ether is preferably an oligomer, and its number average molecular weight (Mn) is preferably 500 to 3500.

[0056] Examples of monomer (B) include crosslinkable monomers and monofunctional monomers. A monomer that reacts with the terminal group of compound (A) is preferred in that it can better exhibit the effects of the present invention.

[0057] Examples of crosslinkable monomers include polyfunctional (meth)acrylic acid esters such as ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and glycerin 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 crosslinkable monomers such as divinylbenzene, divinylnaphthalene, and diallyl phthalate. In terms of better exhibiting the effects of the present invention, aromatic crosslinkable monomers are preferred as the crosslinkable monomer, and divinylbenzene is more preferred. There may be only one crosslinkable monomer or two or more.

[0058] Examples of monofunctional monomers include C1-C16 alkyl(meth)acrylic acid esters such as methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, and cetyl(meth)acrylate; aromatic monofunctional monomers such as styrene, α-methylstyrene, ethyl vinylbenzene, vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, vinyl biphenyl, and vinylnaphthalene; dicarboxylic acid ester monomers such as dimethyl maleate, diethyl fumarate, dimethyl fumarate, and diethyl fumarate; maleic anhydride; N-vinylcarbazole; and (meth)acrylonitrile. In terms of better exhibiting the effects of the present invention, aromatic monofunctional monomers are preferred as monofunctional monomers, and styrene and ethyl vinylbenzene are more preferred. There may be only one monofunctional monomer or two or more.

[0059] Polymers (P) can typically be formed by the reaction of compound (A) and monomer (B).

[0060] The reaction between compound (A) and monomer (B) can be carried out by any suitable reaction, as long as it does not impair the effects of the present invention. A suspension polymerization reaction is a preferred example of such a reaction.

[0061] In suspension polymerization reactions, typically, an oil phase is added to an aqueous phase to suspend the mixture and carry out the polymerization reaction. The aqueous and oil phases may contain any suitable solvent, as long as it does not impair the effects of the present invention. Examples of such solvents include aqueous media and non-reactive solvents, as described later. There may be only one solvent or two or more solvents.

[0062] When carrying out the reaction between compound (A) and monomer (B), any suitable additive (C) that is neither compound (A) nor monomer (B) may be used, as long as it does not impair the effects of the present invention. Additive (C) may be one type or two or more types. The additive referred to herein does not include solvents such as aqueous media or non-reactive solvents as described later.

[0063] The content of additive (C) is preferably 0% to 40% by weight, more preferably 0% to 30% by weight, even more preferably 0% to 20% by weight, and particularly preferably 0% to 10% by weight, relative to the total amount of compound (A) and monomer (B).

[0064] As additive (C), any suitable additive can be used as long as it does not impair the effects of the present invention. Examples of such additive (C) include non-crosslinkable polymers, dispersion stabilizers, surfactants, and polymerization initiators.

[0065] By including a non-crosslinkable polymer as additive (C), phase separation between the polymer (P) and the solvent generated during the reaction is promoted, which can facilitate shell formation.

[0066] Examples of non-crosslinkable polymers include at least one selected from the group consisting of polyolefins, styrene-based polymers, (meth)acrylic acid-based polymers, and styrene-(meth)acrylic acid-based polymers.

[0067] Examples of polyolefins include polyethylene, polypropylene, and poly-α-olefins. From the viewpoint of solubility in monomer compositions, it is preferable to use side-chain crystalline polyolefins using long-chain α-olefins as raw materials, low molecular weight polyolefins produced with metallocene catalysts, or olefin oligomers.

[0068] Examples of styrene-based polymers include polystyrene, styrene-acrylonitrile copolymers, and acrylonitrile-butadiene-styrene copolymers.

[0069] Examples of (meth)acrylic acid polymers include polymethyl (meth)acrylate, polyethyl (meth)acrylate, polybutyl (meth)acrylate, and polypropyl (meth)acrylate.

[0070] Examples of styrene-(meth)acrylic acid polymers include styrene-methyl(meth)acrylate copolymer, styrene-ethyl(meth)acrylate copolymer, styrene-butyl(meth)acrylate copolymer, and styrene-propyl(meth)acrylate copolymer.

[0071] ≪1-3. Relative permittivity of hollow resin particles≫ The relative permittivity of the hollow resin particles according to the embodiments of the present invention 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 relative permittivity of the hollow resin particles according to the embodiments of the present invention is within the above range, the effects of the present invention can be more fully realized. If the relative permittivity of the hollow resin particles according to the embodiments of the present invention is greater than 2.5, a sufficient low-dielectric effect cannot be obtained even if the hollow resin particles are mixed with, for example, a thermosetting resin.

[0072] The relative permittivity of hollow resin particles according to embodiments of the present invention can be calculated by referring to, for example, "Dielectric Constant of Mixed Systems" (Applied Physics, Vol. 27, No. 8 (1958)). If ε is the relative permittivity of the mixed system of the dispersion medium and hollow resin particles, ε1 is the relative permittivity of the substrate that serves as the dispersion medium (for example, a resin composition such as polyimide or epoxy), ε2 is the relative permittivity of the hollow resin particles, and φ is the volume fraction of the hollow resin particles in the mixed system, then the following equation holds. That is, if ε, ε1, and φ are determined experimentally, the relative permittivity ε2 of the hollow resin particles can be calculated.

number

[0073] Furthermore, the volume fraction φ of the hollow resin particles in the mixed system of the dispersion medium and hollow resin particles can be determined as follows.

number

[0074] The density of the hollow resin particles was measured using a pycnometer (manufactured by Cortec Co., Ltd., TQC 50mL specific gravity bottle) and a liquid polymer product named "ARUFON (trademark) UP-1080" (manufactured by Toagosei Co., Ltd., density 1.05 g / cm³). 3 This can be determined experimentally using the following method. Specifically, hollow resin particles and ARUFON UP-1080 are defoamed and stirred using a planetary agitator (KURABO Corporation, "Mazelstar KK-250") so that the proportion of hollow resin particles is 10% by weight, and an evaluation mixture is prepared. The evaluation mixture is filled into a 50 mL pycnometer, and the weight of the filled evaluation mixture is calculated by subtracting the weight of the empty pycnometer from the weight of the pycnometer filled with the mixture. From this value, the density of the hollow resin particles can be calculated using the following formula.

number

[0075] ≪1-4. Applications of Hollow Resin Particles≫ The hollow resin particles according to the embodiments of the present invention can be used in a variety of applications. In terms of making better use of the effects of the present invention, the hollow resin particles according to the embodiments of the present invention are suitable for semiconductor materials, and are typically suitable for use in resin compositions for semiconductor materials. In addition to the above-mentioned use in resin compositions for semiconductor materials, the hollow resin particles according to the embodiments of the present invention can also be applied to applications such as paint compositions, cosmetics, paper coating compositions, heat insulating compositions, light diffusing compositions, and light diffusing films.

[0076] <Resin composition for semiconductor materials> The hollow resin particles according to the embodiments of the present invention can achieve low dielectric strength and low dielectric loss tangent, and exhibit excellent heat resistance, making them suitable for use in resin compositions for semiconductor components.

[0077] A resin composition for semiconductor components according to an embodiment of the present invention includes hollow resin particles according to an embodiment of the present invention.

[0078] Semiconductor components refer to the components that make up a semiconductor, such as semiconductor packages and semiconductor modules. In this specification, a resin composition for semiconductor components refers to a resin composition used in semiconductor components.

[0079] A semiconductor package is a component in which an IC chip is an essential component, and is constructed using at least one material selected from molding resin, underfill material, molded underfill material, die bonding material, prepreg for semiconductor package substrates, metal-clad laminate for semiconductor package substrates, and build-up material for printed circuit boards for semiconductor packages.

[0080] A semiconductor module is a component in which a semiconductor package is an essential component, and which is composed of at least one component selected from prepregs for printed circuit boards, metal-clad laminates for printed circuit boards, build-up materials for printed circuit boards, solder resist materials, coverlay films, electromagnetic shielding films, and adhesive sheets for printed circuit boards.

[0081] <Paint composition> The hollow resin particles according to the embodiments of the present invention can impart an excellent appearance to the coating film containing them, and are therefore suitable for use in paint compositions.

[0082] A paint composition according to an embodiment of the present invention contains hollow resin particles according to an embodiment of the present invention.

[0083] The paint composition according to the embodiment of the present invention preferably comprises at least one selected from a binder resin and a UV-curable resin. The binder resin may be one type or two or more types. The UV-curable resin may be one type or two or more types.

[0084] Any suitable binder resin can be used as the binder resin, as long as it does not impair the effects of the present invention. Examples of such binder resins include resins soluble in organic solvents or water, and emulsion-type aqueous resins that can be dispersed in water. Specifically, examples of binder resins include acrylic resins, alkyd resins, polyester resins, polyurethane resins, chlorinated polyolefin resins, and amorphous polyolefin resins.

[0085] As the UV-curable resin, any suitable UV-curable resin can be used as long as it does not impair the effects of the present invention. Examples of such UV-curable resins include polyfunctional (meth)acrylate resins and polyfunctional urethane acrylate resins, with polyfunctional (meth)acrylate resins being preferred, and polyfunctional (meth)acrylate resins having three or more (meth)acryloyl groups in one molecule being more preferred. Specific examples of polyfunctional (meth)acrylate resins having three or more (meth)acryloyl groups in one molecule 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.

[0086] When a paint composition according to an embodiment of the present invention contains at least one selected from a binder resin and a UV-curable resin, the proportion of these components can be any appropriate proportion depending on the purpose. Typically, the amount of hollow resin particles according to an embodiment of the present invention is preferably 5% to 50% by weight, more preferably 10% to 50% by weight, and even more preferably 20% to 40% by weight, relative to the total amount of the binder resin (in terms of solid content in the case of an emulsion-type aqueous resin) and at least one selected from a UV-curable resin and the hollow resin particles according to an embodiment of the present invention.

[0087] When UV-curable resins are used, a photopolymerization initiator is preferably used in combination. Any suitable photopolymerization initiator can be used as the photopolymerization initiator, as long as it does not impair the effects of the present invention. Examples of such photopolymerization initiators include acetophenones, benzoins, phosphine oxides, ketals, α-hydroxyalkylphenones, α-aminoalkylphenones, anthraquinones, thioxanthones, azo compounds, peroxides (as described in Japanese Patent Publication No. 2001-139663, etc.), 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, onium salts, borate salts, activated halogen compounds, and α-acyloxime esters.

[0088] The paint composition according to the embodiment of the present invention may contain a solvent. The solvent may be one type or two or more types. When the paint composition according to the embodiment of the present invention contains a solvent, any appropriate proportion can be adopted depending on the purpose.

[0089] As the solvent, any suitable solvent can be used as long as it does not impair the effects of the present invention. Preferably, such a solvent is one that can dissolve or disperse the binder resin or UV-curable resin. Examples of such solvents for oil-based paints 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 dioxane, ethylene glycol diethyl ether, and ethylene glycol monobutyl ether. Examples of solvents for water-based paints include water and alcohols.

[0090] The paint compositions according to embodiments of the present invention may be diluted to adjust the viscosity as needed. Any suitable diluent can be used as the diluent, depending on the purpose. Examples of such diluents include the solvents mentioned above. There may be one diluent or two or more diluents.

[0091] The coating compositions according to embodiments of the present invention may optionally contain other components, such as surface modifiers, flow modifiers, ultraviolet absorbers, light stabilizers, curing catalysts, extender pigments, coloring pigments, metal pigments, mica powder pigments, and dyes.

[0092] When forming a coating film using a coating composition according to an embodiment of the present invention, any suitable coating method can be adopted depending on the purpose. Examples of such coating methods include spray coating, roll coating, brush coating, coating reverse roll coating, gravure coating, die coating, comma coating, and spray coating.

[0093] When forming a coating film using a coating composition according to an embodiment of the present invention, any suitable method of formation can be adopted depending on the purpose. For example, such a method involves applying the coating to any coated surface of a substrate to create a coating film, drying the coating film, and then curing the coating film as necessary to form the coating film. Examples of substrates include metals, wood, glass, and plastics (PET (polyethylene terephthalate), PC (polycarbonate), acrylic resin, TAC (triacetylcellulose), etc.).

[0094] <Thermal insulation resin composition> The hollow resin particles according to the embodiments of the present invention can impart excellent heat insulation properties to the coating film containing them, and are therefore suitable for use in heat insulating resin compositions. The coating film containing the hollow resin particles according to the embodiments of the present invention can exhibit excellent reflectivity in the wavelength range from ultraviolet light to near-infrared light.

[0095] The heat-insulating resin composition according to an embodiment of the present invention includes hollow resin particles according to an embodiment of the present invention.

[0096] The heat-insulating resin composition according to the embodiments of the present invention preferably comprises at least one selected from a binder resin and a UV-curable resin. The binder resin and UV-curable resin can be described in the above-described explanation for paint compositions.

[0097] The heat-insulating resin composition according to the embodiment of the present invention may contain a solvent. The description of the paint composition described above can be used as a reference to the solvent.

[0098] The heat-insulating resin compositions according to embodiments of the present invention may be diluted to adjust their viscosity as needed. The diluents described above for paint compositions can be used as reference.

[0099] The heat-insulating resin composition according to the embodiment of the present invention may optionally contain other components, such as surface conditioners, flow modifiers, ultraviolet absorbers, light stabilizers, curing catalysts, extender pigments, coloring pigments, metal pigments, mica powder pigments, and dyes.

[0100] When forming a coating film using the heat-insulating resin composition according to an embodiment of the present invention, the coating method and forming method can be described by referring to the above-described explanation of the paint composition.

[0101] <Light-diffusing resin composition> The hollow resin particles according to the embodiments of the present invention can impart excellent light-diffusing properties to coating films containing them, and are therefore suitable for use in light-diffusing resin compositions.

[0102] A light-diffusing resin composition according to an embodiment of the present invention includes hollow resin particles according to an embodiment of the present invention.

[0103] The light-diffusing resin composition according to the embodiments of the present invention preferably comprises at least one selected from a binder resin and a UV-curable resin. The binder resin and UV-curable resin can be described in the above-mentioned description of the coating composition.

[0104] The light-diffusing resin composition according to the embodiment of the present invention may contain a solvent. The description of the paint composition described above can be used as a reference for the solvent.

[0105] The light-diffusing resin compositions according to embodiments of the present invention may be diluted to adjust their viscosity as needed. The diluents described above for paint compositions can be used as reference.

[0106] The light-diffusing resin composition according to the embodiment of the present invention may optionally contain other components, such as coating surface modifiers, flow rate modifiers, ultraviolet absorbers, light stabilizers, curing catalysts, extender pigments, coloring pigments, metal pigments, mica powder pigments, and dyes.

[0107] When forming a coating film using a light-diffusing resin composition according to an embodiment of the present invention, the coating method and forming method can be described by referring to the above-described explanation of the paint composition.

[0108] <Light Diffusing Film> The hollow resin particles according to the embodiment of the present invention can impart excellent light-diffusing properties to a film having a coating film containing them, and therefore can be suitably used in light-diffusing films.

[0109] The light-diffusing film according to an embodiment of the present invention includes hollow resin particles according to an embodiment of the present invention.

[0110] A light-diffusing film according to an embodiment of the present invention comprises a light-diffusing layer formed from a light-diffusing resin composition according to an embodiment of the present invention and a substrate. The light-diffusing layer may or may not be the outermost layer of the light-diffusing film. The light-diffusing film according to an embodiment of the present invention may include any other suitable layer depending on the purpose. Examples of such other layers include a protective layer, a hard coat layer, a planarizing layer, a high refractive index layer, an insulating layer, a conductive resin layer, a conductive metal nanoparticle layer, a conductive metal oxide nanoparticle layer, and a primer layer.

[0111] 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 board. Examples of plastics that make up plastic film, plastic sheet, plastic lens, and plastic panel include PET (polyethylene terephthalate), PC (polycarbonate), acrylic resin, and TAC (triacetylcellulose).

[0112] ≪≪2. Method for Manufacturing Hollow Resin Particles≫≫ A method for producing hollow resin particles according to an embodiment of the present invention involves reacting 20 to 80 parts by weight of compound (A) having an ether structure represented by formula (1) with 20 to 80 parts by weight of monomer (B) that reacts with compound (A) (the total amount of compound (A) and monomer (B) being 100 parts by weight) in an aqueous medium in the presence of a non-reactive solvent. [ka]

[0113] According to the above manufacturing method, hollow resin particles according to embodiments of the present invention can be easily produced.

[0114] Hollow resin particles according to embodiments of the present invention can be obtained by reacting compound (A) and monomer (B) in an aqueous medium in the presence of a non-reactive solvent. Typically, hollow resin particles according to embodiments of the present invention can be produced by subjecting compound (A) and monomer (B) to a suspension polymerization reaction.

[0115] Suspension polymerization is typically a method that uses an aqueous phase containing a water-based medium and an oil phase containing compound (A), monomer (B), and a non-reactive solvent. Preferably, the oil phase containing compound (A), monomer (B), and non-reactive solvent is added to the aqueous phase containing the water-based medium, dispersed, and heated to carry out suspension polymerization.

[0116] The dispersion can be any suitable method, as long as it allows the oil phase to exist in droplet form in the aqueous phase, and does not impair the effects of the present invention. Typical dispersion methods include those using homomixers or homogenizers, such as polytron homogenizers, ultrasonic homogenizers, and high-pressure homogenizers.

[0117] The polymerization temperature can be any suitable temperature within a range that does not impair the effects of the present invention, as long as it is suitable for suspension polymerization. Preferably, such a polymerization temperature is 30°C to 80°C.

[0118] The polymerization time can be any appropriate time, as long as it is suitable for suspension polymerization and does not impair the effects of the present invention. Such a polymerization time is preferably 1 to 48 hours.

[0119] Post-heating, which is preferably performed after polymerization, is a suitable treatment for obtaining high-quality hollow resin particles.

[0120] The temperature of the post-heating, which is preferably performed after polymerization, can be any suitable temperature within a range that does not impair the effects of the present invention. The temperature of such post-heating is preferably 70°C to 120°C.

[0121] The duration of the post-heating, which is preferably performed after polymerization, can be any appropriate time within a range that does not impair the effects of the present invention. Such post-heating is preferably 1 to 24 hours.

[0122] For compound (A) and monomer (B), the explanation in the section on <polymer (P)> in <1-2. shell portion> of <<1. hollow resin particles>> can be directly applied.

[0123] The proportions of compound (A) and monomer (B) can be directly derived from the explanation in the section on <polymer (P)> under <1-2. shell portion> of <<1. hollow resin particles>>.

[0124] Examples of aqueous media include water, and mixed media of water and lower alcohols (methanol, ethanol, etc.).

[0125] The amount of aqueous medium used can be any appropriate amount, as long as it does not impair the effects of the present invention. Typically, the amount of aqueous medium used is such that the suspension polymerization reaction, in which an oil phase is added to the aqueous phase and suspended, proceeds appropriately. It is preferably 100 to 5000 parts by weight, and more preferably 150 to 2000 parts by weight, per 100 parts by weight of the total amount of compound (A), monomer (B), and nonreactive solvent.

[0126] The non-reactive solvent is a solvent that does not undergo a chemical reaction with either compound (A) having an ether structure represented by formula (1) or monomer (B) that reacts with compound (A), and is preferably an organic solvent. The non-reactive solvent typically acts as a hollowing agent that creates air spaces in the particles. Examples of non-reactive solvents include heptane, hexane, toluene, cyclohexane, methyl acetate, ethyl acetate, methyl ethyl ketone, chloroform, and carbon tetrachloride. The boiling point of the non-reactive solvent is preferably less than 100°C, as this facilitates removal from the hollow resin particles.

[0127] The non-reactive solvent used as a hollowing agent may be a single solvent or a mixture of solvents.

[0128] The amount of non-reactive solvent added is preferably 20 to 250 parts by weight per 100 parts by weight of the total amount of compound (A) and monomer (B).

[0129] When carrying out the reaction between compound (A) and monomer (B), any suitable additive (C) that is neither compound (A) nor monomer (B) may be used, as long as it does not impair the effects of the present invention. Additive (C) may be one type or two or more types. The additive referred to herein does not include solvents such as aqueous media or non-reactive solvents.

[0130] The content of additive (C) is preferably 0% to 40% by weight, more preferably 0% to 30% by weight, even more preferably 0% to 20% by weight, and particularly preferably 0% to 10% by weight, relative to the total amount of compound (A) and monomer (B).

[0131] As additive (C), any suitable additive can be used as long as it does not impair the effects of the present invention. Examples of such additive (C) include non-crosslinkable polymers, dispersion stabilizers, surfactants, and polymerization initiators.

[0132] For non-crosslinkable polymers, the explanation in the section on <Polymer (P)> under <1-2. Shell portion> of <<1. Hollow resin particles>> can be directly applied.

[0133] Examples of dispersion stabilizers include polyvinyl alcohol, polycarboxylic acids, celluloses (hydroxyethylcellulose, carboxymethylcellulose, etc.), and polyvinylpyrrolidone. Inorganic water-soluble polymer compounds such as sodium tripolyphosphate can also be used. Furthermore, phosphates such as calcium phosphate, magnesium phosphate, aluminum phosphate, and zinc phosphate; pyrophosphates such as calcium pyrophosphate, magnesium pyrophosphate, aluminum pyrophosphate, and zinc pyrophosphate; and poorly water-soluble inorganic compounds such as calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, and colloidal silica can also be used. The use of magnesium pyrophosphate is preferred because it is relatively easy to remove from hollow resin particles and does not easily remain on the surface of hollow resin particles.

[0134] The amount of dispersion stabilizer added is preferably 0.5 to 10 parts by weight per 100 parts by weight of the aqueous medium. The dispersion stabilizer may be one type or two or more types.

[0135] Examples of surfactants include anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants.

[0136] Examples of anionic surfactants include non-reactive anionic surfactants such as alkyl sulfate salts, alkyl phosphate salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkanesulfonates, alkyldiphenyl ether sulfonates, dialkyl sulfosuccinates, monoalkyl sulfosuccinates, and polyoxyethylene alkylphenyl ether phosphates, as well as reactive anionic surfactants such as polyoxyethylene-1-(allyloxymethyl)alkyl ether sulfate ammonium salt, polyoxyethylene alkylpropenylphenyl ether sulfate ammonium salt, and polyoxyalkylene alkenyl ether sulfate ammonium salt. Note that surfactants are not limited to salt structures; for example, alkyl sulfate esters and alkyl phosphate esters can also be used. Specifically, examples include lauryl sulfate and lauryl phosphate.

[0137] Examples of cationic surfactants include alkyltrimethylammonium salts, alkyltriethylammonium salts, dialkyldimethylammonium salts, dialkyldiethylammonium salts, and N-polyoxyalkylene-N,N,N-trialkylammonium salts.

[0138] Examples of amphoteric surfactants include lauryldimethylamine oxide, phosphate ester salts, and phosphite ester surfactants.

[0139] Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polysorbitan fatty acid esters, polyoxyethylene alkylamines, glycerin fatty acid esters, and oxyethylene-oxypropylene block polymers.

[0140] The amount of surfactant added is preferably 0.01% to 5% by weight relative to the total amount of compound (A), monomer (B), and nonreactive solvent. The surfactant may be one type or two or more types.

[0141] As a polymerization initiator, any suitable polymerization initiator can be used as long as it does not impair the effects of the present invention. Examples of such polymerization initiators include organic peroxides such as lauroyl peroxide, benzoyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, t-butylperoxy-2-ethylhexanoate, and di-t-butyl peroxide; and azo compounds such as 2,2'-azobisisobutyronitrile, 1,1'-azobiscyclohexanecarbonitride, and 2,2'-azobis(2,4-dimethylvaleronitrile).

[0142] The content of the polymerization initiator is preferably in the range of 0.1% to 5% by weight relative to the total amount of compound (A) and monomer (B). There may be only one polymerization initiator or two or more. [Examples]

[0143] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means "parts by weight" and "%" means "percent by weight".

[0144] <Measurement of volume-average particle diameter (Examples 1-7, Example 10, Comparative Example 1)> The volume-average particle diameter of the particles was measured using the Coulter method as follows. The volume-average particle size of the particles was measured using a Coulter Multisizer® 3 (a measuring device manufactured by Beckman Coulter, Inc.). The measurements were performed using an aperture calibrated according to the Multisizer® 3 User's Manual issued by Beckman Coulter, Inc. The aperture used for measurement was selected appropriately depending on the size of the particles being measured. For example, a 50 μm aperture was selected if the assumed volume-average particle size of the particles being measured was between 1 μm and 10 μm; a 100 μm aperture was selected if the assumed volume-average particle size of the particles being measured was greater than 10 μm and 30 μm or less; a 280 μm aperture was selected if the assumed volume-average particle size of the particles was greater than 30 μm and 90 μm or less; and a 400 μm aperture was selected if the assumed volume-average particle size of the particles was greater than 90 μm and 150 μm or less. If the volume-average particle diameter after measurement differed from the expected volume-average particle diameter, the aperture was changed to one of the appropriate size, and the measurement was repeated. The Current (aperture current) and Gain were set appropriately according to the size of the selected aperture. For example, when an aperture with a size of 50 μm was selected, the Current (aperture current) was set to -800 and the Gain to 4; when an aperture with a size of 100 μm was selected, the Current (aperture current) was set to -1600 and the Gain to 2; and when apertures with sizes of 280 μm and 400 μm were selected, the Current (aperture current) was set to -3200 and the Gain to 1. For the measurement sample, 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 Co., Ltd., "TOUCHMIXER MT-31") and an ultrasonic cleaner (Velvo-Clear Co., Ltd., "ULTRASONIC CLEANER VS-150") to obtain a dispersion. During the measurement, the beaker was gently stirred to prevent the introduction of air bubbles, and the measurement was terminated when 100,000 particles had been measured. The volume-average particle diameter was calculated as the arithmetic mean of the volume-based particle size distribution of the 100,000 particles.

[0145] <Measurement of average particle diameter (Examples 8 and 9, Comparative Example 2)> Using the dynamic light scattering method, the Z-average particle diameter of the hollow resin particles or particles was measured, and the measured Z-average particle diameter was taken 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 were diluted with ion-exchanged water and adjusted to a 0.1 wt% aqueous dispersion, and then irradiated with laser light. The intensity of the scattered light scattered from the hollow resin particles or particles was measured as a change in time in microseconds. Then, the intensity distribution of the scattered light caused by the detected hollow resin particles or particles was fitted to a normal distribution, and the Z-average particle diameter of the hollow resin particles or particles was determined by the cumulant analysis method for calculating the average particle diameter. The measurement of this Z-average particle diameter can be easily carried out with 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, "Zetasizer Nano ZS"). Usually, commercially available particle diameter measuring devices are equipped with data analysis software, and the Z-average particle diameter can be calculated by the data analysis software automatically analyzing the measurement data.

[0146] <Cross-section observation> The dried particles were mixed with a photocurable resin D-800 (manufactured by JEOL Ltd.), and a cured product was obtained by irradiating with ultraviolet light. Then, the cured product was cut with nippers, the cross-section was smoothed using a cutter, and the sample was coated using a sputtering device "Auto Fine Coater JFC-1300" manufactured by JEOL Ltd. Next, the cross-section of the sample was photographed using a secondary electron detector of a scanning electron microscope "SU1510" manufactured by Hitachi High-Technologies Corporation.

[0147] <TEM measurement: Observation of the presence or absence of hollow and shape of hollow resin particles or particles> Hollow resin particles or particles in dry powder form were surface-treated (10 Pa, 5 mA, 10 seconds) using a "Neoc-Pro" osmium coater coating device manufactured by Meiwa Forsis Co., Ltd. Next, the hollow resin particles or particles were observed using a TEM (transmission electron microscope, "H-7600" manufactured by Hitachi High-Technologies Corporation) to confirm the presence or absence of hollowness and the shape of the hollow resin particles or particles. At this time, the acceleration voltage was set to 80 kV, and images were taken at a magnification of 5000x or 10,000x.

[0148] <Measurement of the 5% thermogravimetric loss temperature when the temperature is raised at 10°C / min under a nitrogen atmosphere> The 5% thermogravimetric loss temperature was measured using the "TG / DTA6200, AST-2" differential thermogravimetric analyzer manufactured by SII Nanotechnology Co., Ltd. The sampling method and temperature conditions were as follows. A platinum measuring container was filled with 10.5 ± 0.5 mg of the sample, ensuring there were no gaps at the bottom, to prepare the sample for measurement. Under a nitrogen gas flow rate of 230 mL / min, the 5% thermogravimetric temperature was measured using alumina as the reference material. The TG / DTA curve was obtained by heating the sample from 30°C to 500°C at a heating rate of 10°C / min. Using the analysis software attached to the instrument, the temperature at which a 5% weight loss occurred was calculated from the obtained curve and defined as the 5% thermogravimetric temperature.

[0149] [Example 1] A difunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Corporation), which has an ether structure represented by formula (1), was mixed with 2.5 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Material Corporation, containing 81%, 19% being ethyl vinylbenzene (EVB)), 5.0 g of heptane, 0.05 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (trade name "V-65", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator, and 0.004 g of lauryl phosphate to prepare the oil phase. 32 g of a 2 wt% aqueous dispersion of magnesium pyrophosphate was used as the aqueous phase, to which the oil phase was added. A suspension was prepared using a Polytron homogenizer "PT10-35" (manufactured by Central Science 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. After dehydration by filtration, the solid components were separated, and the slurry was purified by repeated washing with water. Finally, particles (1) were obtained by drying at 60°C. A cross-sectional photograph of the obtained particle (1) is shown in Figure 2. It was confirmed that the obtained particle (1) is a mixture of hollow resin particles in which the hollow enclosed by the shell consists of a single hollow region and hollow resin particles in which the hollow enclosed by the shell has a porous structure. The average particle size of the obtained particles (1) was 16.3 μm. The temperature at which the obtained particle (1) underwent a 10°C / min heating increase was 306°C, resulting in a 5% thermogravimetric loss. Table 1 shows the proportions of each ingredient.

[0150] [Example 2] Particle (2) was obtained in the same manner as in Example 1, except that 3.0 g of a bifunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Corporation), which has an ether structure represented by formula (1), and 2.0 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Material Corporation, 81% content, 19% is ethyl vinylbenzene (EVB)) were used. A cross-sectional photograph of the obtained particle (2) is shown in Figure 3. It was confirmed that the obtained particle (2) is a hollow resin particle in which the hollow surrounded by the shell consists of a single hollow region. The average particle size of the obtained particles (2) was 15.2 μm. The temperature at which the obtained particles (2) underwent a 5% thermogravimetric analysis was 320°C when heated at a rate of 10°C / min in a nitrogen atmosphere. Table 1 shows the proportions of each ingredient.

[0151] [Example 3] Particle (3) was obtained in the same manner as in Example 1, except that 3.5 g of a bifunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Corporation), which has an ether structure represented by formula (1), and 1.5 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Material Corporation, 81% content, 19% is ethyl vinylbenzene (EVB)) were used. A cross-sectional photograph of the obtained particle (3) is shown in Figure 4. It was confirmed that the obtained particle (3) is a hollow resin particle in which the hollow region surrounded by the shell consists of a single hollow region. The average particle size of the obtained particles (3) was 13.9 μm. The temperature at which the obtained particles (3) underwent a 10°C / min heating increase was 309°C, resulting in a 5% thermogravimetric loss. Table 1 shows the proportions of each ingredient.

[0152] [Example 4] Particle (4) was obtained in the same manner as in Example 1, except that 2.5 g of reactive low molecular weight polyphenylene ether (trade name "Noryl® SA9000-111 resin", manufactured by SABIC Corporation), which has an ether structure represented by formula (1), was used instead of 2.5 g of a bifunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Corporation), which has an ether structure represented by formula (1). A cross-sectional photograph of the obtained particle (4) is shown in Figure 5. It was confirmed that the obtained particle (4) is a hollow resin particle with a porous structure consisting of a hollow space surrounded by a shell. The average particle size of the obtained particles (4) was 16.5 μm. The temperature at which the obtained particles (4) underwent a 5% thermogravimetric analysis was 373°C when heated at a rate of 10°C / min in a nitrogen atmosphere. Table 1 shows the proportions of each ingredient.

[0153] [Example 5] Particle (5) was obtained in the same manner as in Example 2, except that 3.0 g of a reactive low molecular weight polyphenylene ether (trade name "Noryl® SA9000-111 resin", manufactured by SABIC Corporation), which is a compound having an ether structure represented by formula (1), was used instead of 3.0 g of a difunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Corporation), which is a compound having an ether structure represented by formula (1). A cross-sectional photograph of the obtained particle (5) is shown in Figure 6. It was confirmed that the obtained particle (5) is a hollow resin particle with a porous structure consisting of a hollow space surrounded by a shell. The average particle size of the obtained particles (5) was 15.6 μm. The temperature at which the obtained particles (5) underwent a 5% thermogravimetric analysis was 420°C when heated at a rate of 10°C / min in a nitrogen atmosphere. Table 1 shows the proportions of each ingredient.

[0154] [Example 6] Particle (6) was obtained in the same manner as in Example 1, except that instead of 2.5 g of a bifunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Corporation), 2.5 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Material Co., Ltd., 81% content, 19% is ethyl vinylbenzene (EVB)), and 5.0 g of heptane, 1.8 g of reactive low molecular weight polyphenylene ether (trade name "Noryl® SA9000-111 resin", manufactured by SABIC Corporation), 1.2 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Material Co., Ltd., 81% content, 19% is ethyl vinylbenzene (EVB)), 5.0 g of heptane, and 2.0 g of toluene were used as compounds having an ether structure represented by formula (1). A cross-sectional photograph of the obtained particle (6) is shown in Figure 7. It was confirmed that the obtained particle (6) is a hollow resin particle with a porous structure consisting of a hollow space surrounded by a shell. The average particle size of the obtained particles (6) was 15.1 μm. The 5% thermogravimetric loss temperature of the obtained particles (6) when heated at a rate of 10°C / min under a nitrogen atmosphere was 415°C. Table 1 shows the proportions of each ingredient.

[0155] [Example 7] The procedure was carried out in the same manner as in Example 1, except that instead of 2.5 g of a bifunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Corporation), 2.5 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Material Co., Ltd., 81% content, 19% is ethyl vinylbenzene (EVB)), and 5.0 g of heptane, 4.0 g of reactive low molecular weight polyphenylene ether (trade name "Noryl® SA9000-111 resin", manufactured by SABIC Corporation), 1.0 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Material Co., Ltd., 81% content, 19% is ethyl vinylbenzene (EVB)), 4.0 g of heptane, and 1.0 g of cyclohexane were used as compounds having an ether structure represented by formula (1), to obtain particles (7). A cross-sectional photograph of the obtained particle (7) is shown in Figure 8. It was confirmed that the obtained particle (7) is a hollow resin particle with a porous structure consisting of a hollow space surrounded by a shell. The average particle size of the obtained particles (7) was 13.1 μm. The temperature at which the obtained particles (7) underwent a 10°C / min heating increase was 428°C, resulting in a 5% thermogravimetric loss. Table 1 shows the proportions of each ingredient.

[0156] [Example 8] A difunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Corporation), which has an ether structure represented by formula (1), was mixed with 1.5 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Material Corporation, containing 81% DVB, 19% of which is ethyl vinylbenzene (EVB)), 3.0 g of heptane, and 0.09 g of perloyl L (manufactured by NOF Corporation) as a polymerization initiator to prepare an oil phase. Next, 34 g of deionized water and 0.0128 g of Rapisol A-80 (NOF Corporation) were mixed to prepare the aqueous phase. The oil phase was added to the aqueous phase, and a suspension was prepared using an ultrasonic homogenizer (BRANSON, "SONIFIER450", conditions: DutyCycle=50%, OutputControl=5, processing time 3 minutes). The resulting suspension was heated at 70°C for 4 hours to carry out the reaction. The resulting slurry was heated at 100°C for 24 hours to obtain dried particles (8). Figure 9 shows a TEM image of the obtained particle (8). It was confirmed that the obtained particle (8) is a hollow resin particle with a porous structure consisting of a hollow space surrounded by a shell. The average particle size of the obtained particles (8) was 320 nm. The temperature at which the obtained particles (8) underwent a 5% thermogravimetric loss was 315°C when heated at a rate of 10°C / min in a nitrogen atmosphere. Table 1 shows the proportions of each ingredient.

[0157] [Example 9] An oil phase was prepared by mixing 1.08 g of reactive low molecular weight polyphenylene ether (trade name "Noryl® SA9000-111 resin", manufactured by SABIC Corporation), which has an ether structure represented by formula (1); 0.72 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Material Corporation, 81% content, 19% is ethyl vinylbenzene (EVB)); 3.0 g of heptane; 1.2 g of toluene; and 0.03 g of perloyl L (manufactured by NOF Corporation) as a polymerization initiator. Next, 34 g of deionized water and 0.0085 g of Rapisol A-80 (NOF Corporation) were mixed to prepare the aqueous phase. The oil phase was added to the aqueous phase, and a suspension was prepared using an ultrasonic homogenizer (BRANSON, "SONIFIER450", conditions: DutyCycle=50%, OutputControl=5, processing time 3 minutes). The reaction was carried out by heating the obtained suspension at 70°C for 4 hours. Dry particles (9) were obtained by heating the resulting slurry at 100°C for 24 hours. Figure 10 shows a TEM image of the obtained particle (9). It was confirmed that the obtained particle (9) is a hollow resin particle with a porous structure consisting of a hollow space surrounded by a shell. The average particle size of the obtained particles (9) was 379 nm. The temperature at which the obtained particles (9) underwent a 10°C / min heating rate resulted in a 5% thermogravimetric loss of 399°C. Table 1 shows the proportions of each ingredient.

[0158] [Example 10] The procedure was carried out in the same manner as in Example 1, except that 2.0 g of a bifunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Corporation), which has an ether structure represented by formula (1), and 3.0 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Material Corporation, 81% content, 19% is ethyl vinylbenzene (EVB)) were used to obtain particles (10). A cross-sectional photograph of the obtained particle (10) is shown in Figure 11. It was confirmed that the obtained particle (10) is a hollow resin particle with a porous structure consisting of a hollow space surrounded by a shell. The average particle size of the obtained particles (10) was 14.4 μm. The temperature at which the obtained particles (10) underwent a nitrogen atmosphere and were heated at a rate of 10°C / min was 312°C, resulting in a 5% thermogravimetric loss. Table 1 shows the proportions of each ingredient.

[0159] [Example 11] The procedure was carried out in the same manner as in Example 1, except that 2.5 g of a bifunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Corporation) and 2.5 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Material Corporation, 81% content, 19% is ethyl vinylbenzene (EVB)) were replaced with 2.0 g of reactive low molecular weight polyphenylene ether (trade name "Noryl® SA9000-111 resin", manufactured by SABIC Corporation) and 3.0 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Material Corporation, 81% content, 19% is ethyl vinylbenzene (EVB)) as compounds having an ether structure represented by formula (1). A cross-sectional photograph of the obtained particle (11) is shown in Figure 12. It was confirmed that the obtained particle (11) is a hollow resin particle with a porous structure consisting of a hollow space surrounded by a shell. The average particle size of the obtained particles (11) was 12.7 μm. The temperature at which the obtained particles (11) underwent a 5% thermogravimetric analysis was 366°C when heated at a rate of 10°C / min in a nitrogen atmosphere. Table 1 shows the proportions of each ingredient.

[0160] [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 Wako Pure Chemical Industries, Ltd.) as a polymerization initiator, and 0.004 g of lauryl phosphate. 32 g of a 2 wt% aqueous dispersion of magnesium pyrophosphate was added to the aqueous phase, and a suspension was prepared using a Polytron homogenizer PT10-35 (Central Science 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, and the solid components were separated by dehydration by filtration. After purification by repeated washing with water, the mixture was dried at 60°C to obtain particles (C1) as a dry powder. A cross-sectional photograph of the obtained particle (C1) is shown in Figure 13. It was confirmed that the obtained particle (C1) is a hollow resin particle in which the hollow region surrounded by the shell consists of a single hollow region. The average particle size of the obtained particles (C1) was 8.3 μm. The 5% thermogravimetric loss temperature of the obtained particles (C1) when heated at a rate of 10°C / min under a nitrogen atmosphere was 245°C. Table 1 shows the proportions of each ingredient.

[0161] [Comparative Example 2] An oil phase was prepared by mixing 1.74 g of methyl methacrylate (MMA), 1.74 g of dipentaerythritol hexaacrylate (ADPH) (Shin-Nakamura Chemical Co., Ltd.), 2.4 g of toluene, 0.126 g of polystyrene (non-crosslinked, weight-average molecular weight 300,000), and 0.104 g of perloyl L (polymerization initiator, NOF Corporation). Next, 34g of deionized water and 0.034g of Rapizole A-80 (surfactant, NOF Corporation) were mixed to prepare the aqueous phase. An oil phase was added to the aqueous phase, and a suspension was prepared using an ultrasonic homogenizer (BRANSON, "SONIFIER450", conditions: DutyCycle=50%, OutputControl=5, processing time 3 minutes). Polymerization was carried out by heating the obtained suspension at 70°C for 4 hours to obtain a slurry. The obtained slurry was heated at 100°C for 24 hours to obtain particles (C2) as a dry powder. Figure 14 shows a TEM image of the obtained particle (C2). It was confirmed that the obtained particle (C2) is a hollow resin particle in which the hollow region surrounded by the shell consists of a single hollow region. The average particle size of the obtained particles (C2) was 478 nm, and the particle density was 0.614 g / cm³. 3 That was the case. The temperature at which the obtained particles (C2) underwent a 10°C / min heating cycle resulted in a 5% thermogravimetric loss of 327°C. Table 1 shows the proportions of each ingredient.

[0162] [Table 1]

[0163] <Performance Evaluation 1: Relative Permittivity and Dielectric Loss Tangent Evaluation 1> 0.4 g of the particles obtained in each example and comparative example, along with 10 g of ultra-high heat-resistant polyimide varnish (product name "SPIXAREA HR(registered trademark)002", manufactured by Somar Co., Ltd.), were defoamed and stirred using a planetary stirring defoamer (manufactured by KURABO Co., Ltd., "Mazelstar KK-250") to prepare evaluation mixtures. The evaluation mixture was coated onto a 5 mm thick glass plate using an applicator 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, and then cooled to room temperature to obtain a film sample containing each particle. The relative 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.

[0164] [Table 2]

[0165] The results in Table 2 confirm that the hollow resin particles provided by the present invention have the effect of lowering the relative permittivity and dielectric loss tangent of the substrate, and are effective for the purpose of reducing the dielectric and dielectric loss tangent of semiconductor materials.

[0166] <Performance Evaluation 2: Relative Permittivity and Dielectric Loss Tangent Evaluation 2> A mixture for evaluation was prepared by defoaming and stirring 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.) using a planetary stirring defoamer ("Mazelstar KK-250" manufactured by KURABO Co., Ltd.). The evaluation mixture was coated onto a 5 mm thick glass plate using an applicator set to a wet thickness of 250 μm. The ethyl acetate was removed by heating at 60°C for 30 minutes, 90°C for 10 minutes, 150°C for 30 minutes, and 200°C for 30 minutes, and then cooled to room temperature to obtain a film sample containing each particle. The relative 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.

[0167] [Table 3]

[0168] The results in Table 3 confirm that the hollow resin particles provided by the present invention have the effect of lowering the relative permittivity and dielectric loss tangent of the substrate, and are effective for the purpose of reducing the dielectric constant and dielectric loss tangent of semiconductor materials.

[0169] <Performance Evaluation 3: Moisture Content Evaluation> The particles obtained in each example and comparative example were subjected to moisture absorption treatment under the following conditions. The particles obtained in each example and comparative example were placed in a constant temperature and humidity chamber at a temperature of 40±1°C and a relative humidity of 95% for 96 hours, then removed and cooled for 30 minutes in an environment of (temperature 20±1°C, humidity 65±5%). 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, set in a Karl Fischer moisture analyzer "CA-200" and a moisture vaporizer "VA-236S" manufactured by Mitsubishi Chemical Analytec Co., Ltd. The anode and cathode liquids used during measurement were "Aquamicron® AX" and "Aquamicron® CXU," both manufactured by Mitsubishi Chemical Corporation. The measurement (vaporization) temperature was 250°C. Nitrogen 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 alone at the sampling location was measured twice, and the average value was used as the blank value. The blank value was subtracted from each measurement result and divided by the sample weight to obtain the moisture content (weight %) of the sample. The moisture content (weight %) of the sample was calculated using the following formula. Moisture content (weight %) = [Actual moisture content (μg) - Blank moisture content (μg)] ÷ 1,000,000 ÷ Sample weight (g) × 100 As a final result, the moisture content (by weight) of the sample was calculated by averaging the results of three measurements. The results are shown in Table 4.

[0170] [Table 4]

[0171] The results in Table 4 show that the hollow resin particles provided by the present invention have a lower moisture content after moisture absorption treatment compared to conventional hollow resin particles, making them suitable for the purpose of reducing the dielectric and dielectric loss tangent of semiconductor materials.

[0172] <Performance Evaluation 4: Thermal Insulation Evaluation> To 10g of commercially available water-based paint (manufactured by Asahi Paint Co., Ltd., product name "Water-based Multipurpose Color Clear"), 2.5g of the particles (1) obtained in Example 1 were added, and the mixture was defoamed and stirred using a planetary agitator and defoamer (manufactured by KURABO Co., Ltd., "Mazelstar KK-250") to prepare a paint for evaluation. The evaluation coating was applied to the black side of the opacity test paper using an applicator set to a wet thickness of 250 μm, and then thoroughly dried at room temperature to obtain a sample plate for light reflectivity evaluation. The reflectance of the light reflectivity evaluation sample plate to ultraviolet light, visible light, and near-infrared light was evaluated in the following order. A UV-Vis-Near-Infrared spectrophotometer (Shimadzu Corporation, "Solid Spec3700") was used to measure reflectance, and the reflectance characteristics of the coated surface of a sample plate for light reflectance evaluation, from UV to near-infrared light (wavelengths 300nm to 2500nm), were measured as reflectance (%). The measurements were performed using a 60mmΦ integrating sphere and Spectralon as the standard white plate. The results obtained are shown in Figure 15. As shown in Figure 15, it was found that the reflectance was high, exceeding 40%, at almost all wavelengths from ultraviolet light to near-infrared light.

[0173] <Performance Evaluation 5: Coating Appearance Evaluation> Two parts by weight of the particles (1) obtained in Example 1 and 20 parts by weight of a commercially available acrylic water-based gloss paint (manufactured by Kanpe Papio Co., Ltd., product name "Super Hit") were mixed for 3 minutes using a stirring and defoaming device, and then defoamed for 1 minute to obtain a paint composition. The obtained coating composition was applied to an ABS resin (acrylonitrile-butadiene-styrene resin) plate using a coating apparatus equipped with a blade with a clearance of 75 μm, and then dried to obtain a coating film. Furthermore, the obtained paint composition was spray-coated onto a 3 mm thick acrylic plate to create a 50 μm thick matte coating. The resulting coating was free of bumps (protrusions) and exhibited excellent matte properties.

[0174] <Performance Evaluation 6: Light Diffusion Evaluation> A light-diffusing resin composition was obtained by mixing 7.5 parts by weight of the 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 a solvent using a stirring and defoaming device for 3 minutes and then defoaming for 1 minute. The obtained light-diffusing resin composition was applied to a 125 μm thick PET film using a coating apparatus equipped with a blade with a clearance of 50 μm, and then dried at 70°C for 10 minutes to obtain a light-diffusing film. The total light transmittance and haze of the obtained light-diffusing films were measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name "NDH 2000") in accordance with JIS K 7361-1:1997 and JIS K 7136:2000, respectively. The haze value increases as the diffusivity of the light transmitted through the light-diffusing film increases. The measurement results showed a haze of 40.2% and a total light transmittance of 81.5%, confirming that the obtained light-diffusing film exhibited excellent light-diffusing properties. [Industrial applicability]

[0175] Hollow resin particles according to embodiments of the present invention, and hollow resin particles obtained by the manufacturing method according to embodiments of the present invention, can be used in semiconductor materials and the like. Hollow resin particles according to embodiments of the present invention, and hollow resin particles obtained by the manufacturing method according to embodiments of the present invention, can be applied, for example, to resin compositions for semiconductor components, paint compositions, heat insulating compositions, light diffusing compositions, and light diffusing films.

Claims

1. A hollow resin particle having a shell portion and a hollow portion surrounded by the shell portion, The average particle size is 0.1 μm to 50.0 μm. The shell portion comprises a polymer (P) having an ether structure represented by formula (1), The polymer (P) is obtained by the reaction of a monomer (B) containing an aromatic crosslinkable monomer and an aromatic monofunctional monomer, and a compound (A) which is a polyphenylene ether having an ether structure represented by formula (1) and terminal groups that react with monomer (B). The terminal group has a polymerizable unsaturated double bond, Hollow resin particles. 【Chemistry 1】

2. The hollow resin particles according to claim 1, wherein the 5% thermoweight loss temperature when the hollow resin particles are heated at 10°C / min in a nitrogen atmosphere is 300°C or higher.

3. Hollow resin particles according to claim 1 or 2, for use in a resin composition for semiconductor components.

4. Hollow resin particles according to claim 1 or 2, for use in a paint composition.

5. Hollow resin particles according to claim 1 or 2, for use in a heat insulating resin composition.

6. Hollow resin particles according to claim 1 or 2, for use in a light-diffusing resin composition.

7. Hollow resin particles according to claim 1 or 2, for use in a light-diffusing film.

8. A resin composition for semiconductor components comprising hollow resin particles according to claim 1 or 2.

9. A paint composition comprising hollow resin particles according to claim 1 or 2.

10. A heat insulating resin composition comprising hollow resin particles according to claim 1 or 2.

11. A light-diffusing resin composition comprising hollow resin particles according to claim 1 or 2.

12. A light-diffusing film comprising hollow resin particles according to claim 1 or 2.

13. A method for producing hollow resin particles according to any one of claims 1 to 7, 20 to 80 parts by weight of compound (A) having an ether structure represented by formula (1) and 80 to 20 parts by weight of monomer (B) that reacts with compound (A) (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. The monomer (B) comprises an aromatic crosslinkable 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). The terminal group has a polymerizable unsaturated double bond, A method for producing hollow resin particles. 【Chemistry 2】

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