Hollow resin particles, method for producing the same, and use thereof

Abstract

Provided are: hollow resin particles having a hollow portion in the particles and exhibiting excellent heat resistance. Also provided is a method for easily producing such hollow resin particles. Furthermore, provided is a use of such hollow resin particles. The hollow resin particles of the embodiments of the present invention are hollow resin particles having a hollow portion in the particles, the hollow resin particles having an ether structure represented by formula (1), and the average particle diameter of the hollow resin particles being 0.1 μm to 100 μm.

Description

Technical Field

[0001] This invention relates to hollow resin particles, their manufacturing methods, and their uses. Background Technology

[0002] Resin particles are used to impart light scattering properties to transparent resins, to make coatings / inks matte, to impart scratch resistance, to give cosmetics slip properties, and to prevent films from sticking together, among other applications.

[0003] To impart various properties, the control of resin particle shape was investigated. For example, hollow resin particles with hollow sections introduced inside the particles were studied.

[0004] Patent Document 1 describes hollow resin particles as suitable for imparting opacity to coatings such as paints and paper coating compositions. Patent Document 1 shows that the hollow resin particles are lightweight because their interiors are hollow, and light is diffusely reflected in the hollow portions. Therefore, they exhibit excellent optical properties such as opacity, whiteness, and gloss, and also possess heat insulation effects. Specifically, Patent Document 1 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 many fields such as thermal recording materials (thermal recording paper, 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 monomers, primarily composed of acrylic polyfunctional monomers such as trimethylolpropane tri(meth)acrylate and dipentaerythritol hexaacrylate, with a hydrophobic solvent.

[0006] Patent Document 3 shows that the shell is formed from free radical reactive monofunctional monomers and crosslinking monomers, and the hollow particles with a single-phase structure are suitable for low dielectricization / low dielectric loss tangent of the insulating layer of multilayer printed circuit boards. Patent Document 3 describes that styrene-based hollow resin particles are obtained by suspension polymerization of divinylbenzene, which is a hollow resin particle, with a saturated hydrocarbon 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 fading due to sebum and sweat secreted from the skin and maintaining a light feel. Patent Document 4 describes acrylic porous particles formed from methyl methacrylate and trimethylolpropane tri(meth)acrylate as porous particles.

[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, pore-forming agents, adsorbents, lightweighting agents, thermal insulation materials, thermal insulation coatings, white pigments, inkjet acceptors, and slow-release agents. Specifically, Patent Document 5 describes acrylic porous particles formed from methyl methacrylate and the like.

[0009] Patent Document 6 shows that porous hollow polymer particles (hollow porous particles) exhibit excellent sustained-release properties, light diffusivity, liquid absorption, subjective sensory properties, solvent resistance, and mechanical strength in their fragrances. Specifically, Patent Document 6 describes a method for obtaining acrylic hollow porous particles by suspension polymerization of monomers, primarily acrylic monomers such as methyl methacrylate and 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. Specifically, Patent Document 7 describes a method for obtaining acrylic hollow porous particles by suspension polymerization of monomers, mainly composed of acrylic monomers such as methyl methacrylate and trimethylolpropane tri(meth)acrylate, with a hydrophobic solvent.

[0011] Patent Document 8 describes particles that exhibit higher heat resistance and solvent resistance than particles formed from vinyl polymers (general polymers) using acrylic acid, styrene, etc., as raw materials, and is classified as engineering plastic particles. Specifically, Patent Document 8 describes particles formed from polyamide, polyphenylene ether, polyetherimide, polyarylate, polyamideimide, and epoxy resin.

[0012] Recently, resin particles with high heat resistance have been required for various applications.

[0013] The hollow particles, porous particles, and hollow porous particles described in Patent Documents 1 to 7 are formed from vinyl polymers (general polymers) using acrylic acid, styrene, etc. as raw materials, and it cannot be said that they have sufficient heat resistance.

[0014] While the particles described in Patent Document 8 have excellent heat resistance, no solution has been provided for controlling the particle structure, such as porous, hollow, or hollow porous particles.

[0015] Existing technical documents

[0016] Patent documents

[0017] Patent Document 1: Japanese Patent Application Publication No. 2002-080503

[0018] Patent Document 2: Japanese Patent No. 6513273

[0019] Patent Document 3: Japanese Patent No. 4171489

[0020] Patent Document 4: Japanese Patent Application Publication No. 2003-081738

[0021] Patent Document 5: Japanese Patent Application Publication No. 2014-111728

[0022] Patent Document 6: Japanese Patent Application Publication No. 2009-120806

[0023] Patent Document 7: Japanese Patent No. 4445495

[0024] Patent Document 8: Japanese Patent No. 5387796 Summary of the Invention

[0025] The problem the invention aims to solve

[0026] This invention addresses the aforementioned problems and its main objective is to provide a hollow resin particle with a hollow portion within the particle, exhibiting excellent heat resistance. Furthermore, it provides a simple method for manufacturing such hollow resin particles. Finally, it provides applications for these hollow resin particles.

[0027] Solution for solving the problem

[0028] The hollow resin particles in the embodiments of the present invention are

[0029] Hollow resin particles with hollow sections inside,

[0030] The hollow resin particles have an ether structure represented by formula (1).

[0031] The average particle size of the hollow resin particles is 0.1 μm to 100 μm.

[0032]

[0033] In one embodiment, the hollow portion comprises a hollow region.

[0034] In one embodiment, the hollow portion comprises multiple hollow regions.

[0035] In one embodiment, the hollow portion is a porous structure.

[0036] In one embodiment, the hollow resin particles of the present invention have: a shell portion and the aforementioned hollow portion surrounded by the shell portion.

[0037] In one embodiment, the 5% thermal weight loss temperature of the hollow resin particles when heated at 10°C / min under a nitrogen atmosphere is 300°C or higher.

[0038] In one embodiment, the hollow resin particles of the present invention are used in a resin composition for semiconductor components.

[0039] In one embodiment, the hollow resin particles of the present invention are used in a coating composition.

[0040] In one embodiment, the hollow resin particles of the present invention are used in a heat-insulating resin composition. In another embodiment, the hollow resin particles of the present invention are used in a light-diffusing resin composition.

[0041] In one embodiment, the hollow resin particles of the present invention are used in a light-diffusing film.

[0042] The resin composition for semiconductor components according to embodiments of the present invention comprises hollow resin particles according to embodiments of the present invention.

[0043] The coating composition of the embodiments of the present invention comprises the hollow resin particles of the embodiments of the present invention.

[0044] The insulating resin composition of the embodiments of the present invention comprises the hollow resin particles of the embodiments of the present invention.

[0045] The light-diffusing resin composition of embodiments of the present invention comprises the hollow resin particles of embodiments of the present invention.

[0046] The light-diffusing film of the embodiments of the present invention comprises hollow resin particles of the embodiments of the present invention.

[0047] The manufacturing method of the embodiments of the present invention is as follows:

[0048] The method for manufacturing hollow resin particles according to embodiments of the present invention,

[0049] The manufacturing method involves reacting 20 to 100 parts by weight of a compound (A) having an ether structure represented by formula (1) with 80 to 0 parts by weight of a monomer (B) that reacts with the compound (A) (the total amount of the compound (A) and the monomer (B) is set to 100 parts by weight) in an aqueous medium in the presence of a non-reactive solvent.

[0050]

[0051] The effects of the invention

[0052] According to embodiments of the present invention, hollow resin particles having hollow portions within the granules and exhibiting excellent heat resistance can be provided. Furthermore, a method for easily manufacturing such hollow resin particles can be provided. Moreover, applications of such hollow resin particles can be provided. Attached Figure Description

[0053] Figure 1 A schematic sectional view to illustrate the structure of the hollow section.

[0054] Figure 2 This is a cross-sectional photograph of the hollow resin particles (1) obtained in Example 1.

[0055] Figure 3 This is a cross-sectional photograph of the hollow resin particles (2) obtained in Example 2.

[0056] Figure 4 This is a cross-sectional photograph of the hollow resin particles (3) obtained in Example 3.

[0057] Figure 5 This is a cross-sectional photograph of the hollow resin particles (4) obtained in Example 4.

[0058] Figure 6 This is a cross-sectional photograph of the hollow resin particles (5) obtained in Example 5.

[0059] Figure 7 This is a cross-sectional photograph of the hollow resin particles (6) obtained in Example 6.

[0060] Figure 8 This is a cross-sectional photograph of the hollow resin particles (7) obtained in Example 7.

[0061] Figure 9 This is a cross-sectional photograph of the hollow resin particles (8) obtained in Example 8.

[0062] Figure 10 This is a cross-sectional photograph of the hollow resin particles (9) obtained in Example 9.

[0063] Figure 11 This is a cross-sectional photograph of the hollow resin particles (10) obtained in Example 10.

[0064] Figure 12 This is a TEM image of the hollow resin particles (11) obtained in Example 11.

[0065] Figure 13 This is a TEM image of the hollow resin particles (12) obtained in Example 12.

[0066] Figure 14This is a cross-sectional photograph of the resin particles (13) with a porous structure obtained in Example 13.

[0067] Figure 15 This is a cross-sectional photograph of the hollow resin particles (14) obtained in Example 14.

[0068] Figure 16 This is a cross-sectional photograph of the hollow resin particles (15) obtained in Example 15.

[0069] Figure 17 This is a cross-sectional photograph of the hollow resin particles (16) obtained in Example 16.

[0070] Figure 18 This is a cross-sectional photograph of the hollow resin particles (17) obtained in Example 17.

[0071] Figure 19 A cross-sectional photograph of the particles (C1) obtained in Comparative Example 1.

[0072] Figure 20 The image shows the ultraviolet-visible-near-infrared reflectance spectrum of the hollow resin particles (1) obtained in Example 1. Detailed Implementation

[0073] The embodiments of the present invention will be described below, but the present invention is not limited to these embodiments.

[0074] 《1. Hollow Core Resin Particles》

[0075] 1-1. Structure and Properties of Hollow Resin Particles

[0076] The hollow resin particles in the embodiments of the present invention are hollow resin particles having a hollow portion inside. Here, "hollow" means a state in which the interior is filled with a substance other than resin, such as gas or liquid; more preferably, it refers to a state in which the interior is filled with gas to further demonstrate the effects of the present invention.

[0077] The hollow resin particles of the present invention only need to have a hollow portion inside the particle. They can have a structure in which a portion of the hollow portion inside the particle on the particle surface is open to the outside of the particle, or they can have a structure with a shell portion and a hollow portion surrounded by the shell portion.

[0078] Hollow part such as Figure 1 As shown in the summary sectional view of (a), it can contain one hollow region, or as shown in the figure. Figure 1 (b) shows a schematic cross-sectional view containing multiple hollow areas.

[0079] The hollow part can also be like Figure 1As shown in the schematic cross-sectional views of (c) and (d), the structure is composed of a porous material. When the hollow portion is a porous structure, it can be either a single hollow region (continuous pores) or multiple hollow regions (independent pores).

[0080] When the hollow part has a porous structure, such as Figure 1 As shown in (c), a hollow portion within a portion of the particle surface can become an open structure to the outside of the particle, such as... Figure 1 As shown in (d), it can also have a structure having a shell portion and a hollow portion surrounded by the shell portion.

[0081] The average particle size of the hollow resin particles in embodiments of the present invention is preferably 0.1 μm to 100 μm, more preferably 0.1 μm to 80 μm, even more preferably 0.2 μm to 50 μm, and particularly 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 are further manifested. If the average particle size of the hollow resin particles in embodiments of the present invention exceeds the above range and is too small, the thickness of the resin layer constituting the hollow portion becomes relatively thin, thus raising concerns that the hollow resin particles may not have sufficient strength. If the average particle size of the hollow resin particles in embodiments of the present invention exceeds the above range and is too large, there is concern that it becomes difficult to induce phase separation between the polymer and the solvent resulting from the polymerization of monomer components in suspension polymerization, thereby making the formation of the hollow portion more difficult.

[0082] For the hollow resin particles of the embodiments of the present invention, the 5% thermogravimetric temperature when heated at 10°C / min under a nitrogen atmosphere is preferably 300°C or higher, more preferably 320°C or higher, further preferably 340°C or higher, and particularly preferably 360°C or higher. The upper limit of the above-mentioned 5% thermogravimetric temperature is practically preferably 500°C or lower. If the 5% thermogravimetric temperature of the hollow resin particles of the embodiments of the present invention when heated at 10°C / min under a nitrogen atmosphere is within the above-mentioned range, the hollow resin particles of the embodiments of the present invention can exhibit excellent heat resistance. If the 5% thermogravimetric temperature of the hollow resin particles of the embodiments of the present invention when heated at 10°C / min under a nitrogen atmosphere exceeds the above-mentioned range but is too small, there is a concern that the heat resistance may become insufficient.

[0083] For the hollow resin particles of the embodiments of the present invention, the moisture content after standing for 96 hours at 40°C and 95% RH 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 particularly preferably 0.35% by weight or less. The lower the moisture content, the better, preferably 0% by weight or more. If the moisture content after standing for 96 hours at 40°C and 95% RH is within the above range, the effects of the present invention are further demonstrated. If the moisture content after standing for 96 hours at 40°C and 95% RH exceeds the above range and is too high, there is a concern that the water absorption rate of the hollow resin particles will increase.

[0084] The hollow resin particles of the embodiments of the present invention have an ether structure represented by formula (1). Specifically, the resin portion of the hollow resin particles of the embodiments of the present invention has an ether structure represented by formula (1).

[0085]

[0086] The hollow resin particles of embodiments of the present invention preferably comprise a polymer (P) having an ether structure represented by formula (1). By comprising such polymer (P), the effects of the present invention are further realized in the hollow resin particles of embodiments of the present invention.

[0087] The polymer (P) can be a single type or two or more types.

[0088] Regarding the content ratio of polymer (P) in the hollow resin particles of the embodiments of the present invention, in order to further demonstrate the effects of the present invention, it is preferred to be 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.

[0089] The hollow resin particles in embodiments of the present invention may contain any other suitable components without impairing the effects of the present invention.

[0090] <Polymer (P)>

[0091] As the polymer (P), any suitable polymer can be used as long as it has an ether structure represented by formula (1) without impairing the effects of the present invention. In terms of further embodying the effects of the present invention, such polymer (P) is preferably 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).

[0092] The compound (A) having an ether structure represented by formula (1) may be only one or more. The monomer (B) reacting with the compound having an ether structure represented by formula (1) may be only one or more.

[0093] Regarding the ratio of compound (A) to monomer (B), if 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).

[0094] As one embodiment of the above preferred ratio, a more preferred ratio is (50 parts by weight to 90 parts by weight): (50 parts by weight to 10 parts by weight), a further preferred ratio is (55 parts by weight to 80 parts by weight): (45 parts by weight to 20 parts by weight), and a particularly preferred ratio is (60 parts by weight to 70 parts by weight): (40 parts by weight to 30 parts by weight).

[0095] As another embodiment of the above preferred ratio, more preferred is (20 parts by weight to 80 parts by weight): (80 parts by weight to 20 parts by weight), further preferred is (30 parts by weight to 70 parts by weight): (70 parts by weight to 30 parts by weight), and particularly preferred is (40 parts by weight to 60 parts by weight): (60 parts by weight to 40 parts by weight).

[0096] If the content of compound (A) is too low and exceeds the above range, there is a concern that the heat resistance will become insufficient.

[0097] As compound (A), any suitable compound can be used as long as it has an ether structure represented by formula (1) without impairing the effects of the present invention. In terms of further embodying the effects of the present invention, polyphenylene ether is preferably an example of such compound (A). Commercially available polyphenylene ethers include, for example, those under the trade names "Noryl" (manufactured by SABIC Corporation), "Iupiace" (manufactured by Mitsubishi Chemical Corporation), "Xyron" (manufactured by Asahi Kasei Corporation), and "OPE-2St" (manufactured by Mitsubishi Gas Chemical Corporation).

[0098] From the perspective of compatibility with non-reactive solvents described later, and from the perspective of being able to more easily produce hollow resin particles with excellent heat resistance, polyphenylene ether is preferably an oligomer, preferably with a number average molecular weight (Mn) of 500 to 3500.

[0099] Examples of monomers (B) include crosslinking monomers and monofunctional monomers. In a manner that further enhances the effects of the invention, monomers that react with the terminal groups of compound (A) are preferred.

[0100] 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. In aspects that further enhance the effects of the present invention, aromatic crosslinking monomers are preferred, and divinylbenzene is more preferred. There may be only one type of crosslinking monomer, or there may be two or more types.

[0101] Examples of monofunctional monomers include alkyl methacrylates with 1 to 16 carbon atoms, such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, and hexadecyl methacrylate; aromatic monofunctional monomers such as styrene, α-methylstyrene, ethyl vinylbenzene, vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, vinylbiphenyl, and vinylnaphthalene; dicarboxylic acid ester monomers such as dimethyl maleate, diethyl fumarate, and diethyl fumarate; maleic anhydride; N-vinylcarbazole; and (meth)acrylonitrile. In terms of further enhancing the effects of the present invention, aromatic monofunctional monomers are preferred, and styrene and ethyl vinylbenzene are more preferred. There may be only one type of monofunctional monomer, or there may be two or more types.

[0102] Polymers (P) can be formed by the reaction of compound (A) with monomer (B).

[0103] The reaction between compound (A) and monomer (B) can be carried out by any suitable reaction without impairing the effects of the present invention. Suspension polymerization is preferred as such a reaction.

[0104] In suspension polymerization, a typical method involves adding an oil phase to an aqueous phase to suspend it and then carrying out the polymerization reaction. The aqueous and oil phases may contain any suitable solvent, provided it does not impair the effects of the invention. Examples of such solvents include aqueous media and non-reactive solvents, which will be described later. The solvent may be one type or two or more types.

[0105] 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" here excludes solvents such as aqueous media and non-reactive solvents, which will be described later.

[0106] 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 particularly preferably 0% to 10% by weight.

[0107] As additive (C), any suitable additive may be used within the scope that does not impair the effects of the present invention. Examples of such additive (C) include non-crosslinked polymers, dispersion stabilizers, surfactants, and polymerization initiators.

[0108] By including a non-crosslinked polymer as an additive (C), the phase separation of the polymer (P) generated during the reaction with the solvent can be promoted, thereby facilitating shell formation.

[0109] 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.

[0110] Examples of polyolefins include polyethylene, polypropylene, and polyalphaolefins. From the viewpoint of solubility in monomer compositions, the use of long-chain α-olefin side-chain crystalline polyolefins, low molecular weight polyolefins produced by metallocene catalysts, or olefin oligomers is preferred.

[0111] Examples of styrene-based polymers include polystyrene, styrene-acrylonitrile copolymers, and acrylonitrile-butadiene-styrene copolymers.

[0112] Examples of (meth)acrylic polymers include poly(meth)acrylate, poly(meth)acrylate, poly(meth)acrylate, poly(meth)acrylate, poly(meth)acrylate, and poly(meth)acrylate.

[0113] Examples of styrene-(meth)acrylate polymers include styrene-(meth)acrylate methyl acrylate copolymer, styrene-(meth)acrylate ethyl acrylate copolymer, styrene-(meth)acrylate butyl acrylate copolymer, and styrene-(meth)acrylate propyl acrylate copolymer.

[0114] 1-2. Relative Permittivity of Hollow Resin Particles

[0115] The relative permittivity of the hollow resin particles in 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 in the embodiments of the present invention is within the above range, the effects of the present invention can be further demonstrated. When the relative permittivity of the hollow resin particles in the embodiments of the present invention is higher than 2.5, even if the hollow resin particles are mixed with, for example, thermosetting resins, a sufficiently low dielectric effect cannot be obtained.

[0116] The relative permittivity of the hollow resin particles in embodiments of the present invention can be calculated, for example, with reference to "Dielectric Constant of Mixed Systems" (Applied Physics, Vol. 27, No. 8 (1958)). Let ε be the relative permittivity of the mixture of the dispersion medium and the hollow resin particles, let ε1 be the relative permittivity of the substrate (e.g., a resin composition such as polyimide or epoxy resin) that will become the dispersion medium, let ε2 be the relative permittivity of the hollow resin particles, and let ε be the volume fraction of the hollow resin particles in the mixture. When ε, ε1, ..., the following formula holds. That is, if ε, ε1, ... are experimentally determined... The relative permittivity ε2 of the hollow resin particles can then be calculated.

[0117]

[0118] It should be noted that the volume fraction of the hollow resin particles in the mixture of the dispersion medium and the hollow resin particles is... It can be calculated using the following formula.

[0119]

[0120] The density of the hollow resin particles can be determined using a specific gravity bottle (manufactured by COTEC Corporation, TQC 50mL specific gravity bottle) and the product name "ARUFON UP-1080" (manufactured by Toa Synthetic Co., Ltd., density 1.05 g / cm³) as a liquid polymer. 3 This was determined experimentally. Specifically, hollow resin particles were used at a ratio of 10% by weight. A planetary agitator and defoamer (Mazerustar KK-250, manufactured by Kurabo Industries Ltd.) were used to defoam and stir the hollow resin particles with ARUFONUP-1080 to prepare an evaluation mixture. The evaluation mixture was then filled into a 50 mL hydrometer bottle. The weight of the filled evaluation mixture was calculated by subtracting the weight of the empty hydrometer bottle from the weight of the bottle filled with the mixture. The density of the hollow resin particles can be calculated from this value using the following formula.

[0121]

[0122] 1-3. Applications of Hollow Core Resin Granules

[0123] The hollow resin particles of the embodiments of the present invention are representatively applicable 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, semiconductor assemblies).

[0124] <Resin Compositions for Semiconductor Components>

[0125] The hollow resin particles of the embodiments of the present invention exhibit excellent heat resistance. In addition, they can achieve low dielectric constant and low dielectric loss tangent, thus making them suitable for use in resin compositions for semiconductor components.

[0126] The resin composition for semiconductor components according to embodiments of the present invention comprises hollow resin particles according to embodiments of the present invention.

[0127] Semiconductor components refer to components that constitute semiconductors, such as semiconductor packages and semiconductor assemblies. In this specification, resin compositions for semiconductor components refer to resin compositions used in semiconductor components.

[0128] A semiconductor package refers to an IC chip as an essential component, constructed using at least one component selected from molding resin, underfill material, mold underfill material, chip bonding material, prepreg for semiconductor package substrate, metal-clad laminate for semiconductor package substrate, and laminated material for printed circuit board for semiconductor package.

[0129] A semiconductor component refers to a component that uses a semiconductor package as an essential constituent element and is constructed using at least one component selected from prepreg for printed circuit boards, metal-clad laminate for printed circuit boards, multilayer material for printed circuit boards, solder resist, cover film, electromagnetic wave shielding film, and adhesive sheet for printed circuit boards.

[0130] <Coating Composition>

[0131] The hollow resin particles of the embodiments of the present invention can impart an excellent appearance to the coating film containing them, and are therefore suitable for use in coating compositions.

[0132] The coating composition of the embodiments of the present invention comprises the hollow resin particles of the embodiments of the present invention.

[0133] The coating composition of embodiments of the present invention preferably comprises at least one selected from binder resins and UV-curable resins. The binder resin may be only one type or may be two or more types. The UV-curable resin may be only one type or may be two or more types.

[0134] As the binder resin, any suitable binder resin can be used within the scope that 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.

[0135] As the UV-curable resin, any suitable UV-curable resin can be used within the range that 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. As a polyfunctional (meth)acrylate resin having three or more (meth)acryloyl groups in one molecule, examples include, for instance, 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.

[0136] In embodiments of the present invention, when the coating composition comprises at least one selected from binder resins and UV-curing resins, the content ratio can be any suitable ratio depending on the purpose. Typically, relative to the total amount of at least one selected from binder resins (in the case of emulsion-type aqueous resins, converted to solids content) and UV-curing resins with the hollow resin particles of embodiments of the present invention, the hollow resin particles of embodiments 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.

[0137] When using a UV-curable resin, it is preferable to use a photopolymerization initiator in conjunction. As the photopolymerization initiator, any suitable photopolymerization initiator can be used within the range that does not impair the effects of the present invention. Examples of such photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, α-hydroxyalkylphenyl ketones, α-aminoalkylphenyl ketones, anthraquinones, thioxanthones, azo compounds, peroxides (described in Japanese Patent Application Publication No. 2001-139663, etc.), 2,3-dialkyldione compounds, disulfide compounds, fluorinated amine compounds, aromatic sulfonium compounds, onium salts, borates, active halogen compounds, and α-acyl oxime esters.

[0138] The coating compositions of embodiments of the present invention may contain solvents. There may be only one type of solvent, or there may be two or more types. When the coating compositions of embodiments of the present invention contain solvents, the content ratio can be any suitable ratio depending on the purpose.

[0139] As a solvent, any suitable solvent may be used within the range that does not impair the effects of the present invention. Preferably, such a solvent is one that can dissolve or disperse the adhesive resin or UV-curable resin. Examples of such solvents include, for oil-based coatings, 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 used in water-based coatings include, for example, water and alcohols.

[0140] The coating composition of the embodiments of the present invention can also be diluted to adjust the viscosity as needed. Any suitable diluent can be used depending on the purpose. Examples of such diluents include the aforementioned solvents. There can be only one diluent or two or more diluents.

[0141] The coating composition of embodiments of the present invention may include other components as needed, such as surface conditioners, flow conditioners, ultraviolet absorbers, light stabilizers, curing catalysts, extender pigments, coloring pigments, metallic pigments, mica powder pigments, and dyes.

[0142] When forming a coating film using the coating composition of the embodiments of the present invention, any suitable coating method can be adopted as the coating method depending on the purpose. Examples of such coating methods include spray coating, roller coating, brush coating, reverse roller coating, gravure coating, die coating, comma coating, and spray coating.

[0143] When forming a coating film using the coating composition of the embodiments of the present invention, any suitable forming method can be adopted depending on the purpose. For example, such a forming method can be described as follows: a coating film is prepared by coating an arbitrary coating surface of a substrate; after drying the coating film, it is cured as needed to form a coating film. Examples of substrates include metals, wood, glass, and plastics (PET (polyethylene terephthalate), PC (polycarbonate), acrylic resins, TAC (triacetyl cellulose), etc.).

[0144] <Insulating Resin Composition>

[0145] The hollow resin particles of the embodiments of the present invention impart excellent thermal insulation properties to coatings containing them, and are therefore suitable for use in thermal insulation resin compositions. Coatings containing the hollow resin particles of the embodiments of the present invention exhibit excellent reflectivity in the wavelength range from ultraviolet to near-infrared light.

[0146] The insulating resin composition of the embodiments of the present invention comprises the hollow resin particles of the embodiments of the present invention.

[0147] The heat-insulating resin composition of embodiments of the present invention preferably comprises at least one selected from adhesive resins and UV-curing resins. For information regarding adhesive resins and UV-curing resins, please refer to the description of the aforementioned coating composition.

[0148] The heat-insulating resin composition of embodiments of the present invention may contain a solvent. Regarding the solvent, the description of the aforementioned coating composition can be referenced.

[0149] The insulating resin composition of the embodiments of the present invention can be diluted as needed to adjust the viscosity. The description of the aforementioned coating composition can be used as a diluent.

[0150] The heat-insulating resin composition of the embodiments of the present invention may contain other components as needed, such as coating conditioners, flow conditioners, ultraviolet absorbers, light stabilizers, curing catalysts, extender pigments, coloring pigments, metallic pigments, mica powder pigments, and dyes.

[0151] As for the coating method and formation method when forming a coating film using the heat-insulating resin composition according to the embodiments of the present invention, the description of the aforementioned coating composition can be referenced.

[0152] <Light-diffusing resin composition>

[0153] The hollow resin particles of the embodiments of the present invention can impart excellent light diffusing properties to the coatings containing them, and therefore are suitable for use in light-diffusing resin compositions.

[0154] The light-diffusing resin composition of embodiments of the present invention comprises the hollow resin particles of embodiments of the present invention.

[0155] The light-diffusing resin composition of embodiments of the present invention preferably comprises at least one selected from adhesive resins and UV-curing resins. The description of the aforementioned coating composition can be referenced regarding adhesive resins and UV-curing resins.

[0156] The light-diffusing resin composition of embodiments of the present invention may contain a solvent. Regarding the solvent, the description of the aforementioned coating composition can be referenced.

[0157] The light-diffusing resin composition of the embodiments of the present invention can be diluted as needed to adjust the viscosity. The description of the aforementioned coating composition can be used as a diluent.

[0158] The light-diffusing resin composition of embodiments of the present invention may contain other components as needed, such as coating conditioners, flow conditioners, ultraviolet absorbers, light stabilizers, curing catalysts, extender pigments, coloring pigments, metallic pigments, mica powder pigments, and dyes.

[0159] As for the coating method and formation method when forming a coating film using the light-diffusing resin composition according to the embodiments of the present invention, the description of the aforementioned coating composition can be referenced.

[0160] <Light Diffusion Thin Film>

[0161] The hollow resin particles of the embodiments of the present invention can impart excellent light diffusion properties to films having coatings containing them, and therefore are also suitable for use in light diffusion films.

[0162] The light-diffusing film of the embodiments of the present invention comprises hollow resin particles of the embodiments of the present invention.

[0163] The light-diffusing film of embodiments of the present invention comprises: a light-diffusing layer formed from the light-diffusing resin composition of embodiments of the present invention and a substrate. It should be noted that the light-diffusing layer may or may not be the outermost layer of the light-diffusing film. The light-diffusing film of embodiments of the present invention may include any other suitable layers depending on the purpose. Examples of such other layers include, for instance, 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 particle layer, a conductive metal oxide particle layer, and a base coating layer.

[0164] Examples of substrates include metals, wood, glass, plastic films, plastic sheets, plastic lenses, plastic panels, cathode ray tubes, fluorescent display tubes, and liquid crystal display panels. Examples of plastics constituting plastic films, plastic sheets, plastic lenses, and plastic panels include PET (polyethylene terephthalate), PC (polycarbonate), acrylic resins, and TAC (triacetyl cellulose).

[0165] "2. Manufacturing Method of Hollow Resin Particles"

[0166] The method for manufacturing hollow resin particles according to embodiments of the present invention involves reacting 20 to 100 parts by weight of a compound (A) having an ether structure represented by formula (1) with 80 to 0 parts by weight of a monomer (B) that reacts with the compound (A) (the total amount of the compound (A) and the monomer (B) is set to 100 parts by weight) in an aqueous medium in the presence of a non-reactive solvent.

[0167]

[0168] According to the above manufacturing method, hollow resin particles of the embodiments of the present invention can be easily manufactured. Hollow resin particles of the 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, the hollow resin particles of the embodiments of the present invention can be manufactured by subjecting compound (A) and monomer (B) to a suspension polymerization reaction.

[0169] Suspension polymerization is typically carried out using an aqueous phase containing an aqueous medium and an oil phase containing a compound (A), a monomer (B), and a non-reactive solvent. Preferably, the oil phase containing the compound (A), the monomer (B), and a non-reactive solvent is added to the aqueous phase containing the aqueous medium, dispersed therein, and then heated to carry out suspension polymerization.

[0170] Dispersion is achieved simply by ensuring that the oil phase exists in droplet form within the aqueous phase; any suitable dispersion method can be employed without compromising the effectiveness of the invention. Representative examples of such dispersion methods include those using homogenizers or homogenizers, such as the PoLytron homogenizer, ultrasonic homogenizer, and high-pressure homogenizer.

[0171] The polymerization temperature need only be suitable for suspension polymerization; any suitable polymerization temperature can be used within the range that does not impair the effects of the present invention. Preferably, the polymerization temperature is 30°C to 80°C. The polymerization time need only be suitable for suspension polymerization; any suitable polymerization time can be used within the range that does not impair the effects of the present invention. Preferably, the polymerization time is 1 hour to 48 hours.

[0172] Post-polymerization heating is a preferred treatment to obtain hollow resin particles with high degree of completion.

[0173] The post-polymerization heating temperature can be any suitable temperature within the range that does not impair the effects of the present invention. Preferably, the post-heating temperature is 70°C to 120°C.

[0174] The post-polymerization heating time can be any suitable time without impairing the effects of the invention. Preferably, this post-heating time is 1 hour to 24 hours.

[0175] As for compounds (A) and monomers (B), the descriptions in the section "1-1. Structure and Properties of Hollow Resin Particles" of "Polymers (P)" can be directly cited.

[0176] The ratio of compound (A) to monomer (B) can be directly referenced from the description in the section "Polymer (P)" of "1-1. Structure and Properties of Hollow Resin Particles" in "1. Hollow Resin Particles". Examples of aqueous media include water and mixtures of water and lower alcohols (methanol, ethanol, etc.).

[0177] 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 typically the appropriate amount for the reaction to proceed in a suspension polymerization reaction in which an oil phase is added to an aqueous phase for suspension, relative to 100 parts by weight of the total amount of compound (A), monomer (B), and non-reactive solvent, preferably 100 to 5000 parts by weight, more preferably 150 to 2000 parts by weight.

[0178] The non-reactive solvent is a solvent that does not chemically react with either the compound (A) having an ether structure represented by formula (1) or the monomer (B) reacting with compound (A), preferably an organic solvent. The non-reactive solvent typically functions as a cavitation agent that provides 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 the hollow resin particles, a non-reactive solvent with a boiling point below 100°C is preferred.

[0179] The non-reactive solvent used as a cavitation agent can be a single solvent or a mixture of solvents.

[0180] The amount of non-reactive solvent added is 100 parts by weight relative to the total amount of compound (A) and monomer (B), preferably 20 to 250 parts by weight.

[0181] 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 additive referred to herein does not include solvents such as aqueous media or non-reactive solvents.

[0182] 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 particularly preferably 0% to 10% by weight.

[0183] As additive (C), any suitable additive may be used within the scope that does not impair the effects of the present invention. Examples of such additive (C) include non-crosslinked polymers, dispersion stabilizers, surfactants, and polymerization initiators.

[0184] For non-crosslinked polymers, the description in the section "Polymers (P)" of "1-1. Structure and Properties of Hollow Resin Particles" can be directly cited.

[0185] Examples of dispersing stabilizers include polyvinyl alcohol, polycarboxylic acid, cellulose compounds (hydroxyethyl cellulose, carboxymethyl cellulose, etc.), and polyvinylpyrrolidone. Additionally, inorganic water-soluble polymers such as sodium tripolyphosphate can 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 water-poorly 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. Magnesium pyrophosphate is preferred because it is easier to remove from hollow resin particles and less likely to remain on the surface of the hollow resin particles. The amount of dispersing stabilizer added relative to 100 parts by weight of the aqueous medium is preferably 0.5 to 10 parts by weight. There can be only one type of dispersing stabilizer or two or more types.

[0186] As surfactants, examples include anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants.

[0187] 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 salts, polyoxyethylene alkylpropylene phenyl ether sulfate ammonium salts, and polyoxyethylene alkenyl ether sulfate ammonium salts. It should be noted that the surfactant is not limited to a salt structure; for example, alkyl sulfates and alkyl phosphates can also be used. Specifically, lauryl sulfate and lauryl phosphate are examples.

[0188] Examples of cationic surfactants include alkyltrimethylammonium salts, alkyltriethylammonium salts, dialkyldimethylammonium salts, dialkyldiethylammonium salts, and N-polyoxyalkylene-N,N,N-trialkylammonium salts.

[0189] Examples of amphoteric surfactants include lauryl dimethylamine oxide, phosphate salts, and phosphite surfactants.

[0190] 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, glycerol fatty acid esters, and oxyethylene-oxypropylene block polymers. 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. There may be only one surfactant or two or more surfactants. It should be noted that increasing the surfactant content ratio makes it easier to construct... Figure 1 As shown in (c), the hollow portion within a portion of the particle surface becomes a porous structure open to the outside of the particle. Figure 1 As shown in (d), the shell portion and the hollow portion surrounded by the shell portion form a porous structure. Therefore, by controlling the content ratio of the surfactant, the structure of the hollow resin particles in the embodiments of the present invention can be controlled.

[0191] As a polymerization initiator, 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 organic peroxides such as lauroyl peroxide, benzoyl peroxide, o-chlorobenzoyl peroxide, o-methoxybenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, tert-butylperoxy-2-ethylhexanoate, and di-tert-butyl peroxide; azo compounds such as 2,2'-azobisisobutyronitrile, 1,1'-azobiscyclohexaneformitrile, and 2,2'-azobis(2,4-dimethylpentanonitrile); etc.

[0192] The content ratio of the polymerization initiator relative to the total amount of compound (A) and monomer (B) is preferably in the range of 0.1% to 5% by weight. There may be only one type of polymerization initiator, or there may be two or more types.

[0193] Example

[0194] The present invention will be specifically described below with reference to specific embodiments, but the present invention is not limited to these embodiments. In addition, unless otherwise stated, "parts" means "parts by weight" and "%" means "% by weight".

[0195] <Determination of volume average particle size (Examples 1-10, 13, Comparative Example 1)>

[0196] The volume average particle size was determined as follows according to the Coulter method.

[0197] 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 pore sizes calibrated according to the Beckman Coulter, Inc. MuLtisizer 3 user manual. It should be noted that the appropriate pore size is selected based on the particle size: 50 μm for particles with an expected volume average particle size of 1 μm or more but less than 10 μm; 100 μm for particles with an expected volume average particle size greater than 10 μm but less than 30 μm; 280 μm for particles with an expected volume average particle size greater than 30 μm but less than 90 μm; and 400 μm for particles with an expected volume average particle size greater than 90 μm but less than 150 μm. If the measured volume average particle size differs from the expected volume average particle size, the measurement is repeated using a pore size of appropriate dimensions. Current and Gain are set appropriately based on the selected pore size. For example, when selecting a pore size of 50 μm, Current is set to -800 and Gain to 4; when selecting a pore size of 100 μm, Current is set to -1600 and Gain to 2; and when selecting pore sizes of 280 μm and 400 μm, Current is set to -3200 and Gain to 1.

[0198] As the sample for the assay, a touch mixer (manufactured by Yamato Scientific Co., Ltd., "TOUCHMIXER MT-31") and an ultrasonic cleaner (manufactured by VELVO-CLEAR, "ULTRASONIC CLEANER VS-150") were used to disperse 0.1 g of particles in 10 mL of a 0.1 wt% nonionic surfactant aqueous solution as the dispersion. During the assay, the mixture was slowly stirred until no air bubbles entered the beaker, and the assay was terminated after measuring 100,000 particles. It should be noted that the volume-average particle size was set as the arithmetic mean of the particle size distribution of 100,000 particles on a volume basis.

[0199] <Determination of average particle size (Examples 11, 12)>

[0200] The Z-mean particle size of hollow resin particles or granules is determined by dynamic light scattering method, and the measured Z-mean particle size is taken as the average particle size of the hollow resin particles or granules.

[0201] Specifically, firstly, the obtained slurry-like hollow resin particles or granules are diluted with deionized water. A laser is then applied to the aqueous dispersion adjusted to 0.1% by weight, and the intensity of the scattered light from the hollow resin particles or granules is measured over time in microseconds. Next, the detected scattering intensity distribution originating from the hollow resin particles or granules is applied to a normal distribution, and the Z-mean particle size of the hollow resin particles or granules is determined using a cumulative analysis method to calculate the average particle size.

[0202] The determination of the Z-mean particle size can be easily performed using commercially available particle size measuring devices. The following examples and comparative examples use a particle size measuring device (Malvern, "ZETASIZER NANO ZS") to determine the Z-mean particle size. Typically, commercially available particle size measuring devices are equipped with data analysis software that automatically analyzes the measurement data to calculate the Z-mean particle size.

[0203] <Cross-section observation>

[0204] The dried granules were mixed with photocurable resin D-800 (manufactured by NEC Corporation) and irradiated with ultraviolet light to obtain a cured product. The cured product was then cut with tweezers, and the cross-section was smoothed using a cutting machine. The sample was then coated using an Auto Fine Coater JFC-1300 sputtering apparatus (manufactured by NEC Corporation). Next, the cross-section of the sample was photographed using the secondary electron detector of a SU1510 scanning electron microscope (manufactured by HitacHi-TecHnoLoGies Corporation).

[0205] <TEM Measurement: Observation of the presence, absence, and shape of hollow resin particles>

[0206] For hollow resin particles or granules as dry powder, surface treatment was performed using an "Osmiumcoater Neoc-Pro" coating apparatus manufactured by Meiwafosis Co., Ltd. (10 Pa, 5 mA, 10 seconds). Then, the hollow resin particles or granules were observed using TEM (transmission electron microscope, Hi-7600 manufactured by HiGH-TecHnoLoGies Corporation) to confirm the presence and shape of the hollow resin particles or granules. At this time, the accelerating voltage was set to 80 kV, and the magnification was set to 5000x or 10,000x for imaging.

[0207] <Determination of 5% thermogravimetric temperature when heating at 10°C / min under nitrogen atmosphere>

[0208] The 5% thermogravimetric temperature was determined using a differential thermal and thermogravimetric analysis (DTA) apparatus manufactured by SII NanoTecHnoLoGy Inc., namely the "TG / DTA6200, AST-2". The sampling method and temperature conditions are as follows.

[0209] 10.5 ± 0.5 mg of sample was filled seamlessly into the bottom of a platinum measuring vessel as the sample for the determination. Using alumina as a reference material and based on a nitrogen flow rate of 230 mL / min, the 5% thermogravimetric temperature (TGT) was determined. The TG / DTA curve was obtained by heating the sample from 30 °C to 500 °C at a heating rate of 10 °C / min. The temperature at which 5% weight loss occurred was calculated using the analytical software provided with the apparatus from this curve and was taken as the 5% TGT.

[0210] [Example 1]

[0211] An oil phase was prepared by mixing 2.5 g of a difunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Co., Ltd.) having an ether structure represented by formula (1), 2.5 g of divinylbenzene (DVB) 810 (manufactured by NIPPON STEELCHemicaL & MateriaL Co., Ltd., 81% content, 19% ethylvinylbenzene (EVB)), 5.0 g of heptane, 0.05 g of 2,2'-azobis(2,4-dimethylpentanilonitrile) (trade name "V-65", manufactured by FUJIFILM WakoPure CHemicaL Corporation) as a polymerization initiator, and 0.004 g of lauryl phosphate.

[0212] 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 Commerce, Inc.). 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 then separated by filtration-based dehydration, and the mixture was purified by repeated washing with water. The slurry was then dried at 60°C to obtain particles (1).

[0213] The cross-sectional photograph of the obtained particle (1) is shown in the figure. Figure 2 It can be confirmed that the obtained particles (1) are a mixture of hollow resin particles containing a hollow region surrounded by a shell and hollow resin particles composed of a porous structure surrounded by a shell.

[0214] The average particle size of the obtained particles (1) was 16.3 μm.

[0215] The 5% thermal weight loss temperature of the obtained particles (1) under nitrogen atmosphere at a heating rate of 10 °C / min was 306 °C.

[0216] The mixing amounts are shown in Table 1.

[0217] [Example 2]

[0218] The same procedure as in Example 1 was followed to obtain particles (2). 3.0 g of a difunctional polyphenylene ether oligomer (trade name “OPE-2St 1200”, manufactured by Mitsubishi Gas Chemical Co., Ltd.) having an ether structure represented by formula (1) and 2.0 g of divinylbenzene (DVB) 810 (manufactured by NIPPON STEELCHemica L & Materia L Co., Ltd., containing 81% of the product and 19% of ethylvinylbenzene (EVB)) were prepared.

[0219] The cross-sectional photograph of the obtained particle (2) is shown in the figure. Figure 3 It can be confirmed that the obtained particles (2) are hollow resin particles surrounded by a shell and containing a hollow region.

[0220] The average particle size of the obtained particles (2) was 15.2 μm.

[0221] The 5% thermal weight loss temperature of the obtained particles (2) under nitrogen atmosphere at a heating rate of 10 °C / min was 320 °C.

[0222] The mixing amounts are shown in Table 1.

[0223] [Example 3]

[0224] The same procedure as in Example 1 was followed to obtain particles (3). 3.5 g of a difunctional polyphenylene ether oligomer (trade name “OPE-2St 1200”, manufactured by Mitsubishi Gas Chemical Co., Ltd.) having an ether structure represented by formula (1) and 1.5 g of divinylbenzene (DVB) 810 (manufactured by NIPPON STEELCHemica L & Materia L Co., Ltd., containing 81% of the product and 19% of ethylvinylbenzene (EVB)) were prepared.

[0225] The cross-sectional photograph of the obtained particle (3) is shown in the figure. Figure 4 It can be confirmed that the obtained particles (3) are hollow resin particles containing a hollow region surrounded by a shell.

[0226] The average particle size of the obtained particles (3) was 13.9 μm.

[0227] The 5% thermal weight loss temperature of the obtained particles (3) under nitrogen atmosphere at a heating rate of 10 °C / min was 309 °C.

[0228] The mixing amounts are shown in Table 1.

[0229] [Example 4]

[0230] 2.5 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 an ether structure represented by formula (1), was used instead of 2.5 g of difunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Co., Ltd.), which is a compound having an ether structure represented by formula (1). Otherwise, the procedure was carried out in the same manner as in Example 1 to obtain particles (4).

[0231] The cross-sectional photograph of the obtained particle (4) is shown in the figure. Figure 5 It can be confirmed that the obtained particles (4) are hollow resin particles composed of a porous structure surrounded by a shell.

[0232] The average particle size of the obtained particles (4) was 16.5 μm.

[0233] The 5% thermal weight loss temperature of the obtained particles (4) under nitrogen atmosphere at a heating rate of 10 °C / min was 373 °C.

[0234] The mixing amounts are shown in Table 1.

[0235] [Example 5]

[0236] 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 an ether structure represented by formula (1), was used instead of 3.0 g of difunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Co., Ltd.), which is a compound having an ether structure represented by formula (1). Otherwise, the same procedure as in Example 2 was followed to obtain particles (5).

[0237] The cross-sectional photograph of the obtained particle (5) is shown in the figure. Figure 6 It can be confirmed that the obtained particles (5) are hollow resin particles composed of a porous structure surrounded by a shell.

[0238] The average particle size of the obtained particles (5) was 15.6 μm.

[0239] The 5% thermal weight loss temperature of the obtained particles (5) under nitrogen atmosphere at a heating rate of 10 °C / min was 420 °C.

[0240] The mixing amounts are shown in Table 1.

[0241] [Example 6]

[0242] Without adding 0.004 g of lauryl phosphate to the oil phase, 30 g of 1.5 wt% aqueous solution of polyvinyl alcohol (GH-14L) was used instead of 32 g of 2 wt% aqueous dispersion of magnesium pyrophosphate as the aqueous phase. Otherwise, the process was carried out in the same manner as in Example 1 to obtain particles (6).

[0243] The cross-sectional photograph of the obtained particle (6) is shown in the figure. Figure 7 It can be confirmed that the obtained particles (6) are a mixture of hollow resin particles containing a hollow region surrounded by a shell and hollow resin particles composed of a porous structure surrounded by a shell.

[0244] The average particle size of the obtained particles (6) was 20.7 μm.

[0245] The 5% thermal weight loss temperature of the obtained particles (6) under nitrogen atmosphere at a heating rate of 10 °C / min was 302 °C.

[0246] The mixing amounts are shown in Table 1.

[0247] [Example 7]

[0248] Without adding 0.004 g of lauryl phosphate to the oil phase, 30 g of 1.5 wt% aqueous solution of polyvinyl alcohol (GH-14L) was used instead of 32 g of 2 wt% aqueous dispersion of magnesium pyrophosphate as the aqueous phase. Otherwise, the process was carried out in the same manner as in Example 2 to obtain particles (7).

[0249] The cross-sectional photograph of the obtained particle (7) is shown in the figure. Figure 8 It can be confirmed that the obtained particles (7) are hollow resin particles surrounded by a shell and containing a hollow region.

[0250] The average particle size of the obtained particles (7) was 18.3 μm.

[0251] The 5% thermal weight loss temperature of the obtained particles (7) under nitrogen atmosphere at a heating rate of 10 °C / min was 315 °C.

[0252] The mixing amounts are shown in Table 1.

[0253] [Example 8]

[0254] Without adding 0.004 g of lauryl phosphate to the oil phase, 30 g of 1.5 wt% aqueous solution of polyvinyl alcohol (GH-14L) was used instead of 32 g of 2 wt% aqueous dispersion of magnesium pyrophosphate as the aqueous phase. Otherwise, the process was carried out in the same manner as in Example 5 to obtain particles (8).

[0255] The cross-sectional photograph of the obtained particle (8) is shown in the figure. Figure 9 It can be confirmed that the obtained particles (8) are hollow resin particles composed of a porous structure surrounded by a shell.

[0256] The average particle size of the obtained particles (8) was 19.4 μm.

[0257] The 5% thermal weight loss temperature of the obtained particles (8) under nitrogen atmosphere at a heating rate of 10 °C / min was 411 °C.

[0258] The mixing amounts are shown in Table 1.

[0259] [Example 9]

[0260] The reactive low molecular weight polyphenylene ether (trade name "Noryl (registered trademark) SA9000-111 resin", manufactured by SABIC Corporation), 1.8 g, divinylbenzene (DVB) 810 (manufactured by NIPPON STEEL Chemical & Material Co., Ltd., 81% content, 19% ethylvinylbenzene (EVB)), 5.0 g, and toluene 2.0 g were used instead of the difunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Co., Ltd.), which is a compound having an ether structure represented by formula (1). 2.5 g of 81% of the product (19% of ethyl vinylbenzene (EVB)) and 5.0 g of heptane were prepared in the same manner as in Example 1 to obtain granules (9).

[0261] The cross-sectional photograph of the obtained particle (9) is shown in the figure. Figure 10 It can be confirmed that the obtained particles (9) are hollow resin particles composed of a porous structure surrounded by a shell.

[0262] The average particle size of the obtained particles (9) was 15.1 μm.

[0263] The 5% thermal weight loss temperature of the obtained particles (9) under nitrogen atmosphere at a heating rate of 10 °C / min was 415 °C.

[0264] The mixing amounts are shown in Table 1.

[0265] [Example 10]

[0266] 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 an ether structure represented by formula (1), 1.0 g of divinylbenzene (DVB) 810 (manufactured by NIPPON STEEL Chemical & Material Co., Ltd., 81% content, 19% ethylvinylbenzene (EVB)), 4.0 g of heptane, and 1.0 g of cyclohexane instead 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 & Material Co., Ltd.), and 5.0 g of heptane as a compound having an ether structure represented by formula (1), the same procedure as in Example 1 was followed to obtain particles (10).

[0267] The cross-sectional photograph of the obtained particle (10) is shown in the figure. Figure 11 It can be confirmed that the obtained particles (10) are hollow resin particles composed of a porous structure surrounded by a shell.

[0268] The average particle size of the obtained particles (10) was 13.1 μm.

[0269] The 5% thermal weight loss temperature of the obtained particles (10) under nitrogen atmosphere at a heating rate of 10 °C / min was 428 °C.

[0270] The mixing amounts are shown in Table 1.

[0271] [Example 11]

[0272] 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., which is a compound having an ether structure represented by formula (1), 1.5 g of divinylbenzene (DVB) 810 (manufactured by NIPPON STEELC Chemical & Material 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.

[0273] Next, 34g of ion-exchanged water was mixed with 0.0128g 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 Ultrasonics Corporation, "SONIFIER450", conditions: Duty Cycle = 50%, Output Control = 5, processing time 3 minutes). The resulting suspension was heated at 70°C for 4 hours to allow the reaction to proceed. The resulting slurry was heated at 100°C for 24 hours to dry, yielding particles (11).

[0274] The TEM image of the obtained particle (11) is shown in the figure. Figure 12 It can be confirmed that the obtained particles (11) are hollow resin particles composed of a porous structure surrounded by a shell.

[0275] The average particle size of the obtained particles (11) is 320 nm.

[0276] The 5% thermal weight loss temperature of the obtained particles (11) under nitrogen atmosphere at a heating rate of 10 °C / min was 315 °C.

[0277] The mixing amounts are shown in Table 1.

[0278] [Example 12]

[0279] 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 an ether structure represented by formula (1), 0.72 g of divinylbenzene (DVB) 810 (manufactured by NIPPON STEEL Chemical & Material Co., Ltd., 81% content, 19% ethylvinylbenzene (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.

[0280] 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 Ultrasonics Corporation, "SONIFIER450", conditions: Duty Cycle = 50%, Output Control = 5, processing time 3 minutes). The resulting suspension was heated at 70°C for 4 hours to allow the reaction to proceed. The resulting slurry was heated at 100°C for 24 hours to dry, yielding particles (12).

[0281] The TEM image of the obtained particle (12) is shown in the figure. Figure 13 It can be confirmed that the obtained particles (12) are hollow resin particles with a porous structure surrounded by a shell.

[0282] The average particle size of the obtained particles (12) is 379 nm.

[0283] The 5% thermal weight loss temperature of the obtained particles (12) under nitrogen atmosphere at a heating rate of 10 °C / min was 399 °C.

[0284] The mixing amounts are shown in Table 1.

[0285] [Example 13]

[0286] In addition to adding 0.15 g of sodium lauryl sulfate to the aqueous phase instead of 0.004 g of lauryl phosphate, particles (13) were obtained in the same manner as in Example 5.

[0287] The cross-sectional photograph of the obtained particle (13) is shown in the figure. Figure 14 It can be confirmed that the obtained particles (13) are resin particles composed of a porous structure.

[0288] The average particle size of the obtained particles (13) was 5.4 μm.

[0289] The 5% thermal weight loss temperature of the obtained particles (13) under nitrogen atmosphere at a heating rate of 10 °C / min was 415 °C.

[0290] The mixing amounts are shown in Table 1.

[0291] [Example 14]

[0292] The same procedure as in Example 1 was followed to obtain particles (14). 2.0 g of a difunctional polyphenylene ether oligomer (trade name “OPE-2St 1200”, manufactured by Mitsubishi Gas Chemical Co., Ltd.) having an ether structure represented by formula (1) and 3.0 g of divinylbenzene (DVB) 810 (manufactured by NIPPON STEELC Chemical & Material Co., Ltd., containing 81% of the product, 19% of which is ethylvinylbenzene (EVB)) were prepared.

[0293] The cross-sectional photograph of the obtained particle (14) is shown in the figure. Figure 15 It can be confirmed that the obtained particles (14) are hollow resin particles with a porous structure surrounded by a shell.

[0294] The average particle size of the obtained particles (14) was 14.4 μm.

[0295] The 5% thermal weight loss temperature of the obtained particles (14) under nitrogen atmosphere at a heating rate of 10 °C / min was 312 °C.

[0296] The mixing amounts are shown in Table 1.

[0297] [Example 15]

[0298] Using 2.0 g of reactive low molecular weight polyphenylene ether (trade name "Noryl (registered trademark) SA9000-111 resin", manufactured by SABIC Corporation) as a compound having an ether structure represented by formula (1), and 3.0 g of divinylbenzene (DVB) 810 (manufactured by NIPPON STEEL Chemical & Material Co., Ltd., 81% content, 19% ethylvinylbenzene (EVB)) instead of difunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Co., Ltd.) and divinylbenzene (DVB) 810 (manufactured by NIPPON STEEL Chemical & Material Co., Ltd., 81% content, 19% ethylvinylbenzene (EVB)) 2.5 g as a compound having an ether structure represented by formula (1), and otherwise proceeding in the same manner as in Example 1, particles (15) were obtained.

[0299] The cross-sectional photograph of the obtained particle (15) is shown in the figure. Figure 16 It can be confirmed that the obtained particles (15) are hollow resin particles composed of a porous structure surrounded by a shell.

[0300] The average particle size of the obtained particles (15) was 12.7 μm.

[0301] The 5% thermal weight loss temperature of the obtained particles (15) under nitrogen atmosphere at a heating rate of 10 °C / min was 366 °C.

[0302] The mixing amounts are shown in Table 1.

[0303] [Example 16]

[0304] Using 1.5 g of reactive low molecular weight polyphenylene ether (trade name "Noryl (registered trademark) SA9000-111 resin", manufactured by SABIC Corporation) as a compound having an ether structure represented by formula (1), and 3.5 g of divinylbenzene (DVB) 810 (manufactured by NIPPON STEEL Chemical & Material Co., Ltd., 81% content, 19% ethylvinylbenzene (EVB)) instead of difunctional polyphenylene ether oligomer (trade name "OPE-2ST 1200", manufactured by Mitsubishi Gas Chemical Co., Ltd.) and divinylbenzene (DVB) 810 (manufactured by NIPPON STEEL Chemical & Material Co., Ltd., 81% content, 19% ethylvinylbenzene (EVB)) 2.5 g as a compound having an ether structure represented by formula (1), the procedure was carried out in the same manner as in Example 1 to obtain particles (16).

[0305] The cross-sectional photograph of the obtained particle (16) is shown in the figure. Figure 17 It can be confirmed that the obtained particles (16) are hollow resin particles with a porous structure surrounded by a shell.

[0306] The average particle size of the obtained particles (16) was 10.9 μm.

[0307] The 5% thermal weight loss temperature of the obtained particles (16) under nitrogen atmosphere at a heating rate of 10 °C / min was 371 °C.

[0308] The mixing amounts are shown in Table 1.

[0309] [Example 17]

[0310] Using 1.0 g of reactive low molecular weight polyphenylene ether (trade name "Noryl (registered trademark) SA9000-111 resin", manufactured by SABIC Corporation) as a compound having an ether structure represented by formula (1), and 4.0 g of divinylbenzene (DVB) 810 (manufactured by NIPPON STEEL Chemical & Material Co., Ltd., 81% content, 19% ethylvinylbenzene (EVB)) instead of difunctional polyphenylene ether oligomer (trade name "OPE-2ST 1200", manufactured by Mitsubishi Gas Chemical Co., Ltd.) and divinylbenzene (DVB) 810 (manufactured by NIPPON STEEL Chemical & Material Co., Ltd., 81% content, 19% ethylvinylbenzene (EVB)) 2.5 g as a compound having an ether structure represented by formula (1), and 2.5 g of divinylbenzene (DVB) 810 (manufactured by NIPPON STEEL Chemical & Material Co., Ltd., 81% content, 19% ethylvinylbenzene (EVB)) 2.5 g, the same procedure as in Example 1 was followed to obtain particles (17).

[0311] The cross-sectional photograph of the obtained particle (17) is shown in the figure. Figure 18 It can be confirmed that the obtained particles (17) are hollow resin particles composed of a porous structure surrounded by a shell.

[0312] The average particle size of the obtained particles (17) was 11.3 μm.

[0313] The 5% thermal weight loss temperature of the obtained particles (17) under nitrogen atmosphere at a heating rate of 10 °C / min was 382 °C.

[0314] The mixing amounts are shown in Table 1.

[0315] [Comparative Example 1]

[0316] 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-dimethylpentanones) (trade name "V-65", manufactured by FUJIFILM Wako Pure Chemical Corporation) as a polymerization initiator, and 0.004 g of lauryl phosphate.

[0317] 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 Commerce, Inc.). 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 then separated by filtration-based dehydration, and the mixture was repeatedly washed with water for purification. Finally, it was dried at 60°C to obtain granules (Cl) as a dried powder.

[0318] The cross-sectional photograph of the obtained particle (C1) is shown in the figure. Figure 19 It can be confirmed that the obtained particles (C1) are hollow resin particles containing a hollow region and surrounded by a shell.

[0319] The average particle size of the obtained particles (C1) was 8.3 μm.

[0320] The 5% thermal weight loss temperature of the obtained particles (C1) under nitrogen atmosphere at a heating rate of 10 °C / min was 245 °C.

[0321] The mixing amounts are shown in Table 1.

[0322] [Table 1]

[0323]

[0324] <Performance Evaluation 1: Evaluation of Relative Permittivity / Dielectric Loss Tangent>

[0325] Using a planetary agitator (Mazerustar KK-250, manufactured by Kurabo Industries Ltd.), 0.4 g of the particles obtained in each example and comparative example were agitated with 10 g of ultra-high heat resistant polyimide varnish (trade name "SPIXAREA HR (registered trademark) 002", manufactured by SOMAR CORPORATION) to prepare an evaluation mixture.

[0326] Using a smearer with a wet thickness set to 250 μm, the evaluation mixture was applied to a 5 mm thick glass plate. The plate was then heated at 120 °C for 10 min, 180 °C for 180 min, and 270 °C for 60 min to remove the solvent. After cooling to room temperature, a thin film sample containing each particle was obtained. The relative permittivity / dielectric loss tangent of the obtained thin film was evaluated using the cavity resonance method (measurement frequency: 5.8 GHz). The results are shown in Table 2.

[0327] [Table 2]

[0328] The results in Table 2 confirm that the hollow resin particles provided by the present invention have the effect of reducing the relative permittivity / dielectric loss tangent of the substrate, and are effective in achieving the goal of reducing the dielectric constant and the dielectric loss tangent of semiconductor materials.

[0329] <Performance Evaluation 2: Evaluation of Relative Permittivity / Dielectric Loss Tangent 2>

[0330] An evaluation mixture was prepared by degassing 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 agitator (Mazerustar KK-250, manufactured by Kurabo Industries Ltd.) to produce a mixture for evaluation.

[0331] Using a smearer with a wet thickness set to 250 μm, the evaluation mixture was coated onto a 5 mm thick glass plate. The plate was then heated at 60 °C for 30 min, 90 °C for 10 min, 150 °C for 30 min, and 200 °C for 30 min to remove ethyl acetate. After cooling to room temperature, a thin film sample containing the individual particles was obtained. The relative permittivity / dielectric loss tangent of the obtained film was evaluated using the cavity resonance method (measurement frequency: 5.8 GHz). The results are shown in Table 3.

[0332] [Table 3]

[0333] The results in Table 3 confirm that the hollow resin particles provided by the present invention have the effect of reducing the relative permittivity / dielectric loss tangent of the substrate, and are effective in achieving the goal of reducing the dielectric constant and the dielectric loss tangent of semiconductor materials.

[0334] <Performance Evaluation 3: Moisture Content Evaluation>

[0335] The particles obtained in each embodiment and comparative example were subjected to moisture absorption treatment under the following conditions.

[0336] The particles obtained in each example and comparative example were placed in a constant temperature and humidity bath at 40±1℃ and 95% relative humidity. After 96 hours, they were removed and cooled for 30 minutes at (20±1℃ and 65±5%). After cooling, the moisture content was measured.

[0337] Moisture content was determined as follows: 0.1 g of particles obtained in each example and comparative example was used as a sample and installed on a “CA-200” Karl Fischer moisture analyzer and a “VA-236S” moisture vaporization apparatus manufactured by Mitsubishi Chemical Analytech Co., Ltd. The anolyte and catholyte used during the measurement were “AQUAMICRON (registered trademark) AX” and “AQUAMICRON (registered trademark) CXU” manufactured by Mitsubishi Chemical Co., Ltd., respectively. The measurement (vaporization) temperature was set to 250°C. Nitrogen gas was used as the carrier gas. The carrier gas flow rate was set to 150 mL / min. The sample was tested three times. The moisture content of the air at the sample collection site was measured twice, and the average value was used as a blank value. The moisture content (wt%) of the sample was calculated by subtracting the blank value from each measurement result and dividing by the sample weight. The moisture content (wt%) of the sample was calculated using the following formula.

[0338] Moisture content (wt%) = [Measured moisture content (μg) - Blank moisture content (μg)] ÷ 1,000,000 ÷ Sample weight (g) × 100

[0339] As a final result, the average of the three measurements was taken as the moisture content (wt%) of the sample. The results are shown in Table 4.

[0340] [Table 4]

[0341] As shown in Table 4, the hollow resin particles provided by the present invention have a lower moisture content after moisture absorption treatment compared with existing hollow resin particles, and are also suitable for achieving the purpose of low dielectric constant and low dielectric loss tangent in semiconductor materials.

[0342] <Performance Evaluation 4: Thermal Insulation Evaluation>

[0343] 10g of commercially available water-based paint (manufactured by ASAHIPEN CORPORATION, trade name "Water-based Multipurpose ColorClear") was mixed with 2.5g of granules (1) obtained in Example 1, and the mixture was deaerated and stirred using a planetary agitator (manufactured by Kurabo Industries Ltd., "Mazerustar KK-250") to prepare an evaluation paint.

[0344] The evaluation coating was applied to the black side of the opacity test paper using a smearer with a wet thickness set to 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 according to the following points.

[0345] A UV-Vis-NIR spectrophotometer (Shimadzu Corporation, "Solid Spec3700") was used as the reflectance measuring device. The reflectance characteristics of the coated surface of the light reflectance evaluation sample plate from ultraviolet to near-infrared light (wavelength 300 nm to 2500 nm) were measured as reflectance (%). It should be noted that a 60 mmΦ integrating sphere was used for the measurement, and a spectral mode was used in the standard white plate.

[0346] The results are shown in Figure 20 .like Figure 20 As shown, it has a high reflectivity of over 40% across almost all wavelengths from ultraviolet to near-infrared light.

[0347] <Performance Evaluation 5: Coating Appearance Evaluation>

[0348] Using a stirring and degassing device, 2 parts by weight of the particles (1) obtained in Example 1 were mixed with 20 parts by weight of commercially available acrylic water-based glossy coating (manufactured by Kanpe Hapio Co., Ltd., trade name "Super Hit") for 3 minutes, and then degassed for 1 minute to obtain the coating composition.

[0349] The obtained coating composition was applied to an ABS resin (acrylonitrile-butadiene-styrene resin) plate using a coating device with blades having a gap of 75 μm, and then dried to obtain a coating film.

[0350] In addition, the obtained coating composition was blown onto a 3 mm thick acrylic sheet and coated to form a 50 μm thick matte coating film. The resulting coating film showed no particles (protrusions) and exhibited good matte properties.

[0351] <Performance Evaluation 6: Light Diffusivity Evaluation>

[0352] Using a stirring degassing device, 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 solvent were mixed for 3 minutes and degassed for 1 minute to obtain a light-diffusing resin composition.

[0353] The light-diffusing resin composition was coated onto a 125 μm thick PET film using a coating device with blades having a 50 μm gap, and then dried at 70 °C for 10 minutes to obtain a light-diffusing film.

[0354] The total transmittance and haze of the light-diffusing film were measured using a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., trade name "NDH 2000") according to JIS K 7361-1:1997 and JIS K 7136:2000, respectively. The higher the diffusivity of light transmitted through the light-diffusing film (transmitted light), the higher the haze value.

[0355] The results were as follows: haze was 40.2% and total transmittance was 81.5%, confirming that the obtained light-diffusing film has excellent light diffusion properties.

[0356] Industrial availability

[0357] 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-insulating compositions, light-diffusing compositions, and light-diffusing films.

Claims

1. A hollow resin particle, having a hollow portion within the particle, The hollow resin particles comprise a polymer (P) having an ether structure represented by formula (1). The polymer (P) is obtained by reacting compound (A) with monomer (B), wherein monomer (B) reacts with the terminal group of compound (A). The compound (A) is a polyphenylene ether oligomer having an ether structure represented by formula (1) and a number-average molecular weight of 500-3500. The monomer (B) comprises aromatic crosslinking monomers and aromatic monofunctional monomers. The hollow resin particles have an average particle size of 0.1 μm to 100 μm. The aromatic crosslinking monomer is selected from at least one of the group consisting of divinylbenzene, divinylnaphthalene, and diallyl phthalate. The aromatic monofunctional monomer is selected from at least one group consisting of styrene, α-methylstyrene, ethyl vinylbenzene, vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, vinyl biphenyl, and vinylnaphthalene. When the total amount of compound (A) and monomer (B) is set to 100 parts by weight, the ratio of compound (A) to monomer (B) by weight is 20 to 80 parts by weight: 80 to 20 parts by weight. 。 2. The hollow resin particles according to claim 1, wherein, The hollow portion can be any of the following structures: containing one hollow region, containing multiple hollow regions, or composed of a porous structure.

3. The hollow resin particle according to claim 2, having a shell portion and the hollow portion surrounded by the shell portion.

4. The hollow resin particles according to any one of claims 1 to 3, wherein, The 5% thermal weight loss temperature of the hollow resin particles under a nitrogen atmosphere at a heating rate of 10°C / min is above 300°C.

5. The hollow resin particles according to claim 1, used in a resin composition for semiconductor components.

6. The hollow resin particles according to claim 1, used in a coating composition.

7. The hollow resin particles according to claim 1, used in a thermal insulation resin composition.

8. The hollow resin particles according to claim 1, used in a light-diffusing resin composition.

9. The hollow resin particles according to claim 1, used in a light-diffusing film.

10. A resin composition for semiconductor components comprising hollow resin particles according to any one of claims 1 to 4.

11. A coating composition comprising hollow resin particles according to any one of claims 1 to 4.

12. A heat-insulating resin composition comprising hollow resin particles according to any one of claims 1 to 4.

13. A light-diffusing resin composition comprising hollow resin particles according to any one of claims 1 to 4.

14. A light-diffusing film comprising hollow resin particles according to any one of claims 1 to 4.

15. A method for manufacturing hollow resin particles, comprising the method for manufacturing hollow resin particles according to any one of claims 1 to 9. The manufacturing method involves a suspension polymerization reaction of 20 to 80 parts by weight of a compound (A) having an ether structure represented by formula (1) and 80 to 20 parts by weight of a monomer (B) reacting with the compound (A) in an aqueous medium in the presence of a non-reactive solvent, wherein... The total amount of compound (A) and monomer (B) is set at 100 parts by weight. The compound (A) is a polyphenylene ether oligomer with a number average molecular weight of 500-3500. The monomer (B) reacts with the terminal group of the compound (A). The monomer (B) comprises aromatic crosslinking monomers and aromatic monofunctional monomers. The aromatic crosslinking monomer is selected from at least one of the group consisting of divinylbenzene, divinylnaphthalene, and diallyl phthalate. The aromatic monofunctional monomer is selected from at least one group consisting of styrene, α-methylstyrene, ethyl vinylbenzene, vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, vinyl biphenyl, and vinylnaphthalene. 。

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