Hollow resin particle, method of producing the same, and use of the same

Abstract

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

Description

Technical Field

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

Background Art

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

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

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

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

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

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

[0008] As hollow resin particles, it has been reported that by blending hollow resin particles obtained by polymerizing a polyfunctional monomer and a monofunctional monomer into a resin, an organic insulating material excellent in insulating properties, having a low dielectric constant and a low dielectric loss tangent can be obtained. As specific monomers, styrene, methyl methacrylate, divinylbenzene, trimethylolpropane tri(meth)acrylate, etc. are used (Patent Document 4).

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

[0010] Generally, for acrylic resins, it is known that the values of the dielectric constant and the dielectric loss tangent are high, the heat resistance is insufficient, and the water absorption rate is high. From this, the acrylic hollow resin particles described in Patent Document 1 and Patent Document 2 are not suitable for the purpose of reducing the dielectric constant and the dielectric loss tangent of the resin layer, the purpose of imparting high heat resistance to the resin layer, and the purpose of suppressing the water absorption of the resin layer.

[0011] The styrene-based hollow resin particles described in Patent Document 3 are made of a material (crosslinkable polystyrene) with a lower relative permittivity and dielectric loss tangent than acrylic-based hollow resin particles. Therefore, they can be said to be effective particles for the purpose of reducing the relative permittivity and dielectric loss tangent of the resin layer. However, in their production, saturated hydrocarbons having 8 to 18 carbon atoms (specifically, hexadecane) are used, so it is difficult to remove the solvent from the hollow part by distillation or the like, and saturated hydrocarbons having 8 to 18 carbon atoms remain in the obtained styrene-based hollow resin particles, and it is difficult to obtain styrene-based hollow resin particles in which the hollow part is completely replaced with air. Further, in order to obtain styrene-based hollow resin particles in which the hollow part is completely replaced with air, the production cost is high for solvent removal as described above. Furthermore, the styrene-based hollow resin particles described in Patent Document 3 have insufficient heat resistance.

[0012] The hollow resin particles described in Patent Document 4 use a styrene-based monomer and an acrylic-based monomer having high relative permittivity and dielectric loss tangent values in combination, so the reduction of the relative permittivity and dielectric loss tangent of the resin layer is insufficient. Further, Patent Document 4 shows the 10% weight loss temperature by TG-DTA measurement under nitrogen atmosphere and a temperature rising condition of 10 °C / min as an index of heat resistance, but the heat resistance is insufficient.

[0013] The hollow resin particles described in Patent Document 5, like the styrene-based hollow resin particles described in Patent Document 3, use saturated hydrocarbons having 8 to 18 carbon atoms (more specifically, hexadecane) in their production, so it is difficult to remove the solvent from the hollow part by distillation or the like, and saturated hydrocarbons having 8 to 18 carbon atoms remain in the obtained styrene-based hollow resin particles, and it is difficult to obtain styrene-based hollow resin particles in which the hollow part is completely replaced with air. Further, in order to obtain styrene-based hollow resin particles in which the hollow part is completely replaced with air, the production cost is high for solvent removal as described above. Furthermore, the styrene-based hollow resin particles described in Patent Document 5 have insufficient heat resistance.

Prior Art Documents

Patent Documents

[0014]

Patent Document 1

[0015] The present invention has been made to solve the above - mentioned conventional problems, and its main object is to provide hollow resin particles having a shell portion and a hollow portion surrounded by the shell portion, which can achieve low dielectric constant and low dielectric tangent, and can exhibit excellent heat resistance. Another object is to provide a method for easily manufacturing such hollow resin particles. Still another object is to provide uses of such hollow resin particles. [Means for Solving the Problems]

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

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

[0018] In one embodiment, the above - mentioned hollow portion consists of one hollow region.

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

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

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

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

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

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

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

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

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

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

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

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

[0031] The light diffusion film according to an embodiment of the present invention contains hollow resin particles according to an embodiment of the present invention.

[0032] The production method according to an embodiment of the present invention is a method for producing hollow resin particles according to an embodiment of the present invention, 20 to 80 parts by weight of a compound (A) having an ether structure represented by formula (1) and 80 to 20 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 100 parts by weight) are reacted in an aqueous medium in the presence of a non-reactive solvent.

Chemical formula

Advantages of the Invention

[0033] According to an embodiment of the present invention, there are provided hollow resin particles having a shell portion and a hollow portion surrounded by the shell portion, which can achieve low dielectric constant and low dielectric tangent, and can exhibit excellent heat resistance. Further, a method for easily producing such hollow resin particles can be provided. Furthermore, uses of such hollow resin particles can be provided.

Brief Description of the Drawings

[0034]

Figure 1

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Figure 8

Figure 9

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Figure 15

Modes for Carrying Out the Invention

[0035] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these embodiments.

[0036] ≪≪1. Hollow Resin Particles≫≫ ≪1-1. Structure and Properties of Hollow Resin Particles≫ The hollow resin particles according to the embodiment of the present invention are hollow resin particles having a shell portion and a hollow portion surrounded by the shell portion. The term "hollow" as used herein means a state in which the interior is filled with a substance other than resin, such as gas or liquid, and preferably means a state filled with gas in terms of more effectively expressing the effects of the present invention.

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

[0038] The shell portion and the hollow portion surrounded by the shell portion may have a porous structure as shown in the schematic cross-sectional view of Fig. 1(c). When the hollow portion has a porous structure in this way, the hollow portion may be composed of one hollow region (continuous pores), a plurality of hollow regions (independent pores), or a mixed form thereof.

[0039] The average particle diameter of the hollow resin particles according to the embodiment of the present invention is preferably 0.1 μm to 50.0 μm, more preferably 0.1 μm to 40.0 μm, still more preferably 0.2 μm to 30.0 μm, and particularly preferably 0.3 μm to 20.0 μm. If the average particle diameter of the hollow resin particles is within the above range, the effects of the present invention can be more effectively exhibited. When the average particle diameter of the hollow resin particles according to the embodiment of the present invention is too small outside the above range, the thickness of the shell portion becomes relatively thin, so that the hollow resin particles may not have sufficient strength. When the average particle diameter of the hollow resin particles according to the embodiment of the present invention is too large outside the above range, phase separation between the polymer generated by polymerization of the monomer component and the solvent during suspension polymerization may be less likely to occur, which may make it difficult to form the shell portion.

[0040] The hollow resin particles according to the embodiments of the present invention preferably have a 5% thermal weight loss temperature of 300 °C or higher, more preferably 320 °C or higher, still more preferably 340 °C or higher, and particularly preferably 360 °C or higher when heated at 10 °C / min in a nitrogen atmosphere. The upper limit of the above 5% thermal weight loss temperature is realistically preferably 500 °C or lower. If the 5% thermal weight loss temperature of the hollow resin particles according to the embodiments of the present invention is within the above range when heated at 10 °C / min in a nitrogen atmosphere, the hollow resin particles according to the embodiments of the present invention can exhibit excellent heat resistance. If the 5% thermal weight loss temperature of the hollow resin particles according to the embodiments of the present invention is too low outside the above range, for example, when the hollow resin particles are mixed with a thermosetting resin, the particles may be deformed by heating for the curing reaction, and the hollow part may be lost, resulting in a possible decrease in the low dielectric effect and the low dielectric tangent effect.

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

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

Chemical formula

[0043] The shell part preferably contains a polymer (P) having an ether structure represented by formula (1). By the shell part containing such a polymer (P), the effects of the present invention can be more effectively exhibited.

[0044] The polymer (P) may be only one kind or two or more kinds.

[0045] The content ratio of the polymer (P) in the shell part is preferably 60% by weight to 100% by weight, more preferably 70% by weight to 100% by weight, still more preferably 80% by weight to 100% by weight, and particularly preferably 90% by weight to 100% by weight in terms of more effectively exhibiting the effects of the present invention.

[0046] The shell part may contain any other appropriate components as long as the effects of the present invention are not impaired.

[0047] <Polymer (P)> As the polymer (P), any appropriate polymer can be adopted as long as it has an ether structure represented by formula (1) and does not impair the effects of the present invention. In terms of more effectively exhibiting the effects of the present invention, such a polymer (P) preferably includes a polymer obtained by the reaction of a compound (A) having an ether structure represented by formula (1) and a monomer (B) that reacts with the compound (A).

[0048] The compound (A) having an ether structure represented by formula (1) may be only one kind or two or more kinds.

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

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

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

[0052] As another embodiment of the above preferable ratio, more preferably, it is (30 parts by weight to 70 parts by weight):(70 parts by weight to 30 parts by weight), still more preferably (35 parts by weight to 65 parts by weight):(65 parts by weight to 35 parts by weight), and particularly preferably (40 parts by weight to 60 parts by weight):(60 parts by weight to 40 parts by weight).

[0053] If the content ratio of compound (A) is too small outside the above range, there is a risk that the heat resistance may be insufficient. If the content ratio of compound (A) is too large outside the above range, it may be difficult to form a shell part and a hollow part surrounded by the shell part.

[0054] As compound (A), any appropriate compound can be adopted as long as it has an ether structure represented by formula (1) without impairing the effects of the present invention. In terms of being able to more effectively exhibit the effects of the present invention, such compound (A) preferably includes polyphenylene ether. Examples of commercially available polyphenylene ethers include the product name "Noryl" (manufactured by SABIC Corporation), the product name "Upi Ace" (manufactured by Mitsubishi Chemical Corporation), the product name "Zylon" (manufactured by Asahi Kasei Corporation), and the product name "OPE-2St" (manufactured by Mitsubishi Gas Chemical Company, Inc.).

[0055] From the viewpoint of compatibility with the non-reactive solvent described later and the point that hollow resin particles excellent in heat resistance can be more easily prepared, the polyphenylene ether is preferably an oligomer, and the number average molecular weight (Mn) is preferably 500 to 3500.

[0056] Examples of the monomer (B) include a crosslinkable monomer and a monofunctional monomer. A monomer that reacts with the terminal group of the compound (A) is preferable in terms of more effectively expressing the effects of the present invention.

[0057] Examples of the crosslinkable monomer include polyfunctional (meth)acrylic acid esters such as ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and glycerin tri(meth)acrylate; polyfunctional acrylamide derivatives such as N,N'-methylenebis(meth)acrylamide and N,N'-ethylenebis(meth)acrylamide; polyfunctional allyl derivatives such as diallylamine and tetraallyloxyethane; and aromatic crosslinkable monomers such as divinylbenzene, divinylnaphthalene, and diallyl phthalate. In terms of more effectively expressing the effects of the present invention, the crosslinkable monomer is preferably an aromatic crosslinkable monomer, and more preferably divinylbenzene. The crosslinkable monomer may be only one kind or two or more kinds.

[0058] Examples of the monofunctional monomer include alkyl (meth)acrylic acid esters having 1 to 16 carbon atoms such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and cetyl (meth)acrylate; aromatic monofunctional monomers such as styrene, α-methylstyrene, ethylvinylbenzene, vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, vinylbiphenyl, and vinylnaphthalene; dicarboxylic acid ester monomers such as dimethyl maleate, diethyl fumarate, dimethyl fumarate, and diethyl fumarate; maleic anhydride; N-vinylcarbazole; and (meth)acrylonitrile. In terms of more effectively expressing the effects of the present invention, the monofunctional monomer is preferably an aromatic monofunctional monomer, and more preferably styrene and ethylvinylbenzene. The monofunctional monomer may be only one kind or two or more kinds.

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

[0060] The reaction between compound (A) and monomer (B) can be carried out by any suitable reaction as long as the effects of the present invention are not impaired. Such a reaction is preferably a suspension polymerization reaction.

[0061] When carrying out the suspension polymerization reaction, typically, an oil phase is added to an aqueous phase and suspended to carry out the polymerization reaction. The aqueous phase and the oil phase may contain any suitable solvent as long as the effects of the present invention are not impaired. Examples of such solvents include aqueous media and non-reactive solvents as described below. The solvent may be only one kind or two or more kinds.

[0062] When carrying out the reaction between compound (A) and monomer (B), any suitable additive (C) that does not correspond to either compound (A) or monomer (B) may be used as long as the effects of the present invention are not impaired. Additive (C) may be only one kind or two or more kinds. The additives referred to here do not include solvents such as aqueous media and non-reactive solvents as described below.

[0063] The content ratio of additive (C) is preferably 0 wt% to 40 wt%, more preferably 0 wt% to 30 wt%, still more preferably 0 wt% to 20 wt%, and particularly preferably 0 wt% to 10 wt% based on the total amount of compound (A) and monomer (B).

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

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

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

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

[0068] Examples of the styrenic polymer include polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, etc.

[0069] Examples of the (meth)acrylic acid-based polymer include polymethyl (meth)acrylate, polyethyl (meth)acrylate, polybutyl (meth)acrylate, polypropyl (meth)acrylate, etc.

[0070] Examples of the styrene-(meth)acrylic acid-based polymer include styrene-methyl (meth)acrylate copolymer, styrene-ethyl (meth)acrylate copolymer, styrene-butyl (meth)acrylate copolymer, styrene-propyl (meth)acrylate copolymer, etc.

[0071] ≪1-3. Dielectric Constant of Hollow Resin Particles≫ The dielectric constant of the hollow resin particles according to the embodiment 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 dielectric constant of the hollow resin particles according to the embodiment of the present invention is within the above range, the effects of the present invention can be more effectively exhibited. When the dielectric constant of the hollow resin particles according to the embodiment of the present invention exceeds 2.5, a sufficient low dielectric effect cannot be obtained even if the hollow resin particles are mixed with, for example, a thermosetting resin.

[0072] The relative permittivity of the hollow resin particles according to the embodiment of the present invention can be calculated, for example, with reference to "Dielectric Constant of Mixed Systems" (Journal of Applied Physics, Vol. 27, No. 8 (1958)). When the relative permittivity of the mixed system of the dispersion medium and the hollow resin particles is ε, the relative permittivity of the base material serving as the dispersion medium (for example, a resin composition such as polyimide or epoxy) is ε1, the relative permittivity of the hollow resin particles is ε2, and the volume fraction of the hollow resin particles in the mixed system is φ, the following formula holds. That is, if ε, ε1, and φ are determined experimentally, the relative permittivity ε2 of the hollow resin particles can be calculated.

Equation

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

Equation

[0074] The density of the hollow resin particles can be determined experimentally using a pycnometer (TQC50 mL specific gravity bottle manufactured by Kotech Co., Ltd.) and a liquid polymer product named "ARUFON (trademark) UP-1080" (manufactured by Toagosei Co., Ltd., density 1.05 g / cm 3 ). Specifically, the hollow resin particles and ARUFON UP-1080 are defoamed and stirred using a planetary stirring defoamer (manufactured by Kurabo Industries Ltd., "Mazers Star KK-250") so that the proportion of the hollow resin particles becomes 10% by weight to prepare an evaluation mixture. The evaluation mixture is filled into a 50 mL pycnometer, and the weight of the filled evaluation mixture is calculated by subtracting the weight of the empty pycnometer from the weight of the pycnometer filled with the mixture. From this value, the density of the hollow resin particles can be calculated using the following formula.

Equation

[0075] ≪1-4. Uses of Hollow Resin Particles≫ The hollow resin particles according to the embodiments of the present invention can be adopted for various applications. In terms of being able to make better use of the effects of the present invention, the hollow resin particles according to the embodiments of the present invention are suitable for semiconductor members, and typically, can be suitably used in resin compositions for semiconductor members. Further, in addition to the use in the above-mentioned resin composition for semiconductor members, the hollow resin particles according to the embodiments of the present invention can also be applied to uses such as, for example, paint compositions, cosmetics, paper coating compositions, heat insulating compositions, light diffusing compositions, light diffusing films, etc.

[0076] <Resin composition for semiconductor member> The hollow resin particles according to the embodiments of the present invention can achieve low dielectric constant and low dielectric loss tangent, and can exhibit excellent heat resistance, so they can be suitably used in resin compositions for semiconductor members.

[0077] The resin composition for semiconductor members according to the embodiments of the present invention contains the hollow resin particles according to the embodiments of the present invention.

[0078] A semiconductor member means a member constituting a semiconductor, and examples thereof include a semiconductor package and a semiconductor module. In this specification, a resin composition for semiconductor members means a resin composition used for semiconductor members.

[0079] A semiconductor package is constituted by using at least one member selected from molding resins, underfill materials, mold underfill materials, die bonding materials, prepregs for semiconductor package substrates, metal-clad laminates for semiconductor package substrates, and build-up materials for printed circuit boards for semiconductor packages, with an IC chip as an essential constituent member.

[0080] A semiconductor module is constituted by using at least one member selected from prepregs for printed circuit boards, metal-clad laminates for printed circuit boards, build-up materials for printed circuit boards, solder resist materials, coverlay films, electromagnetic wave shielding films, and adhesive sheets for printed circuit boards, with a semiconductor package as an essential constituent member.

[0081] <Paint composition> The hollow resin particles according to the embodiment of the present invention can impart excellent appearance to the coating film containing them, and thus can be suitably used in a coating composition.

[0082] The coating composition according to the embodiment of the present invention contains the hollow resin particles according to the embodiment of the present invention.

[0083] The coating composition according to the embodiment of the present invention preferably contains at least one selected from a binder resin and a UV curable resin. The binder resin may be only one kind or two or more kinds. The UV curable resin may be only one kind or two or more kinds.

[0084] As the binder resin, any suitable binder resin can be adopted as long as the effects of the present invention are not impaired. Examples of such binder resins include resins soluble in organic solvents or water, and emulsion-type aqueous resins dispersible in water. Specific examples of the binder resin include acrylic resins, alkyd resins, polyester resins, polyurethane resins, chlorinated polyolefin resins, and amorphous polyolefin resins.

[0085] As the UV curable resin, any appropriate UV curable resin can be employed as long as the effects of the present invention are not impaired. Examples of such UV curable resins include polyfunctional (meth)acrylate resins and polyfunctional urethane acrylate resins. Polyfunctional (meth)acrylate resins are preferred, and polyfunctional (meth)acrylate resins having three or more (meth)acryloyl groups in one molecule are more preferred. Specific examples of the polyfunctional (meth)acrylate resin having three or more (meth)acryloyl groups in one molecule include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, 1,2,4-cyclohexane tetra(meth)acrylate, pentaglycerol triacrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol triacrylate, and tripentaerythritol hexaacrylate.

[0086] When the coating composition according to the embodiment of the present invention contains at least one selected from a binder resin and a UV curable resin, the content ratio can be any appropriate content ratio according to the purpose. Typically, with respect to the total amount of at least one selected from a binder resin (in terms of solid content in the case of an emulsion-type aqueous resin) and a UV curable resin and the hollow resin particles according to the embodiment of the present invention, the hollow resin particles according to the embodiment of the present invention are preferably 5% by weight to 50% by weight, more preferably 10% by weight to 50% by weight, and still more preferably 20% by weight to 40% by weight.

[0087] When a UV curable resin is used, preferably, a photoinitiator is used in combination. As the photoinitiator, any appropriate photoinitiator can be employed as long as the effects of the present invention are not impaired. Examples of such photoinitiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, α-hydroxyalkylphenones, α-aminoalkylphenones, anthraquinones, thioxanthones, azo compounds, peroxides (described in JP-A-2001-139663, etc.), 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfonium salts, onium salts, borate salts, active halogen compounds, and α-acyl oxime esters.

[0088] The coating composition according to an embodiment of the present invention may contain a solvent. The solvent may be only one kind or two or more kinds. When the coating composition according to an embodiment of the present invention contains a solvent, the content ratio thereof can be any appropriate content ratio according to the purpose.

[0089] As the solvent, any appropriate solvent can be employed as long as the effects of the present invention are not impaired. Such a solvent is preferably a solvent that can dissolve or disperse the binder resin or the UV curable resin. Examples of such solvents include, for oil-based paints, 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; ether solvents such as dioxane, ethylene glycol diethyl ether, and ethylene glycol monobutyl ether; and for water-based paints, examples include water and alcohols.

[0090] The coating composition according to an embodiment of the present invention may be diluted in order to adjust the viscosity as necessary. As the diluent, any appropriate diluent can be employed according to the purpose. Examples of such diluents include the solvents described above. The diluent may be only one kind or two or more kinds.

[0091] The paint composition according to an embodiment of the present invention may contain, if necessary, other components, such as a surface conditioner, a fluidity modifier, an ultraviolet absorber, a light stabilizer, a curing catalyst, an extender pigment, a coloring pigment, a metallic pigment, a mica powder pigment, and a dye.

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

[0093] When forming a coating film using the paint composition according to an embodiment of the present invention, any appropriate forming method can be adopted according to the purpose. Examples of such forming methods include a method of forming a coating film by coating an arbitrary coated surface of a substrate to produce a coated film, drying the coated film, and then curing the coated film as necessary. Examples of the substrate include metals, woods, glasses, plastics (such as PET (polyethylene terephthalate), PC (polycarbonate), acrylic resins, and TAC (triacetyl cellulose)).

[0094] <Heat insulating resin composition> The hollow resin particles according to an embodiment of the present invention can be suitably used in a heat insulating resin composition because they can impart excellent heat insulating properties to a coating film containing them. A coating film containing the hollow resin particles according to an embodiment of the present invention can exhibit excellent reflectance in the wavelength range from ultraviolet light to near-infrared light.

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

[0096] The heat insulating resin composition according to an embodiment of the present invention preferably contains at least one selected from a binder resin and a UV curable resin. Regarding the binder resin and the UV curable resin, the description of the paint composition above can be incorporated.

[0097] The heat-insulating resin composition according to an embodiment of the present invention may contain a solvent. Regarding the solvent, the description of the paint composition described above can be incorporated.

[0098] The heat-insulating resin composition according to an embodiment of the present invention may be diluted in order to adjust the viscosity as necessary. Regarding the diluent, the description of the paint composition described above can be incorporated.

[0099] The heat-insulating resin composition according to an embodiment of the present invention may contain other components as necessary, for example, a coating surface conditioner, a fluidity modifier, an ultraviolet absorber, a light stabilizer, a curing catalyst, an extender pigment, a coloring pigment, a metallic pigment, a mica powder pigment, and a dye.

[0100] Regarding the coating method and the forming method when forming a coating film using the heat-insulating resin composition according to an embodiment of the present invention, the description of the paint composition described above can be incorporated.

[0101] <Light-diffusing resin composition> The hollow resin particles according to an embodiment of the present invention can be suitably used in a light-diffusing resin composition because they can impart excellent light diffusibility to a coating film containing them.

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

[0103] The light-diffusing resin composition according to an embodiment of the present invention preferably contains at least one selected from a binder resin and a UV-curable resin. Regarding the binder resin and the UV-curable resin, the description of the paint composition described above can be incorporated.

[0104] The light-diffusing resin composition according to an embodiment of the present invention may contain a solvent. Regarding the solvent, the description of the paint composition described above can be incorporated.

[0105] The light-diffusing resin composition according to an embodiment of the present invention may be diluted in order to adjust the viscosity as necessary. As the diluent, the description of the aforementioned coating composition can be cited.

[0106] The light-diffusing resin composition according to an embodiment of the present invention may contain other components, for example, a coating surface conditioner, a fluidity modifier, an ultraviolet absorber, a light stabilizer, a curing catalyst, an extender pigment, a coloring pigment, a metallic pigment, a mica powder pigment, and a dye, as necessary.

[0107] When forming a coating film using the light-diffusing resin composition according to an embodiment of the present invention, the coating method and the forming method can cite the description of the aforementioned coating composition.

[0108] <Light-diffusing film> The hollow resin particles according to an embodiment of the present invention can preferably be used for a light-diffusing film because they can impart excellent light diffusibility to a film provided with a coating film containing them.

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

[0110] The light-diffusing film according to an embodiment of the present invention includes a light-diffusing layer formed from the light-diffusing resin composition according to an embodiment of the present invention and a substrate. Note that the light-diffusing layer may be the outermost layer of the light-diffusing film or may not be the outermost layer. The light-diffusing film according to an embodiment of the present invention may contain any other appropriate layer according to the purpose. Examples of such other layers include a protective layer, a hard coat layer, a planarization layer, a high refractive index layer, an insulating layer, a conductive resin layer, a conductive metal fine particle layer, a conductive metal oxide fine particle layer, and a primer layer.

[0111] Examples of the base material include metal, wood, glass, plastic film, plastic sheet, plastic lens, plastic panel, cathode ray tube, fluorescent display tube, and liquid crystal display panel. Examples of the plastic constituting the plastic film, plastic sheet, plastic lens, and plastic panel include PET (polyethylene terephthalate), PC (polycarbonate), acrylic resin, and TAC (triacetyl cellulose).

[0112] <<2. Method for Producing Hollow Resin Particles>> In the method for producing hollow resin particles according to an embodiment of the present invention, 20 to 80 parts by weight of a compound (A) having an ether structure represented by formula (1) and 20 to 80 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 100 parts by weight) are reacted in an aqueous medium in the presence of a non-reactive solvent. [Chemical formula]

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

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

[0115] Suspension polymerization is typically suspension polymerization using an aqueous phase containing an aqueous medium and an oil phase containing the compound (A), the monomer (B), and a non-reactive solvent. Preferably, the suspension polymerization is carried out by adding and dispersing an oil phase containing the compound (A), the monomer (B), and a non-reactive solvent to an aqueous phase containing an aqueous medium and heating.

[0116] As long as the oil phase can exist in the form of droplets in the aqueous phase, any appropriate dispersion method can be adopted within the range that does not impair the effects of the present invention. Representative examples of such dispersion methods include dispersion methods using a homomixer or a homogenizer, such as a Polytron homogenizer, an ultrasonic homogenizer, or a high-pressure homogenizer.

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

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

[0119] The post-heating preferably performed after polymerization is a suitable treatment for obtaining hollow resin particles with a high degree of completion.

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

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

[0122] For the compound (A) and the monomer (B), the descriptions in the item <Polymer (P)> of <<<1. Hollow Resin Particles>>> <<<1-2. Shell Part>>> can be directly incorporated by reference.

[0123] The content ratio of the compound (A) and the monomer (B) can be directly incorporated by reference to the descriptions in the item <Polymer (P)> of <<<1. Hollow Resin Particles>>> <<<1-2. Shell Part>>>.

[0124] Examples of the aqueous medium include water, a mixed medium of water and a lower alcohol (such as methanol, ethanol, etc.).

[0125] The amount of the aqueous medium used can be any appropriate amount as long as the effects of the present invention are not impaired. Such an amount of the aqueous medium is typically an amount that allows the suspension polymerization reaction, which is carried out by adding the oil phase to the aqueous phase and suspending it, to proceed appropriately. It is preferably 100 parts by weight to 5000 parts by weight, more preferably 150 parts by weight to 2000 parts by weight, based on 100 parts by weight of the total amount of compound (A), monomer (B), and the non-reactive solvent.

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

[0127] The non-reactive solvent as the hollowing agent may be a single solvent or a mixed solvent.

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

[0129] When reacting compound (A) and monomer (B), any appropriate additive (C) that does not correspond to either compound (A) or monomer (B) may be used as long as the effects of the present invention are not impaired. Additive (C) may be only one kind or two or more kinds. The additives referred to here do not include solvents such as the aqueous medium and the non-reactive solvent.

[0130] The content ratio of additive (C) is preferably 0 wt% to 40 wt%, more preferably 0 wt% to 30 wt%, still more preferably 0 wt% to 20 wt%, and particularly preferably 0 wt% to 10 wt% based on the total amount of compound (A) and monomer (B).

[0131] As additive (C), any appropriate additive can be employed as long as the effects of the present invention are not impaired. Examples of such additive (C) include non-crosslinkable polymers, dispersion stabilizers, surfactants, and polymerization initiators.

[0132] Regarding the non-crosslinkable polymer, the description in the item of <polymer (P)> in <<<1. Hollow resin particles>>> <<<1-2. Shell part>>> can be directly cited.

[0133] Examples of the dispersion stabilizer include polyvinyl alcohol, polycarboxylic acid, celluloses (such as hydroxyethyl cellulose, carboxymethyl cellulose, etc.), polyvinylpyrrolidone, etc. Inorganic water-soluble polymer compounds such as sodium tripolyphosphate can also be used. Furthermore, phosphates such as calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate; pyrophosphates such as calcium pyrophosphate, magnesium pyrophosphate, aluminum pyrophosphate, zinc pyrophosphate; sparingly water-soluble inorganic compounds such as calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, colloidal silica, etc. can also be used. Since it is relatively easy to remove from the hollow resin particles and it is difficult to remain on the surface of the hollow resin particles, the use of magnesium pyrophosphate is preferred.

[0134] The addition amount of the dispersion stabilizer is preferably 0.5 parts by weight to 10 parts by weight based on 100 parts by weight of the aqueous medium. The dispersion stabilizer may be only one kind or two or more kinds.

[0135] Examples of the surfactant include anionic surfactants, cationic surfactants, amphoteric ion surfactants, nonionic surfactants, etc.

[0136] Examples of anionic surfactants include non-reactive anionic surfactants such as alkyl sulfate salts, alkyl phosphate salts, alkylbenzene sulfonate salts, alkylnaphthalene sulfonate salts, alkane sulfonate salts, alkyl diphenyl ether sulfonate salts, dialkyl sulfosuccinate salts, monoalkyl sulfosuccinate salts, and polyoxyethylene alkyl phenyl ether phosphate salts, and reactive anionic surfactants such as polyoxyethylene-1-(allyloxymethyl)alkyl ether sulfate ammonium salts, polyoxyethylene alkyl propenyl phenyl ether sulfate ammonium salts, and polyoxyalkylene alkenyl ether sulfate ammonium salts. Note that the surfactant is not limited to the salt structure, and for example, alkyl sulfate esters and alkyl phosphate esters can also be used. Specifically, lauryl sulfate and lauryl phosphate can be mentioned.

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

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

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

[0140] The addition amount of the surfactant is preferably 0.01% to 5% by weight based on the total amount of the compound (A), the monomer (B), and the non-reactive solvent. The surfactant may be only one kind or two or more kinds.

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

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

Examples

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

[0144] <Measurement of volume average particle diameter (Examples 1 to 7, Example 10, Comparative Example 1)> The volume average particle diameter of the particles was measured by the Coulter method as follows. The volume average particle diameter of the particles was measured using a Coulter Multisizer (registered trademark) 3 (a measuring device manufactured by Beckman Coulter, Inc.). The measurement was carried out using an aperture calibrated in accordance with the Multisizer (registered trademark) 3 Users Manual issued by Beckman Coulter, Inc. Note that for the aperture used in the measurement, when the assumed volume average particle diameter of the particles to be measured is 1 μm or more and 10 μm or less, an aperture having a size of 50 μm is selected; when the assumed volume average particle diameter of the particles to be measured is more than 10 μm and 30 μm or less, an aperture having a size of 100 μm is selected; when the assumed volume average particle diameter of the particles is more than 30 μm and 90 μm or less, an aperture having a size of 280 μm is selected; when the assumed volume average particle diameter of the particles is more than 90 μm and 150 μm or less, an aperture having a size of 400 μm is selected, etc. It was appropriately selected according to the size of the particles to be measured. When the volume average particle diameter after measurement was different from the assumed volume average particle diameter, the aperture having an appropriate size was changed and the measurement was carried out again. Current (aperture current) and Gain were appropriately set according to the size of the selected aperture. For example, when an aperture having a size of 50 μm was selected, Current (aperture current) was set to -800 and Gain was set to 4; when an aperture having a size of 100 μm was selected, Current (aperture current) was set to -1600 and Gain was set to 2; when apertures having sizes of 280 μm and 400 μm were selected, Current (aperture current) was set to -3200 and Gain was set to 1. As the measurement sample, 0.1 g of particles were dispersed in 10 ml of a 0.1 wt% nonionic surfactant aqueous solution using a touch mixer (manufactured by Yamato Scientific Co., Ltd., "TOUCHMIXER MT-31") and an ultrasonic cleaner (manufactured by Vervo Clea Co., Ltd., "ULTRASONIC CLEANER VS-150") to obtain a dispersion, which was used. During the measurement, the inside of the beaker was gently stirred so that no bubbles entered, and the measurement was terminated when 100,000 particles were measured. Note that the volume average particle diameter of the particles was taken as the arithmetic mean in the volume-based particle size distribution of 100,000 particles.

[0145] <Measurement of average particle diameter (Examples 8 and 9, Comparative Example 2)> Using the dynamic light scattering method, the Z-average particle diameter of the hollow resin particles or particles was measured, and the measured Z-average particle diameter was taken as the average particle diameter of the obtained hollow resin particles or particles. That is, first, the obtained slurry-like hollow resin particles or particles were diluted with ion-exchanged water and adjusted to 0.1% by weight of an aqueous dispersion, irradiated with laser light, and the intensity of the scattered light scattered from the hollow resin particles or particles was measured as a function of time in microseconds. Then, the intensity distribution of the scattered light caused by the detected hollow resin particles or particles was fitted to a normal distribution, and the Z-average particle diameter of the hollow resin particles or particles was determined by the cumulant analysis method for calculating the average particle diameter. This measurement of the Z-average particle diameter can be easily carried out with a commercially available particle size measuring device. In the following Examples and Comparative Examples, the Z-average particle diameter was measured using a particle size measuring device (manufactured by Malvern, "Zetasizer Nano ZS"). Usually, commercially available particle size measuring devices are equipped with data analysis software, and the data analysis software can calculate the Z-average particle diameter by automatically analyzing the measurement data.

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

[0147] <TEM measurement: Observation of the presence or absence and shape of the hollow of the hollow resin particles or particles> The surface treatment (10 Pa, 5 mA, 10 seconds) was performed on the hollow resin particles or particles as dry powder using the "Osmium Coater Neoc-Pro" coating device manufactured by Maywa Foasis Co., Ltd. Subsequently, the hollow resin particles or particles were observed with a TEM (transmission electron microscope, "H-7600" manufactured by Hitachi High-Technologies Corporation) to confirm the presence or absence of hollowness and the shape of the hollow resin particles or particles. At this time, the acceleration voltage was set to 80 kV, and the magnification was set to 5000 times or 10,000 times for photography.

[0148] <Measurement of the 5% thermogravimetric reduction temperature when heating at 10 °C / min under a nitrogen atmosphere> The 5% thermogravimetric reduction temperature was measured using a differential thermal thermogravimetric simultaneous measurement device "TG / DTA6200, AST-2" manufactured by SII NanoTechnology Inc. The sampling method and temperature conditions were as follows. The bottom of the platinum measurement container was filled with 10.5 ± 0.5 mg of the sample without gaps to prepare a measurement sample. Under a nitrogen gas flow rate of 230 mL / min, using alumina as a reference substance, the 5% thermogravimetric reduction temperature was measured. The TG / DTA curve was obtained by heating the sample from 30 °C to 500 °C at a heating rate of 10 °C / min. From the obtained curve, the temperature at 5% weight reduction was calculated using the analysis software attached to the device and taken as the 5% thermogravimetric reduction temperature.

[0149] [Example 1] 2.5 g of a bifunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Company, Inc.) as a compound having an ether structure represented by formula (1), 2.5 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Material Co., Ltd., 81% content, 19% is ethyl vinylbenzene (EVB)), 5.0 g of heptane, 0.05 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (trade name "V-65", manufactured by Fujifilm Wako Pure Chemical Corporation) as a polymerization initiator, and 0.004 g of lauryl phosphoric acid were mixed to prepare an oil phase. To 32 g of a 2 wt% aqueous dispersion of magnesium pyrophosphate as the aqueous phase, an oil phase was added, and a suspension was prepared using a Polytron homogenizer "PT10-35" (manufactured by Central Science Trading Co., Ltd.). The obtained suspension was reacted by heating at 50 °C for 24 hours. Hydrochloric acid was added to the obtained slurry to decompose magnesium pyrophosphate, and then the solid content was separated by dehydration by filtration. After purification by repeating washing with water, drying was performed at 60 °C to obtain particles (1). A cross-sectional photograph of the obtained particles (1) is shown in Fig. 2. It was confirmed that the obtained particles (1) were a mixture of hollow resin particles in which the hollow surrounded by the shell consisted of one hollow region and hollow resin particles in which the hollow surrounded by the shell had a porous structure. The average particle diameter of the obtained particles (1) was 16.3 μm. The 5% thermogravimetric weight loss temperature of the obtained particles (1) when heated at 10 °C / min in a nitrogen atmosphere was 306 °C. The formulation amounts and the like are shown in Table 1.

[0150] [Example 2] Except that 3.0 g of a bifunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Company, Inc.) as a compound having an ether structure represented by formula (1) and 2.0 g of divinylbenzene (DVB) (manufactured by Nippon Steel Chemical & Material Co., Ltd., 81% content, 19% is ethylvinylbenzene (EVB)) were used, the same procedure as in Example 1 was carried out to obtain particles (2). A cross-sectional photograph of the obtained particles (2) is shown in Fig. 3. It was confirmed that the obtained particles (2) were hollow resin particles in which the hollow surrounded by the shell consisted of one hollow region. The average particle diameter of the obtained particles (2) was 15.2 μm. The 5% thermogravimetric weight loss temperature of the obtained particles (2) when heated at 10 °C / min in a nitrogen atmosphere was 320 °C. The formulation amounts and the like are shown in Table 1.

[0151] [Example 3] As the compound having an ether structure represented by formula (1), 3.5 g of a bifunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Company, Inc.) was used. Except that 1.5 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Material Co., Ltd., 81% content, 19% is ethylvinylbenzene (EVB)) was used, the procedure was the same as in Example 1 to obtain particles (3). A cross-sectional photograph of the obtained particles (3) is shown in Fig. 4. It was confirmed that the obtained particles (3) were hollow resin particles in which the hollow surrounded by the shell consisted of one hollow region. The average particle diameter of the obtained particles (3) was 13.9 μm. The 5% thermogravimetric weight loss temperature of the obtained particles (3) when heated at 10 °C / min under a nitrogen atmosphere was 309 °C. The compounding amounts and the like are shown in Table 1.

[0152] [Example 4] Instead of 2.5 g of a bifunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Company, Inc.) as the compound having an ether structure represented by formula (1), 2.5 g of a reactive low molecular weight polyphenylene ether (trade name "Noryl® SA9000-111 resin", manufactured by SABIC) as the compound having an ether structure represented by formula (1) was used. Except for this, the procedure was the same as in Example 1 to obtain particles (4). A cross-sectional photograph of the obtained particles (4) is shown in Fig. 5. It was confirmed that the obtained particles (4) were hollow resin particles in which the hollow surrounded by the shell had a porous structure. The average particle diameter of the obtained particles (4) was 16.5 μm. The 5% thermogravimetric weight loss temperature of the obtained particles (4) when heated at 10 °C / min under a nitrogen atmosphere was 373 °C. The compounding amounts and the like are shown in Table 1.

[0153] [Example 5] Instead of using 3.0 g of a bifunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Company, Inc.) as the compound having an ether structure represented by formula (1), 3.0 g of a reactive low molecular weight polyphenylene ether (trade name "Noryl® SA9000-111 resin", manufactured by SABIC) as the compound having an ether structure represented by formula (1) was used, and the procedure was carried out in the same manner as in Example 2 to obtain particles (5). A cross-sectional photograph of the obtained particles (5) is shown in Fig. 6. It was confirmed that the obtained particles (5) were hollow resin particles in which the hollow surrounded by the shell had a porous structure. The average particle diameter of the obtained particles (5) was 15.6 μm. The 5% thermogravimetric weight loss temperature of the obtained particles (5) when heated at 10 °C / min in a nitrogen atmosphere was 420 °C. The formulation amounts and the like are shown in Table 1.

[0154] [Example 6] Instead of using 2.5 g of a bifunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Company, Inc.), 2.5 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Material Co., Ltd., 81% content, 19% is ethylvinylbenzene (EVB)), and 5.0 g of heptane, 1.8 g of a reactive low molecular weight polyphenylene ether (trade name "Noryl® SA9000-111 resin", manufactured by SABIC), 1.2 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Material Co., Ltd., 81% content, 19% is ethylvinylbenzene (EVB)), 5.0 g of heptane, and 2.0 g of toluene were used, and the procedure was carried out in the same manner as in Example 1 to obtain particles (6). A cross-sectional photograph of the obtained particles (6) is shown in Fig. 7. It was confirmed that the obtained particles (6) were hollow resin particles in which the hollow surrounded by the shell had a porous structure. The average particle diameter of the obtained particles (6) was 15.1 μm. The 5% thermogravimetric weight loss temperature when the obtained particles (6) were heated at 10 °C / min in a nitrogen atmosphere was 415 °C. The blending amounts and the like are shown in Table 1.

[0155] [Example 7] Instead of 2.5 g of a bifunctional polyphenylene ether oligomer (trade name “OPE-2St 1200”, manufactured by Mitsubishi Gas Chemical Company, Inc.) as a compound having an ether structure represented by formula (1), 810 of divinylbenzene (DVB) (manufactured by Nippon Steel Chemical & Material Co., Ltd., 81% content product, 19% is ethyl vinylbenzene (EVB)) 2.5 g, and heptane 5.0 g, 4.0 g of a reactive low molecular weight polyphenylene ether (trade name “Noryl® SA9000-111 resin”, manufactured by SABIC) as a compound having an ether structure represented by formula (1), 810 of divinylbenzene (DVB) (manufactured by Nippon Steel Chemical & Material Co., Ltd., 81% content product, 19% is ethyl vinylbenzene (EVB)) 1.0 g, heptane 4.0 g, and cyclohexane 1.0 g were used, and the same procedure as in Example 1 was carried out to obtain particles (7). A cross-sectional photograph of the obtained particles (7) is shown in FIG. 8. It was confirmed that the obtained particles (7) were hollow resin particles in which the hollow surrounded by the shell had a porous structure. The average particle diameter of the obtained particles (7) was 13.1 μm. The 5% thermogravimetric weight loss temperature when the obtained particles (7) were heated at 10 °C / min in a nitrogen atmosphere was 428 °C. The blending amounts and the like are shown in Table 1.

[0156] [Example 8] 1.5 g of a bifunctional polyphenylene ether oligomer (trade name “OPE-2St 1200”, manufactured by Mitsubishi Gas Chemical Company, Inc.) as a compound having an ether structure represented by formula (1), 810 of divinylbenzene (DVB) (manufactured by Nippon Steel Chemical & Material Co., Ltd., 81% content product, 19% is ethyl vinylbenzene (EVB)) 1.5 g, heptane 3.0 g, and 0.09 g of Peroyl L (manufactured by NOF Corporation) as a polymerization initiator were mixed to prepare an oil phase. Next, 34 g of ion-exchanged water and 0.0128 g of Lapizole A-80 (manufactured by NOF Corporation) were mixed to prepare an aqueous phase. The oil phase was added to the aqueous phase, and a suspension was prepared using an ultrasonic homogenizer (manufactured by BRANSON, "SONIFIER450", conditions: Duty Cycle = 50%, Output Control = 5, treatment time 3 minutes). The reaction was carried out by heating the obtained suspension at 70 °C for 4 hours. The obtained slurry was heated at 100 °C for 24 hours to obtain dried particles (8). The TEM photograph of the obtained particles (8) is shown in Fig. 9. It was confirmed that the obtained particles (8) are hollow resin particles in which the hollow surrounded by the shell has a porous structure. The average particle diameter of the obtained particles (8) was 320 nm. The 5% thermogravimetric weight loss temperature of the obtained particles (8) when heated at 10 °C / min in a nitrogen atmosphere was 315 °C. The formulation amounts and the like are shown in Table 1.

[0157] [Example 9] 1.08 g of a reactive low molecular weight polyphenylene ether (trade name "Noryl® SA9000-111 resin", manufactured by SABIC Corporation) as 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% is ethylvinylbenzene (EVB)), 3.0 g of heptane, 1.2 g of toluene, and 0.03 g of Peroyl L (manufactured by NOF Corporation) as a polymerization initiator were mixed to prepare an oil phase. Next, 34 g of ion-exchanged water and 0.0085 g of Lapizole A-80 (manufactured by NOF Corporation) were mixed to prepare an aqueous phase. The oil phase was added to the aqueous phase, and a suspension was prepared using an ultrasonic homogenizer (manufactured by BRANSON, "SONIFIER450", conditions: Duty Cycle = 50%, Output Control = 5, treatment time 3 minutes). The reaction was carried out by heating the obtained suspension at 70 °C for 4 hours. The obtained slurry was heated at 100 °C for 24 hours to obtain dried particles (9). The TEM photograph of the obtained particles (9) is shown in Fig. 10. It was confirmed that the obtained particles (9) are hollow resin particles with a hollow surrounded by a shell and having a porous structure. The average particle diameter of the obtained particles (9) was 379 nm. The 5% thermogravimetric weight loss temperature of the obtained particles (9) when heated at 10 °C / min in a nitrogen atmosphere was 399 °C. The compounding amounts and the like are shown in Table 1.

[0158] 〔Example 10〕 The same procedure as in Example 1 was carried out except that 2.0 g of a bifunctional polyphenylene ether oligomer (trade name “OPE-2St 1200”, manufactured by Mitsubishi Gas Chemical Company, Inc.) 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 product, 19% is ethylvinylbenzene (EVB)) were used to obtain particles (10). The cross-sectional photograph of the obtained particles (10) is shown in Fig. 11. It was confirmed that the obtained particles (10) are hollow resin particles with a hollow surrounded by a shell and having a porous structure. The average particle diameter of the obtained particles (10) was 14.4 μm. The 5% thermogravimetric weight loss temperature of the obtained particles (10) when heated at 10 °C / min in a nitrogen atmosphere was 312 °C. The compounding amounts and the like are shown in Table 1.

[0159] 〔Example 11〕 Instead of 2.5 g of a bifunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Company, Inc.) 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% is ethylvinylbenzene (EVB)), 2.0 g of a reactive low molecular weight polyphenylene ether (trade name "Noryl® SA9000-111 resin", manufactured by SABIC) 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% is ethylvinylbenzene (EVB)) were used, and the procedure was the same as in Example 1 to obtain particles (11). A cross-sectional photograph of the obtained particles (11) is shown in Fig. 12. It was confirmed that the obtained particles (11) are hollow resin particles in which the hollow surrounded by the shell has a porous structure. The average particle diameter of the obtained particles (11) was 12.7 μm. The 5% thermogravimetric weight loss temperature of the obtained particles (11) when heated at 10 °C / min in a nitrogen atmosphere was 366 °C. The formulation amounts and the like are shown in Table 1.

[0160] [Comparative Example 1] 2.5 g of methyl methacrylate, 2.5 g of ethylene glycol dimethacrylate, 5 g of cyclohexane, 0.05 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (trade name "V-65", manufactured by Fujifilm Wako Pure Chemical Corporation) as a polymerization initiator, and 0.004 g of lauryl phosphoric acid were mixed to prepare an oil phase. The oil phase was added to 32 g of a 2 wt% aqueous dispersion of magnesium pyrophosphate as the aqueous phase, and a suspension was prepared using a Polytron homogenizer PT10-35 (manufactured by Central Science Trading Co., Ltd.). The obtained suspension was heated at 50 °C for 24 hours to carry out the reaction. Hydrochloric acid was added to the obtained slurry to decompose magnesium pyrophosphate, and then the solid content was separated by dehydration by filtration and purified by repeating washing with water, and then dried at 60 °C to obtain particles (C1) as a dry powder. The cross-sectional photograph of the obtained particles (C1) is shown in Fig. 13. It was confirmed that the obtained particles (C1) are hollow resin particles in which the hollow surrounded by the shell consists of one hollow region. The average particle diameter of the obtained particles (C1) was 8.3 μm. The 5% thermogravimetric weight loss temperature of the obtained particles (C1) when heated at 10 °C / min in a nitrogen atmosphere was 245 °C. The compounding amounts and the like are shown in Table 1.

[0161] 〔Comparative Example 2〕 1.74 g of methyl methacrylate (MMA), 1.74 g of dipentaerythritol hexaacrylate (ADPH) (Shin-Nakamura Chemical Co., Ltd.), 2.4 g of toluene, 0.126 g of polystyrene (non-crosslinked, weight average molecular weight 300,000), and 0.104 g of Peroyl L (polymerization initiator, NOF Corporation) were mixed to prepare an oil phase. Next, 34 g of ion-exchanged water and 0.034 g of Lapisol A-80 (surfactant, NOF Corporation) were mixed to prepare an aqueous phase. The oil phase was added to the aqueous phase, and a suspension was prepared using an ultrasonic homogenizer (manufactured by BRANSON, "SONIFIER450", conditions: Duty Cycle = 50%, Output Control = 5, treatment time 3 minutes). Polymerization was carried out by heating the obtained suspension at 70 °C for 4 hours to obtain a slurry. The obtained slurry was heated at 100 °C for 24 hours to obtain particles (C2) as a dry powder. The TEM photograph of the obtained particles (C2) is shown in Fig. 14. It was confirmed that the obtained particles (C2) are hollow resin particles in which the hollow surrounded by the shell consists of one hollow region. The average particle diameter of the obtained particles (C2) was 478 nm, and the particle density was 0.614 g / cm 3 It was. The 5% thermogravimetric weight loss temperature of the obtained particles (C2) when heated at 10 °C / min in a nitrogen atmosphere was 327 °C. The compounding amounts and the like are shown in Table 1.

[0162]

Table 1

[0163] <Performance Evaluation 1: Relative Permittivity and Dissipation Factor Evaluation 1> For each example and comparative example, 0.4 g of the obtained particles and 10 g of an ultra-high heat-resistant polyimide varnish (trade name "SPIXAREA HR (registered trademark) 002", manufactured by Somar Co., Ltd.) were defoamed and stirred using a planetary stirring defoamer (manufactured by KURABO Industries Ltd., "Mazer Star KK-250") to prepare an evaluation mixture. The evaluation mixture was applied to a glass plate with a thickness of 5 mm using an applicator set to a wet thickness of 250 μm, and then heated at 120°C for 10 minutes, 180°C for 180 minutes, and 270°C for 60 minutes to remove the solvent, and then cooled to room temperature to obtain film samples containing each particle. The relative permittivity and dissipation factor of the obtained film were evaluated by the cavity resonance method (measurement frequency: 5.8 GHz). The results are shown in Table 2.

[0164]

Table 2

[0165] From the results in Table 2, it can be confirmed that the hollow resin particles provided by the present invention have the effect of lowering the relative permittivity and dissipation factor of the base material, and are effective for the purpose of reducing the relative permittivity and dissipation factor of semiconductor materials.

[0166] <Performance Evaluation 2: Relative Permittivity and Dissipation Factor Evaluation 2> For each example and comparative example, 0.425 g of the obtained particles, 12.1 g of ethyl acetate, and 1.7 g of a solvent-soluble polyimide KPI-MX300F (manufactured by Kawamura Sangyo Co., Ltd.) were defoamed and stirred using a planetary stirring defoamer (manufactured by KURABO Industries Ltd., "Mazer Star KK-250") to prepare an evaluation mixture. The evaluation mixture was applied to a glass plate with a thickness of 5 mm using an applicator set to a wet thickness of 250 μm, and then heated at 60°C for 30 minutes, 90°C for 10 minutes, 150°C for 30 minutes, and 200°C for 30 minutes to remove ethyl acetate. After cooling to room temperature, a film sample containing each particle was obtained. The relative permittivity and dielectric loss tangent of the obtained film were evaluated by the cavity resonance method (measurement frequency: 5.8 GHz). The results are shown in Table 3.

[0167]

Table 3

[0168] From the results in Table 3, it can be confirmed that the hollow resin particles provided by the present invention have the effect of lowering the relative permittivity and dielectric loss tangent of the base material, and it can be seen that they are effective for the purpose of reducing the relative permittivity and dielectric loss tangent of semiconductor materials.

[0169] <Performance Evaluation 3: Moisture Content Evaluation> For the particles obtained in each example and comparative example, a moisture absorption treatment was carried out under the following conditions. The particles obtained in each example and comparative example were placed in a thermostatic and humidistatic chamber at a temperature of 40 ± 1°C and a relative humidity of 95% and taken out after 96 hours, and cooled for 30 minutes in an environment of (temperature 20 ± 1°C, humidity 65 ± 5%). After cooling, the moisture content was measured. The water content was measured by using 0.1 g of the particles obtained in each example and comparative example as samples, and setting them in a "CA-200" Karl Fischer moisture meter and a "VA-236S" moisture vaporizer manufactured by Mitsubishi Chemical Analytech Co., Ltd. For the anolyte and catholyte during the measurement, the product names "Aquamicro (registered trademark) AX" and "Aquamicro (registered trademark) CXU" manufactured by Mitsubishi Chemical Corporation were used, respectively. The measurement (vaporization) temperature was set at 250 °C. Nitrogen was used as the carrier gas. The flow rate of the carrier gas was 150 mL / min. The number of test runs for the sample was 3 times. The water content in only the air at the sample collection location was measured twice, and the average value was taken as the blank value. The blank value was subtracted from each measurement result and divided by the sample weight to obtain the water content (wt%) of the sample. The water content (wt%) of the sample was calculated by the following formula. Water content (wt%) = [Measured water amount (μg) - Blank water amount (μg)] ÷ 1000000 ÷ Sample weight (g) × 100 As the final result, the three measurement results were averaged to obtain the water content (wt%) of the sample. The results are shown in Table 4.

[0170]

Table 4

[0171] From the results in Table 4, it can be seen that the hollow resin particles provided by the present invention have a lower water content after the moisture absorption treatment compared to the conventional hollow resin particles, and are suitable for the purpose of reducing the dielectric constant and dielectric tangent of semiconductor materials.

[0172] <Performance Evaluation 4: Heat Insulation Performance Evaluation> To 10 g of a commercially available aqueous paint (manufactured by Asahi Pen Co., Ltd., product name "Aqueous Multi-Purpose Color Clear"), 2.5 g of the particles (1) obtained in Example 1 was added, and defoaming and stirring were performed using a planetary stirring defoamer (manufactured by Kurabo Industries Ltd., "Mazer Star KK-250") to prepare a paint for evaluation. After applying the evaluation paint to the black side of the hiding power test paper with an applicator set to a wet thickness of 250 μm, it was thoroughly dried at room temperature to obtain a sample plate for evaluating light reflectivity. The reflectance of the sample plate for evaluating light reflectivity with respect to ultraviolet light, visible light, and near-infrared light was evaluated in the following order. An ultraviolet-visible-near-infrared spectrophotometer (manufactured by Shimadzu Corporation, "Solid Spec3700") was used as the reflectance measuring device, and the reflection characteristics of ultraviolet light to near-infrared light (wavelength 300 nm to 2500 nm) on the coated surface of the sample plate for evaluating light reflectivity were measured as reflectance (%). The measurement was performed using a 60 mmΦ integrating sphere and Spectralon as the standard white plate. The results obtained are shown in Fig. 15. As shown in Fig. 15, it was found that a high reflectance of 40% or more was obtained at almost all wavelengths from ultraviolet light to near-infrared light.

[0173] <Performance Evaluation 5: Coating Film Appearance Evaluation> 2 parts by weight of the particles (1) obtained in Example 1 and 20 parts by weight of a commercially available acrylic aqueous glossy paint (manufactured by Kanpe Papio Co., Ltd., trade name "Super Hit") were mixed using a stirring and defoaming device for 3 minutes and defoamed for 1 minute to obtain a paint composition. The obtained paint composition was applied onto an ABS resin (acrylonitrile-butadiene-styrene resin) plate using a coating device equipped with a blade with a clearance of 75 μm, and then dried to obtain a coating film. In addition, the obtained paint composition was spray-coated onto an acrylic plate with a thickness of 3 mm to create a matte coating film with a thickness of 50 μm. The obtained coating film had no bumps (protrusions) and had good matting properties.

[0174] <Performance Evaluation 6: Light Diffusion Evaluation> 7.5 parts by weight of the particles (1) obtained in Example 1, 30 parts by weight of an acrylic resin (manufactured by DIC Corporation, trade name "Acrylic Acid A811"), 10 parts by weight of a crosslinking agent (manufactured by DIC Corporation, trade name "VM-D"), and 50 parts by weight of butyl acetate as a solvent were mixed using a stirring and defoaming device for 3 minutes and defoamed for 1 minute to obtain a light-diffusing resin composition. The obtained light-diffusing resin composition was applied onto a PET film with a thickness of 125 μm using a coating apparatus equipped with a blade having a clearance of 50 μm, and then dried at 70°C for 10 minutes to obtain a light-diffusing film. The total light transmittance and haze of the obtained light-diffusing film were measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., trade name "NDH 2000") in accordance with JIS K 7361-1:1997 and JIS K 7136:2000, respectively. The haze value increases as the diffusibility of the light transmitted through the light-diffusing film (transmitted light) becomes higher. As a result of the measurement, the haze was 40.2% and the total light transmittance was 81.5%, indicating that the obtained light-diffusing film has excellent light-diffusing properties.

Industrial Applicability

[0175] The hollow resin particles according to the embodiment of the present invention and the hollow resin particles obtained by the production method according to the embodiment of the present invention can be used in semiconductor materials and the like. The hollow resin particles according to the embodiment of the present invention and the hollow resin particles obtained by the production method according to the embodiment of the present invention can be applied to, for example, resin compositions for semiconductor members, coating compositions, heat-insulating compositions, light-diffusing compositions, and light-diffusing films.

Claims

1. A hollow resin particle having a shell portion and a hollow portion surrounded by the shell portion, The average particle size is 0.1 μm to 50.0 μm, The shell portion contains a polymer (P) having an ether structure represented by formula (1), The polymer (P) is obtained by reacting a monomer (B) containing an aromatic crosslinkable monomer and an aromatic monofunctional monomer with a compound (A) which is a polyphenylene ether having an end group reactive with the monomer (B) and an ether structure represented by formula (1). Hollow resin particles. 【Chemistry 1】

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

3. The hollow resin particle according to claim 1 or 2, which is used in a resin composition for a semiconductor member.

4. 3. The hollow resin particle according to claim 1 or 2, which is used in a coating composition.

5. The hollow resin particle according to claim 1 or 2, which is used in a heat insulating resin composition.

6. The hollow resin particle according to claim 1 or 2, which is used in a light-diffusing resin composition.

7. The hollow resin particle according to claim 1 or 2, which is used for a light diffusing film.

8. A resin composition for a semiconductor member, comprising the hollow resin particles according to claim 1 or 2.

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

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

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

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

13. A method for producing hollow resin particles according to any one of claims 1 to 7, comprising the steps of: reacting 20 to 80 parts by weight of a compound (A) having an ether structure represented by formula (1) with 80 to 20 parts by weight of a monomer (B) that reacts with the compound (A) (the total amount of the compound (A) and the monomer (B) being taken as 100 parts by weight) in an aqueous medium in the presence of a non-reactive solvent; the monomer (B) contains an aromatic crosslinkable monomer and an aromatic monofunctional monomer, and the compound (A) is a polyphenylene ether having a terminal group reactive with the monomer (B) and an ether structure represented by formula (1); A method for producing hollow resin particles. 【Chemistry 2】

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