Hollow resin particle, resin composition for semiconductor member, and dispersion

Abstract

A hollow resin particle according to an embodiment of the present invention has a shell part and a hollow portion that is surrounded by the shell part. The shell part contains a polymer (P1) that is obtained by a reaction of a monomer component (M). The hollow resin particle has an average particle diameter of 0.1 µm to 1 µm, a dielectric loss tangent of less than 0.0050 at a measurement frequency of 10 GHz, and an SP value of the monomer component (M) of 8.80 or less.

Description

Hollow resin particles, resin compositions and dispersions for semiconductor components

[0001] The present invention relates to hollow resin particles, resin compositions for semiconductor components, and dispersions.

[0002] In semiconductor materials, to handle high-frequency signals for next-generation high-speed communication, there is a need for lower dielectric constant, lower dielectric loss tangent, and thinner layers to suppress transmission loss. Therefore, adding hollow resin particles made of acrylic or styrene to semiconductor materials is being considered to achieve a lower dielectric constant.

[0003] For example, conventional hollow resin particles have been reported that are obtained by suspension polymerization of polymerizable monomers containing crosslinkable hydrocarbon monomers such as divinylbenzene together with a hydrophobic solvent (Patent Document 1). However, in recent years, the semiconductor materials market has been studying miniaturization and performance improvement of electronic circuits, and when hollow resin particles are applied to such applications, the hollow resin particles are required to be made into small particles in order to miniaturize semiconductor materials.

[0004] Furthermore, as conventional hollow resin particles, hollow resin particles obtained by suspension polymerization of polymerizable monomers containing (meth)acrylic acid ester monomers together with a hydrophobic solvent have been reported (Patent Document 2). However, (meth)acrylic acid ester monomers have a poor reduction rate of dielectric loss tangent. In addition, the hollow resin particles described in Patent Document 2 had the problem of high amounts of metal residue and eluted ions depending on the manufacturing process and the surfactant used.

[0005] Furthermore, hollow polymer particles produced by seed polymerization have been reported as conventional hollow resin particles (Patent Document 3). However, the hollow resin particles described in Patent Document 3 have a small proportion of crosslinkable monomers in the monomer polymerized into the particles, resulting in weak particle strength and concerns about crushing during processing. In addition, because they contain an acrylic composition, they have a high dielectric loss tangent value and are unsuitable for the above applications.

[0006] International Publication No. 2024-048093, Japanese Patent Publication No. 2023-101708, Japanese Patent Publication No. 2002-241448

[0007] When adding hollow resin particles to various semiconductor components, if the size of the hollow resin particles is not suitable for the size of the semiconductor component, it may cause irregularities in the base resin of the semiconductor component, potentially leading to deterioration of dielectric loss tangent and adhesion. Therefore, for thin-layer semiconductor components, fine hollow resin particles with an average particle diameter of 1 μm or less are required. Furthermore, conventional hollow resin particles use many surfactants to reduce the average particle diameter, resulting in high amounts of metal residue and eluted ions derived from the surfactants, raising concerns about insulation reliability. In addition, conventional hollow resin particles are manufactured using highly polar monomers to improve the stability of the slurry in suspension polymerization in order to reduce the average particle diameter, which leads to the problem of high dielectric loss tangent.

[0008] Therefore, the present invention has been made to solve the above problems, and its main objective is to provide hollow resin particles that have a small average particle size applicable to various materials, reduce the amount of metal residue and eluted ions, and have excellent low dielectric properties. Furthermore, it aims to provide applications for such hollow resin particles.

[0009] [1] Hollow resin particles according to embodiments 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 contains a polymer (P1) obtained by the reaction of a monomer component (M), has an average particle diameter of 0.1 μm to 1 μm, has a dielectric loss tangent at a measurement frequency of 10 GHz of less than 0.0050, and the SP value of the monomer component (M) is 8.80 or less. [2] In the hollow resin particles described in [1] above, the monomer component (M) contains a crosslinkable monomer (a), and when the monomer component (M) is 100 parts by weight, the crosslinkable monomer (a) may be 40 parts by weight to 100 parts by weight. [3] In the hollow resin particles described in [1] or [2] above, the monomer component (M) contains a monofunctional monomer (b), and when the monomer component (M) is 100 parts by weight, the monofunctional monomer (b) may be 60 parts by weight or less. [4] The hollow resin particles described in any one of the above items [1] to [3] may have a hollow ratio of 20% or more. [5] The hollow resin particles described in any one of the above items [1] to [4] may have a relative permittivity of less than 2.00 at a measurement frequency of 10 GHz. [6] The hollow resin particles described in any one of the above items [1] to [5] may have a total amount of metal residue of Ca, K, Li, Mg, and Na of 20 ppm or less. [7] The hollow resin particles described in any one of the above items [1] to [6] may have an SP value of the above monomer component (M) of less than 8.70. [8] The hollow resin particles described in any one of the above items [1] to [7] may have F - , Cl - NO2 - , Br - NO3 - , PO4 3- , and SO4 2-The total amount of elution may be 200 ppm or less. [9] The hollow resin particles according to any one of [1] to [8] above may have a dielectric loss tangent of less than 0.0030 at a measurement frequency of 10 GHz.

[10] The hollow resin particles according to any one of [1] to [9] above may be used for a resin composition for a semiconductor member.

[11] The resin composition for a semiconductor member according to an embodiment of the present invention contains the hollow resin particles according to any one of [1] to

[10] above.

[12] The dispersion according to an embodiment of the present invention contains the hollow resin particles according to any one of [1] to

[10] above.

[0010] 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, having a small average particle diameter applicable to various members, reduced amounts of metal residues and eluted ions, and excellent low dielectric properties. Further, uses of such hollow resin particles can be provided.

[0011] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these embodiments.

[0012] In this specification, when there is an expression of “(meth)acryl”, it means “acryl and / or methacryl”, when there is an expression of “(meth)acrylate”, it means “acrylate and / or methacrylate”, and when there is an expression of “(meth)acryloyl”, it means “acryloyl and / or methacryloyl”.

[0013] <<<1. Hollow resin particles>>> <<<1-1. Structure and properties of hollow resin particles>>> 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, having an average particle diameter of 0.1 μm to 1 μm, and having a dielectric loss tangent of less than 0.0050 at a measurement frequency of 10 GHz.

[0014] Here, the term "hollow" means a state in which the interior is filled with a substance other than resin, such as a gas or a liquid, etc. In terms of being able to more effectively exhibit the effects of the present invention, preferably, it means a state filled with a gas. In some cases, it may be a state filled with a liquid.

[0015] The hollow portion may consist of one hollow region, or may consist of a plurality of hollow regions or a porous structure. In the hollow resin particles according to an embodiment of the present invention, the hollow portion preferably has a single hollow structure consisting of one hollow region. When the hollow portion is one hollow portion, the resin component constituting the shell portion becomes relatively more, and even when kneaded in coexistence with inorganic particles in the resin composition, the shell portion is less likely to be crushed. Also, when the hollow portion is one hollow portion, it is possible to effectively prevent the intrusion of a base material or the like into the hollow portion.

[0016] When the average particle diameter of the hollow resin particles is 0.1 μm to 1 μm, the hollow resin particles can be used in resin compositions for various applications. The hollow resin particles having such an average particle diameter are suitable, for example, for thinning a semiconductor member. When the average particle diameter of the hollow resin particles is less than 0.1 μm, the thickness of the shell portion becomes relatively thin, and there is a possibility that the hollow resin particles may not have sufficient strength. When the average particle diameter of the hollow resin particles is larger than 1 μm, the applications of the resin composition in which the hollow resin particles can be used are limited. Also, when the average particle diameter of the hollow resin particles is larger than 1 μm, there is a possibility that phase separation between the polymer generated by polymerization of the monomer component during suspension polymerization and the solvent becomes difficult to occur, and thereby it may become difficult to form the shell portion.

[0017] The average particle diameter of the hollow resin particles according to an embodiment of the present invention is preferably 100 nm to 900 nm, more preferably 150 nm to 800 nm, still more preferably 200 nm to 700 nm, and particularly preferably 300 nm to 600 nm. If the average particle diameter of the hollow resin particles according to an embodiment of the present invention is within the above range, the effects of the present invention can be more effectively exhibited.

[0018] The hollow resin particles according to the embodiments of the present invention typically have a hollowness of 20% or more, preferably 30% to 80%, more preferably 35% to 75%, even more preferably 40% to 70%, and particularly preferably 45% to 65%. If the hollowness of the hollow resin particles is within the above range, better dielectric properties can be exhibited. In some cases, the hollow resin particles according to the embodiments of the present invention may have a hollowness of 60% or less, 55% or less, or even 50% or less.

[0019] The hollow resin particles according to the embodiments of the present invention have a relative permittivity at a frequency of 10 GHz, preferably less than 2.00, more preferably 1.90 or less, even more preferably 1.80 or less, and particularly preferably 1.70 or less. If the relative permittivity at a frequency of 10 GHz is within the above range, the hollow resin particles according to the embodiments of the present invention can exhibit excellent low dielectric properties. The lower limit of the relative permittivity at a frequency of 10 GHz for the hollow resin particles according to the embodiments of the present invention is, for example, 1.10 or more.

[0020] The hollow resin particles according to the embodiments of the present invention have a dielectric loss tangent at a frequency of 10 GHz, preferably 0.0040 or less, more preferably 0.0032 or less, even more preferably 0.0030 or less, even more preferably less than 0.0030, particularly preferably 0.0020 or less, and most preferably 0.0015 or less. If the dielectric loss tangent at a frequency of 10 GHz is within the above range, the hollow resin particles according to the embodiments of the present invention can exhibit excellent low dielectric properties. The lower limit of the dielectric loss tangent at a frequency of 10 GHz for the hollow resin particles according to the embodiments of the present invention is, for example, 0.0001 or more.

[0021] The hollow resin particles according to an embodiment of the present invention preferably have a total metal residue amount of Ca, K, Li, Mg, and Na of 20 ppm or less. Herein, the present specification describes the total metal residue amount of Ca, K, Li, Mg, and Na as the "metal residue amount". When the metal residue amount of the hollow resin particles exceeds 20 ppm, the performance of a member obtained by mixing the hollow resin particles with a resin or the like may be degraded by the metal residue. Therefore, there is a possibility that the hollow resin particles may not exhibit excellent low dielectric characteristics or may not exhibit uniform low dielectric characteristics. Further, for example, when hollow resin particles having a large amount of metal residue are used for a semiconductor member, the metal residue eluted from the hollow resin particles may cause ion migration. Furthermore, when the metal residue amount of the hollow resin particles exceeds 20 ppm, it may also cause corrosion. The metal residue amount of the hollow resin particles is more preferably 10 ppm or less, and even more preferably 5 ppm or less.

[0022] The hollow resin particles according to an embodiment of the present invention contain fluoride ions (F - ), chloride ions (Cl - ), nitrite ions (NO2 - ), bromide ions (Br - ), nitrate ions (NO3 - ), phosphate ions (PO4 3- ), and sulfate ions (SO4 2- ), and preferably have a total elution amount of 200 ppm or less. Herein, the present specification refers to F - , Cl - , NO2 - , Br - , NO3 - , PO4 3- , and SO4 2-The total amount of eluted ions is referred to as the "eluted ion amount." If the amount of eluted ions from hollow resin particles exceeds 200 ppm, the ionic components eluted from the hollow resin particles may reduce the performance of the component obtained by mixing the hollow resin particles with resin, etc. Therefore, the hollow resin particles may not be able to exhibit excellent low dielectric properties or uniform low dielectric properties. Furthermore, for example, when hollow resin particles with a large amount of eluted ions are used in semiconductor components, the ionic components eluted from the hollow resin particles may cause ion migration. The amount of eluted ions from hollow resin particles is more preferably 100 ppm or less, even more preferably 50 ppm or less, and particularly preferably 20 ppm or less.

[0023] In this specification, the amount of metal residue in hollow resin particles means the sum of the masses of Ca, K, Li, Mg, and Na per unit mass of hollow resin particles, and the amount of eluted ions in hollow resin particles means the amount of eluted F per unit mass of hollow resin particles. - , Cl - NO2 - , Br - NO3 - , PO4 3- , and SO4 2- This refers to the total mass of the ions. Therefore, in terms of metal residue and eluted ions, 1 ppm = 1 mg / kg.

[0024] The hollow resin particles according to the embodiments of the present invention may be in the form of a dry powder or dispersed in a liquid (dispersion medium).

[0025] ≪1-2. Shell Section≫ The shell section contains a polymer (P1) obtained by the reaction of a monomer component (M), and the SP value of the monomer component (M) is 8.80 or less. The effects of the present invention can be realized by the inclusion of such a polymer (P1) in the shell section.

[0026] Polymer (P1) can thus be defined as something obtained by the reaction of monomer components (M). This is because, since polymer (P1) is formed by the reaction of monomer components (M), it is impossible and impractical to directly identify polymer (P1) by its structure. Therefore, the definition "obtained by the reaction of monomer components (M)" appropriately identifies polymer (P1) as a "substance."

[0027] The SP value (solubility parameter) refers to the solubility parameter δ calculated using the following formula (1), based on the values ​​of ΔF (molar attractive constant) and Δv (molar volume) for various atomic groups, as described by Toshinao Okitsu in "Adhesion," Polymer Society, Vol. 40, No. 8 (1996), pp. 342-350. In formula (1), ΣΔF and ΣΔv are the sums of ΔF and Δv for the various atomic groups constituting the compound (reactive monomer). If the monomer component (M) is a mixture of multiple reactive monomers, the SP value of the monomer component (M) is the sum of the products of the mole fraction of each reactive monomer and δ. For example, if monomer component (M) contains monomers m1, m2, and m3, and the SP value of monomer m1 is δ1, the SP value of monomer m2 is δ2, and the SP value of monomer m3 is δ3, and the mole fraction of monomer m1 in monomer component (M) is φ1, the mole fraction of monomer m2 is φ2, and the mole fraction of monomer m3 is φ3 (φ1 + φ2 + φ3 = 1), then the SP value of monomer component (M) is δ mix ) is calculated by the following formula (2): δ = ΣΔF / ΣΔv ... (1) δ mix =φ1δ1+φ2δ2+φ3δ3...(2)

[0028] The SP value of the monomer component (M) is preferably 8.70 or less, more preferably less than 8.70, even more preferably 8.68 or less, and particularly preferably 8.67 or less. By satisfying the above range for the SP value of the monomer component (M), the hollow resin particles according to the embodiment of the present invention have better low dielectric properties, and in particular, the dielectric loss tangent can be reduced. The SP value of the monomer component (M) is, for example, 7.00 or more, and preferably 8.00 or more.

[0029] The polymer (P1) may be of one type or two or more types.

[0030] The content ratio of the polymer (P1) in the shell portion is preferably 60% to 100% by weight, more preferably 70% to 100% by weight, even more preferably 80% to 100% by weight, and particularly preferably 90% to 100% by weight, in order to better exhibit the effects of the present invention.

[0031] The monomer component (M) preferably contains a crosslinkable monomer (a). Therefore, the polymer (P1) is preferably obtained by polymerizing the monomer component (M) containing the crosslinkable monomer (a) and has structural units derived from the crosslinkable monomer (a).

[0032] Examples of crosslinkable monomers (a) 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, diallyl phthalate, and divinylbiphenyl. In terms of being able to better express the effects of the present invention, aromatic crosslinkable monomers are preferred as crosslinkable monomers (a), and divinylbenzene is more preferred. Crosslinkable monomers (a) may be one type or two or more types.

[0033] The amount of crosslinkable monomer (a) in monomer component (M) is preferably 40 parts by weight or more, more preferably more than 40 parts by weight, even more preferably 45 parts by weight or more, even more preferably 50 parts by weight or more, particularly preferably 55 parts by weight or more, most preferably 60 parts by weight or more, preferably 100 parts by weight or less, more preferably less than 100 parts by weight, even more preferably 99 parts by weight or less, particularly preferably 95 parts by weight or less, when monomer component (M) is 100 parts by weight, in order to better express the effects of the present invention.

[0034] The monomer component (M) preferably contains a monofunctional monomer (b). Therefore, the polymer (P1) is preferably obtained by polymerizing a monomer component (M) containing, for example, a monofunctional monomer (b) and a crosslinkable monomer (a), and has structural units derived from the monofunctional monomer (b) and structural units derived from the crosslinkable monomer (a).

[0035] Examples of monofunctional monomers (b) include aromatic monofunctional monomers such as styrene, α-methylstyrene, ethyl vinylbenzene, vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, vinyl biphenyl, and vinylnaphthalene; C1-C16 alkyl (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and cetyl (meth)acrylate; and hydrophilic monofunctional monomers such as (meth)acrylic acid and compounds represented by the following formula (3). In order to better exhibit the effects of the present invention, it is preferable that monofunctional monomer (b) includes aromatic monofunctional monomers. The aromatic monofunctional monomers are preferably styrene and ethyl vinylbenzene. Monofunctional monomer (b) may be one type or two or more types.

[0036]

[0037] In general formula (3), R 1 represents H or CH3, and R 2 R represents an alkanediyl group having 1 to 10 carbon atoms or an alkenediyl group having 2 to 10 carbon atoms. 3 R represents a single bond, an alkanediyl group with 1 to 10 carbon atoms, an alkenediyl group with 2 to 10 carbon atoms, or a phenylene group; X represents a single bond, an ester bond, an ether bond, or a carbonyl group; n represents a number from 1 to 5; and n R 2 X, R 3 They are independent of each other.

[0038] The content of monofunctional monomer (b) in monomer component (M) is preferably 60 parts by weight or less, more preferably less than 60 parts by weight, even more preferably 55% by weight or less, even more preferably 50% by weight or less, particularly preferably 45 parts by weight or less, most preferably 40 parts by weight or less, preferably 1% by weight or more, and more preferably 5% by weight or more, when monomer component (M) is 100 parts by weight, in order to better express the effects of the present invention. This makes it possible to realize hollow resin particles with excellent dielectric properties.

[0039] The content of aromatic monofunctional monomers in the monomer component (M) is preferably 60 parts by weight or less, more preferably less than 60 parts by weight, even more preferably 55% by weight or less, particularly preferably 50 parts by weight or less, most preferably 45 parts by weight or less, preferably 1 part by weight or more, and more preferably 5 parts by weight or more, when the monomer component (M) is 100 parts by weight, in order to better express the effects of the present invention. This makes it possible to realize hollow resin particles with excellent dielectric properties.

[0040] Monofunctional monomer (b) may include a hydrophilic monofunctional monomer in addition to an aromatic monofunctional monomer. Hydrophilic monofunctional monomer (c) preferably has a carboxyl group. Hydrophilic monofunctional monomer (c) is preferably a compound represented by the above formula (3).

[0041] In general formula (3), R 2The α represents an alkanediyl group having 1 to 10 carbon atoms or an alkenediyl group having 2 to 10 carbon atoms, where the number of carbon atoms in the alkanediyl group is preferably 2 to 6, and more preferably 2 to 4. The alkanediyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkenediyl group is preferably 2 to 6, and more preferably 2 to 4. The alkenediyl group may be linear, branched, or cyclic.

[0042] R 2 Regarding this, examples of alkanediyl groups include methylene group, ethane-1,1-diyl group, ethane-1,2-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, propane-1,3-diyl group, 2-methylpropane-1,3-diyl group, butane-1,3-diyl group, butane-2,3-diyl group, and butane-1,4-diyl group. 2 Examples of alkenediyl groups include ethene-1,2-diyl group, 1-propene-1,3-diyl group, 2-butene-1,4-diyl group, 1-methyl-1-butene-1,4-diyl group, and 2-cyclohexene-1,4-diyl group.

[0043] In general formula (3), R 3 The group represents a single bond, an alkanediyl group having 1 to 10 carbon atoms, an alkenediyl group having 2 to 10 carbon atoms, or a phenylene group. The number of carbon atoms in the alkanediyl group is preferably 2 to 6, and more preferably 2 to 4. The alkanediyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkenediyl group is preferably 2 to 6, and more preferably 2 to 4. The alkenediyl group may be linear, branched, or cyclic.

[0044] R 3 Regarding this, examples of alkanediyl groups include those mentioned above. 3 Regarding this, examples of alkenediyl groups include those mentioned above.

[0045] In general formula (3), X represents a single bond, an ester bond, an ether bond, or a carbonyl group. An ester bond is represented by R. 2 -O-CO-R3 The structure may also be R 2 -CO-O-R 3 It may also have this structure.

[0046] Examples of hydrophilic monofunctional monomers represented by general formula (3) include 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl maleic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl succinic acid, and 2-acryloyloxyethyl phthalic acid.

[0047] Commercially available hydrophilic monofunctional monomers represented by general formula (3) can also be used. For example, one such commercially available product is "Light Ester HO-MS(N)" manufactured by Kyoeisha Chemical Co., Ltd.

[0048] The content of hydrophilic monofunctional monomers in monomer component (M) is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, even more preferably 3 parts by weight or less, particularly preferably 2 parts by weight or less, preferably 0.5 parts by weight or more, and more preferably 1 part by weight or more, when monomer component (M) is 100 parts by weight, in order to better express the effects of the present invention. The effects of the present invention can be better expressed when the content of hydrophilic monofunctional monomers in monomer component (M) is within the above range. Furthermore, when the content of hydrophilic monofunctional monomers in monomer component (M) is within the above range, it is easier to adjust the SP value of monomer component (M) to 8.80 or less, preferably less than 8.70.

[0049] The total content of crosslinkable monomers (a) and monofunctional monomers (b) in monomer component (M), for example, the total content of aromatic crosslinkable monomers, aromatic monofunctional monomers, and hydrophilic monofunctional monomers, is preferably 80 to 100 parts by weight, more preferably 85 to 100 parts by weight, even more preferably 90 to 100 parts by weight, particularly preferably 95 to 100 parts by weight, and most preferably 98 to 100 parts by weight, when monomer component (M) is 100 parts by weight, in order to better express the effects of the present invention.

[0050] The monomer component (M) may include, in addition to the crosslinkable monomer (a) and the monofunctional monomer (b), any other monomer of appropriate reactivity. The other monomer may be one type or two or more types.

[0051] The shell portion may contain any other suitable components as long as they do not impair the effects of the present invention. For example, the shell portion may contain a non-crosslinkable polymer (P2) in addition to the polymer (P1). The non-crosslinkable polymer (P2) may be one type or two or more types. By including the non-crosslinkable polymer (P2), phase separation of the polymerized oil droplets during suspension polymerization can be promoted, making it easier to form uniform particles, and as a result, excellent low dielectric properties or uniform low dielectric properties can be exhibited.

[0052] As the non-crosslinkable polymer (P2), any suitable non-crosslinkable polymer can be used as long as it does not impair the effects of the present invention. Typically, the non-crosslinkable polymer (P2) is a non-polar polymer. As such a non-crosslinkable polymer (P2), a non-crosslinkable polymer with a number average molecular weight of 500 to 200,000 is preferred. If a non-crosslinkable polymer with a number average molecular weight of less than 500 is used, phase separation may not occur easily, which may make it difficult to form the shell portion. If a non-crosslinkable polymer with a number average molecular weight greater than 200,000 is used, the viscosity of the oil droplets increases, resulting in a larger average particle size. This may make it difficult for the polymer, which is formed by the polymerization of monomer components during suspension polymerization, to undergo phase separation between the polymer and the solvent, which may make it difficult to form the shell portion.

[0053] Examples of such non-crosslinkable polymers (P2) include polystyrene, polyethylene, polypropylene, aliphatic olefin polymers having 4 or more carbon atoms (may have a linear or branched side-chain structure), polyphenylene ether, modified polyphenylene ether, polymethyl methacrylate, block copolymer of styrene and butadiene (e.g., styrene-butadiene-styrene block copolymer (SBS)), block copolymer of styrene and isoprene (e.g., styrene-isoprene-styrene block copolymer (SIS)), poly(meth)acrylic acid esters (fatty chains having 1 or more carbon atoms, which may be linear or branched), paraffin, etc. Note that the above-mentioned non-crosslinkable polymers (P2) may undergo hydrogenation reactions to at least some of their unsaturated bonds. The non-crosslinkable polymer (P2) may be a single type or two or more types.

[0054] The non-crosslinkable polymer (P2) may contain a hydrocarbon resin. Any suitable compound can be used as the hydrocarbon resin, as long as it does not impair the effects of the present invention. Examples of hydrocarbon resins include aliphatic / aromatic hydrocarbon resins, aromatic hydrocarbon resins, alicyclic hydrocarbon resins, and aliphatic hydrocarbon resins. Preferably, the hydrocarbon resin is at least one selected from the group consisting of aliphatic / aromatic hydrocarbon resins, aromatic hydrocarbon resins, and aliphatic hydrocarbon resins; more preferably, it is at least one selected from the group consisting of aliphatic / aromatic hydrocarbon resins and aromatic hydrocarbon resins; and even more preferably, it is an aliphatic / aromatic hydrocarbon resin. According to the above, phase separation of polymerization oil droplets during suspension polymerization is promoted, and as a result, better low dielectric properties can be exhibited. These hydrocarbon resins may be used individually or in combination of two or more types.

[0055] Aliphatic / aromatic hydrocarbon resins refer to hydrocarbon resins obtained by copolymerizing aliphatic hydrocarbons and aromatic hydrocarbons. Aliphatic / aromatic hydrocarbon resins are resins polymerized using styrene, vinyltoluene, indene, piperine, etc., as the main raw materials.

[0056] The aliphatic hydrocarbons constituting the aliphatic / aromatic hydrocarbon resin are aliphatic hydrocarbons having polymerizable unsaturated bonds. Typically, these aliphatic hydrocarbons are dienes, which are aliphatic fractions obtained by the thermal decomposition of naphtha. The carbon number of the aliphatic hydrocarbons is, for example, 3 to 7, preferably 4 to 6, and more preferably 5. Examples of such aliphatic hydrocarbons include linear dienes such as isoprene and piperylene, cyclopentadiene, and cyclic dienes such as methylcyclopentadiene, dicyclopentadiene, methyldicyclopentadiene, and dimethyldicyclopentadiene, with linear dienes being preferred. These aliphatic hydrocarbons may be one type or two or more types. The aromatic hydrocarbons constituting the aliphatic / aromatic hydrocarbon resin are typically aromatic compounds having linear or cyclic substituents containing polymerizable unsaturated bonds. Typically, these aromatic hydrocarbons are aromatic fractions obtained by the thermal decomposition of naphtha. The carbon number of the aromatic hydrocarbons is, for example, 7 to 11, preferably 8 to 10. Examples of such aromatic hydrocarbons include cyclic dienes such as styrene, α-methylstyrene, β-methylstyrene, vinyltoluene, divinylbenzene, indene, and methylindene, with styrene, vinyltoluene, and indene being preferred. These aromatic hydrocarbons may be one or two or more. Aliphatic / aromatic hydrocarbon resins are resins polymerized using styrene, vinyltoluene, indene, isoprene, piperine, etc., as the main raw materials. The ratio of aliphatic hydrocarbon components to aromatic hydrocarbon components (aliphatic hydrocarbon / aromatic hydrocarbon) in the aliphatic / aromatic hydrocarbon resin is preferably more than 30%, more preferably 40% or more, preferably 70% or less, more preferably 60% or less, and even more preferably 50% or less. The weight-average molecular weight (Mw) of the aliphatic / aromatic hydrocarbon resin is, for example, 500 to 5,000, preferably 1,000 to 4,800, and more preferably 1,500 to 4,500. The number-average molecular weight (Mn) of the aliphatic / aromatic hydrocarbon resin is, for example, 500 to 2,000, preferably 700 to 1,500, and more preferably 800 to 1,300.

[0057] Aromatic hydrocarbon resins refer to hydrocarbon resins obtained by copolymerizing aromatic hydrocarbons. Aromatic hydrocarbons have, for example, 7 to 11 carbon atoms, preferably 8 to 10, and the aromatic hydrocarbons mentioned above are examples of aromatic hydrocarbons that constitute aliphatic / aromatic hydrocarbon resins. Aromatic hydrocarbon resins are, for example, resins obtained by polymerizing styrene, vinyltoluene, and indene.

[0058] Alicyclic hydrocarbon resins are, for example, resins obtained by hydrogenating aliphatic / aromatic hydrocarbon resins or aromatic hydrocarbon resins.

[0059] Aliphatic hydrocarbon resins are hydrocarbon resins obtained by polymerizing one or more aliphatic hydrocarbons having polymerizable unsaturated bonds.

[0060] The content of the non-crosslinked polymer (P2) in the shell portion is preferably 0% to 40% by weight, more preferably 1% to 30% by weight, and even more preferably 3% to 20% by weight, in order to better exhibit the effects of the present invention. If the content of the non-crosslinked polymer in the shell portion is too high, there is a risk that excellent low dielectric properties cannot be exhibited or that uniform dielectric properties cannot be exhibited.

[0061] ≪1-3. Applications of Hollow Resin Particles≫ Hollow resin particles according to the embodiments of the present invention can be used in various applications. In terms of making better use of the effects of the present invention, hollow resin particles according to the embodiments of the present invention are suitable for semiconductor materials, and are typically suitable for use in resin compositions for semiconductor materials. In addition to the above-mentioned application to resin compositions for semiconductor materials, hollow resin particles according to the embodiments of the present invention can also be applied to applications that can make use of the effects of the present invention, such as paint compositions, heat insulating resin compositions, light diffusing resin compositions, and light diffusing films.

[0062] <<Resin Composition for Semiconductor Materials>> The hollow resin particles according to the embodiment of the present invention have a small particle size and heat resistance, and are therefore suitable for use in resin compositions for semiconductor materials, for example, in thin-layer semiconductor materials, as they can exhibit low dielectric properties.

[0063] The resin composition for semiconductor components according to an embodiment of the present invention contains hollow resin particles according to an embodiment of the present invention. Such a resin composition for semiconductor components is suitable, for example, for use as a encapsulant for semiconductor chips.

[0064] Semiconductor components refer to the components that make up a semiconductor, such as semiconductor packages and semiconductor modules. In this specification, a resin composition for semiconductor components refers to a resin composition used in semiconductor components.

[0065] A semiconductor package is a component in which an IC chip is an essential component, and is constructed using at least one material selected from molding resin, underfill material, molded underfill material, die bonding material, prepreg for semiconductor package substrates, metal-clad laminate for semiconductor package substrates, and build-up material for printed circuit boards for semiconductor packages.

[0066] A semiconductor module is a component in which a semiconductor package is an essential component, and which is composed of at least one component selected from prepregs for printed circuit boards, metal-clad laminates for printed circuit boards, build-up materials for printed circuit boards, solder resist materials, coverlay films, electromagnetic shielding films, and adhesive sheets for printed circuit boards.

[0067] <Paint Composition> The hollow resin particles according to the embodiment of the present invention can impart an excellent appearance to the coating film containing them, and therefore can be suitably used in paint compositions.

[0068] Such a paint composition contains hollow resin particles according to an embodiment of the present invention.

[0069] The paint composition preferably comprises at least one selected from a binder resin and a UV-curable resin. The binder resin may consist of only one type or two or more types. The UV-curable resin may consist of only one type or two or more types.

[0070] Any suitable binder resin can be used as the binder resin, as long as it does not impair the effects of the present invention. Examples of such binder resins include resins soluble in organic solvents or water, and emulsion-type aqueous resins that can be dispersed in water. Specifically, examples of binder resins include acrylic resins, alkyd resins, polyester resins, polyurethane resins, chlorinated polyolefin resins, and amorphous polyolefin resins.

[0071] As the UV-curable resin, any suitable UV-curable resin can be used as long as it does not impair the effects of the present invention. Examples of such UV-curable resins include polyfunctional (meth)acrylate resins and polyfunctional urethane acrylate resins, with polyfunctional (meth)acrylate resins being preferred, and polyfunctional (meth)acrylate resins having three or more (meth)acryloyl groups in one molecule being more preferred. Specific examples of polyfunctional (meth)acrylate resins having three or more (meth)acryloyl groups in one molecule include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, 1,2,4-cyclohexanetetra(meth)acrylate, pentaglycerol triacrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol triacrylate, and tripentaerythritol hexaacrylate.

[0072] When the paint composition contains at least one selected from a binder resin and a UV-curable resin, the proportion of these components can be any appropriate proportion depending on the purpose. Typically, the amount of hollow resin particles according to the embodiment of the present invention is preferably 5% to 50% by weight, more preferably 10% to 50% by weight, and even more preferably 20% to 40% by weight, relative to the total amount of the binder resin (in terms of solids content in the case of an emulsion-type aqueous resin) and at least one selected from a UV-curable resin and the hollow resin particles according to the embodiment of the present invention.

[0073] When a UV-curable resin is used, a photopolymerization initiator is preferably used in combination. Any suitable photopolymerization initiator can be used as the photopolymerization initiator, as long as it does not impair the effects of the present invention. Examples of such photopolymerization initiators include acetophenones, benzoins, phosphine oxides, ketals, α-hydroxyalkylphenones, α-aminoalkylphenones, anthraquinones, thioxanthones, azo compounds, peroxides (as described in Japanese Patent Publication No. 2001-139663, etc.), 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, onium salts, borate salts, activated halogen compounds, and α-acyloxime esters.

[0074] The paint composition may contain a solvent. The solvent may be one type or two or more types. When the paint composition according to the embodiment of the present invention contains a solvent, the content ratio can be any appropriate ratio depending on the purpose.

[0075] As the solvent, any suitable solvent can be used as long as it does not impair the effects of the present invention. Preferably, such a solvent is one that can dissolve or disperse the binder resin or UV-curable resin. Examples of such solvents for oil-based paints include hydrocarbon solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; and ether solvents such as dioxane, ethylene glycol diethyl ether, and ethylene glycol monobutyl ether. Examples of solvents for water-based paints include water and alcohols.

[0076] The paint composition may be diluted to adjust its viscosity as needed. Any suitable diluent can be used as the diluent, depending on the purpose. Examples of such diluents include the solvents mentioned above. There may be one diluent or two or more diluents.

[0077] The paint composition may optionally contain other components, such as surface modifiers, flow modifiers, UV absorbers, light stabilizers, curing catalysts, extender pigments, coloring pigments, metallic pigments, mica powder pigments, and dyes.

[0078] When forming a coating film using a paint composition, any suitable coating method can be adopted depending on the purpose. Examples of such coating methods include spray coating, roll coating, brush coating, coating reverse roll coating, gravure coating, die coating, comma coating, and spray coating.

[0079] When forming a coating film using a coating composition, any suitable method can be adopted depending on the purpose. For example, one such method involves applying the coating to any coated surface of a substrate to create a coating film, drying this coating film, and then curing the coating film as needed to form the coating film. Examples of substrates include metals, wood, glass, and plastics (PET (polyethylene terephthalate), PC (polycarbonate), acrylic resin, TAC (triacetylcellulose), etc.).

[0080] <<Thermal Insulation Resin Composition>> The hollow resin particles according to the embodiment of the present invention can impart excellent thermal insulation properties to the coating film containing them, and are therefore suitable for use in thermal insulation resin compositions. The coating film containing the hollow resin particles according to the embodiment of the present invention can exhibit excellent reflectivity in the wavelength range from ultraviolet light to near-infrared light.

[0081] Such a heat-insulating resin composition includes hollow resin particles according to an embodiment of the present invention.

[0082] The heat-insulating resin composition preferably comprises at least one selected from a binder resin and a UV-curable resin. The descriptions of the binder resin and UV-curable resin described above for paint compositions may be applied.

[0083] The heat-insulating resin composition may contain a solvent. The description of the solvent can be found in the previous explanation for the paint composition.

[0084] The heat-insulating resin composition may be diluted to adjust its viscosity as needed. The diluents described above for paint compositions can be used as reference.

[0085] The heat-insulating resin composition may optionally contain other components, such as surface conditioners, flow modifiers, UV absorbers, light stabilizers, curing catalysts, extender pigments, coloring pigments, metal pigments, mica powder pigments, and dyes.

[0086] When forming a coating film using a heat-insulating resin composition, the coating method and forming method can be described by referring to the above-mentioned explanation of the paint composition.

[0087] <<Light-diffusing resin composition>> The hollow resin particles according to the embodiment of the present invention can impart excellent light-diffusing properties to a coating film containing them, and are therefore suitable for use in a light-diffusing resin composition.

[0088] Such a light-diffusing resin composition includes hollow resin particles according to an embodiment of the present invention.

[0089] The diffusible resin composition preferably comprises at least one selected from a binder resin and a UV-curable resin. The descriptions of the binder resin and UV-curable resin described above for paint compositions may be applied.

[0090] The light-diffusing resin composition may contain a solvent. The description of the solvent can be found in the previous explanation for the paint composition.

[0091] The light-diffusing resin composition may be diluted to adjust its viscosity as needed. The diluents described above for paint compositions can be used as reference.

[0092] The light-diffusing resin composition may optionally contain other components, such as surface modifiers, flow modifiers, ultraviolet absorbers, light stabilizers, curing catalysts, extender pigments, coloring pigments, metal pigments, mica powder pigments, and dyes.

[0093] When forming a coating film using a light-diffusing resin composition, the coating method and forming method can be described in the above-mentioned explanation of the paint composition.

[0094] <<Light Diffusing Film>> The hollow resin particles according to the embodiment of the present invention can impart excellent light diffusing properties to a film having a coating film containing them, and therefore can be suitably used in light diffusing films.

[0095] Such a light-diffusing film contains hollow resin particles according to an embodiment of the present invention.

[0096] The light-diffusing film comprises a light-diffusing layer formed from the aforementioned light-diffusing resin composition and a substrate. The light-diffusing layer may or may not be the outermost layer of the light-diffusing film. The light-diffusing film according to the embodiment of the present invention may include any other suitable layer depending on the purpose. Examples of such other layers include a protective layer, a hard coat layer, a planarizing layer, a high refractive index layer, an insulating layer, a conductive resin layer, a conductive metal nanoparticle layer, a conductive metal oxide nanoparticle layer, and a primer layer.

[0097] Examples of substrates include metal, wood, glass, plastic film, plastic sheet, plastic lens, plastic panel, cathode ray tube, fluorescent display tube, and liquid crystal display board. Examples of plastics that make up plastic film, plastic sheet, plastic lens, and plastic panel include PET (polyethylene terephthalate), PC (polycarbonate), acrylic resin, and TAC (triacetylcellulose).

[0098] 2. Method for Producing Hollow Resin Particles The hollow resin particles according to the embodiments of the present invention can be produced by any suitable method, as long as the effects of the present invention are not impaired.

[0099] A typical method for producing hollow resin particles according to embodiments of the present invention involves dispersing a monomer component (M) and an oil phase containing an organic solvent in an aqueous phase containing an aqueous medium and a surfactant, and carrying out suspension polymerization. The monomer component (M) preferably contains a crosslinkable monomer (a), more preferably contains a crosslinkable monomer (a) and a monofunctional monomer (b), and more preferably contains an aromatic crosslinkable monomer and an aromatic monofunctional monomer.

[0100] The monomer component (M) can be described using the explanation provided in section 1-2, "Shell portion," above.

[0101] The organic solvent may be one type or two or more types. Any suitable organic solvent can be used as the organic solvent, as long as it does not impair the effects of the present invention. Preferably, such organic solvents have a boiling point of less than 100°C. By using an organic solvent with a boiling point of less than 100°C, it becomes easier to remove the solvent from the hollow portion of the resulting hollow resin particles, thereby reducing manufacturing costs.

[0102] Examples of organic solvents with a boiling point below 100°C include heptane, hexane, cyclohexane, methyl acetate, ethyl acetate, methyl ethyl ketone, chloroform, and carbon tetrachloride.

[0103] The amount of organic solvent used can be any appropriate amount, as long as it does not impair the effects of the present invention. For example, such an amount is 10 to 60 parts by weight per 100 parts by weight of monomer component (M).

[0104] The oil phase preferably contains a polymerization initiator. There may be only one polymerization initiator or two or more. Any suitable polymerization initiator can be used as the polymerization initiator, as long as it does not impair the effects of the present invention.

[0105] Examples of polymerization initiators include organic peroxides such as cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, benzoyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, dimethylbis(tert-butylperoxy)hexane, dimethylbis(tert-butylperoxy)hexyn-3, bis(tert-butylperoxyisopropyl)benzene, bis(tert-butylperoxy)trimethylcyclohexane, butyl-bis(tert-butylperoxy)valerate, tert-butyl 2-ethylhexaneperoxyate, dibenzoyl peroxide, paramentane hydroperoxide, tert-butylperoxybenzoate, etc.; 2,2'-azobibisisobutyronitrile, 2,2'-azobi Azobis(2-methylbutyronitrile), 2,2'-azobis(2-isopropylbutyronitrile), 2,2'-azobis(2,3-dimethylbutyronitrile), 2,2'-azobis(2,4-dimethylbutyronitrile), 2,2'-azobis(2-methylcapronitrile), 2,2'-azobis(2,3,3-trimethylbutyronitrile), 2,2'-azobis(2,4,4-trimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile) Examples of azo compounds include lelonitrile, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(4-ethoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(4-n-butoxy-2,4-dimethylvaleronitrile), 1,1'-azobis(cyclohexane-1-carbonitride), 2-(carbamoylazo)isobutyronitrile, and 4,4'-azobis(4-cyanopentanoic acid).

[0106] The polymerization initiator may be one whose 10-hour half-life temperature is 90°C or lower.

[0107] The amount of polymerization initiator used can be any appropriate amount, as long as it does not impair the effects of the present invention. For example, such an amount is 0.1 to 5 parts by weight per 100 parts by weight of monomer component (M).

[0108] The oil phase may contain a non-crosslinkable polymer (P2). The non-crosslinkable polymer (P2) may be one type or two or more types. The explanation of the non-crosslinkable polymer (P2) can be referred to in the section above, "1-2. Shell."

[0109] In addition to the components described above, the oil phase may contain any other suitable components as long as they do not impair the effects of the present invention. Such other components may be one type or two or more types.

[0110] Examples of aqueous media include water, and mixed media of water and lower alcohols (alcohols with 5 or fewer carbon atoms, such as methanol, ethanol, and isopropyl alcohol). As for water, at least one selected from the group consisting of deionized water and distilled water is preferred.

[0111] The amount of aqueous medium used can be any appropriate amount, as long as it does not impair the effects of the present invention. Such an amount is preferably 100 to 2000 parts by weight, and more preferably 200 to 1000 parts by weight, per 100 parts by weight of the oil phase. By adjusting the amount of aqueous medium to the above range, the dispersion stability of monomers during polymerization is improved, and the formation of aggregates of resin particles during polymerization can be suppressed.

[0112] The aqueous phase preferably contains a surfactant. Any suitable surfactant can be used as the surfactant, as long as it does not impair the effects of the present invention. There may be only one surfactant or two or more surfactants. Examples of such surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants.

[0113] Examples of anionic surfactants include sodium oleate; fatty acid soaps such as potassium castor oil soap; polysulfonates; polycarboxylates; alkyl sulfate esters such as sodium lauryl sulfate and ammonium lauryl sulfate; alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate; alkylaryl sulfonates; alkylnaphthalene sulfonates; alkane sulfonates; dialkyl sulfonates; dialkyl sulfosuccinates; alkyl phosphates; alkyl phosphate esters; naphthalene sulfonate formalin condensates or their salts, such as sodium salts of β-naphthalene sulfonate formalin condensates; and polyoxyethylene nonylphenyl ether sulfate esters. Examples include oxyethylene alkylphenyl ether sulfate salts; polyoxyalkylene polycyclic phenyl ether ammonium sulfate salts (commercially available examples include Newcol 707-SF from Nippon Emulsifier Co., Ltd.); polyoxyethylene sulfonated phenyl ether phosphate; polyoxyethylene alkyl ether sulfates such as polyoxyethylene lauryl ether sodium sulfate and polyoxyethylene lauryl ether ammonium sulfate; polyoxyethylene alkyl sulfate salts; polyoxyethylene alkyl phosphate sulfonates; glycerol borate fatty acid esters; polyoxyethylene glycerol fatty acid esters; phosphate ester surfactants; and phosphite ester surfactants. The anionic surfactant may be one type or two or more types. Furthermore, the countercation of the anionic group is preferably an ammonium salt. By using such surfactants, the amount of metal residue can be reduced.

[0114] Examples of cationic surfactants include alkylamine salts such as laurylamine acetate and stearylamine acetate; and quaternary ammonium salts such as lauryltrimethylammonium chloride. There may be only one cationic surfactant or two or more.

[0115] Examples of nonionic surfactants include (meth)acrylate sulfate surfactants (commercial products such as RMA-564, RMA-568, and RMA-1114 from Nippon Emulsifier Co., Ltd.); polyoxyalkylene branched decyl ethers; polyoxyalkylene alkyl ethers such as polyoxyethylene tridecyl ether, polyoxyethylene isodecyl ether, polyoxyethylene lauryl ether, and polyoxyethylene oleyl cetyl ether; polyoxyalkylene aryl ethers such as polyoxyethylene naphthyl ether and polyoxyethylene phenyl ether; polyoxyalkylene alkylaryl ethers; polyether polyols; polyoxyethylene styrene-phenyl ether; polyoxyethylene polyoxypropylene glycol; polyoxyethylene glyceryl isostearate; polyoxyethylene fatty acid esters; sorbitan fatty acid esters; polyoxysorbitan fatty acid esters; polyoxyethylene alkylamines; glycerin fatty acid esters; and oxyethylene-oxypropylene block polymers. The nonionic surfactant may be one type or two or more types.

[0116] Examples of amphoteric surfactants include lauryldimethylamine oxide, alkyldiaminoethylglycine hydrochloride, sodium laurylaminopropionate, and alkylbetaine. The amphoteric surfactant may be present in a single form or in two or more forms.

[0117] A reactive surfactant may be used as the surfactant. A reactive surfactant is a surfactant having a radical polymerizable group, such as a surfactant having a vinyl group. There may be only one type of reactive surfactant or two or more types. When a reactive surfactant is used, the surfactant can be incorporated into the polymer (P1), thereby reducing the amount of metal residue and eluted ions in the hollow resin particles. Furthermore, the incorporation of the reactive surfactant into the polymer (P1) allows the surfactant to be effectively distributed unevenly on the particle surface during suspension polymerization, potentially improving the surfactant effect. As a result, an excellent surfactant effect can be obtained, particle aggregation and coalescence during manufacturing can be suppressed, the generation of substandard particles can be reduced, and more uniform low dielectric properties can be achieved. Note that in this specification, the reactive surfactant is not included in the monomer component (M). That is, the reactive surfactant is not involved in the calculation of the SP value of the monomer component (M).

[0118] Examples of reactive surfactants include anionic surfactants having a vinyl group and nonionic surfactants having a vinyl group.

[0119] Examples of anionic surfactants having a vinyl group include polyoxyethylene-1-(allyloxymethyl)alkyl ether sulfate ammonium, polyoxyethylene styrene-propenylphenyl ether sulfate ammonium, polyoxyalkylene alkenyl ether sulfate ammonium, α-sulfo-ω-(1-alkoxymethyl-2-(2-propenyloxy)ethoxy)-poly(oxy-1,2-ethanediyl)ammonium, polyoxypropylene allyl ether phosphate, and bis(polyoxyethylene phenyl ether) methacrylate sulfate. Furthermore, ammonium salts are preferred as the countercation of the anionic group. By using such surfactants, the average particle size of hollow resin particles can be made smaller. In addition, the amount of metal residue can be reduced.

[0120] Examples of commercially available polyoxyethylene-1-(allyloxymethyl)alkyl ether sulfate ammonium products include the trade names "Aqualon KH-10" and "Aqualon KH-1025" (a 25% by weight aqueous solution of "Aqualon KH-10") manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

[0121] Examples of commercially available polyoxyethylene styrene-propenylphenyl ether sulfate ammonium products include the product names "Aqualon AR-10," "Aqualon AR-20," "Aqualon AR-3025" (a 25% by weight aqueous solution of "Aqualon AR-30"), and "Aqualon AR-1025" (a 25% by weight aqueous solution of "Aqualon AR-10"), all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

[0122] A commercially available product containing polyoxyalkylene alkenyl ether ammonium sulfate is, for example, "Latemul PD-104" manufactured by Kao Corporation.

[0123] Examples of commercially available α-sulfo-ω-(1-alkoxymethyl-2-(2-propenyloxy)ethoxy)-poly(oxy-1,2-ethanediyl)ammonium products include "Adekaria Soap SR-10" and "Adekaria Soap SR-20" manufactured by ADEKA Corporation.

[0124] A commercially available product containing polyoxypropylene allyl ether phosphate is, for example, "Adekaria Soap PP-70" manufactured by ADEKA Corporation.

[0125] A commercially available product containing bis(polyoxyethylene phenyl ether) methacrylate sulfate is, for example, "Antox MS-60" manufactured by Nippon Emulsifier Co., Ltd.

[0126] Examples of nonionic surfactants having a vinyl group include polyoxyethylene styrene-propenylphenyl ether, polyoxyethylene-1-(allyloxymethyl) alkyl ether, and polyoxyalkylene alkenyl ether.

[0127] Examples of commercially available polyoxyethylene styrene-propenylphenyl ether include the product names "Aqualon AN-10," "Aqualon AN-20," "Aqualon AN-30," and "Aqualon AN-5065," manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

[0128] Examples of commercially available polyoxyethylene-1-(allyloxymethyl)alkyl ethers include the product names "Aqualon KN-10," "Aqualon KN-20," "Aqualon KN-30," and "Aqualon KN-5065" manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and the product names "Adekaria Soap ER-10," "Adekaria Soap ER-20," "Adekaria Soap ER-30," and "Adekaria Soap ER-40" manufactured by ADEKA Corporation.

[0129] Examples of commercially available polyoxyalkylene alkenyl ethers include the product names "Latemul PD-420," "Latemul PD-430," and "Latemul PD-450" manufactured by Kao Corporation.

[0130] The surfactant does not have to contain reactive surfactants. The surfactant may also be a non-reactive surfactant. A non-reactive surfactant is, for example, a surfactant other than those listed as reactive surfactants among the surfactants described above. By using a non-reactive surfactant, hollow resin particles with superior dielectric properties can be produced.

[0131] The amount of surfactant used can be any appropriate amount, as long as it does not impair the effects of the present invention. Such an amount is preferably 0.001 to 5 parts by weight, more preferably 0.005 to 3 parts by weight, and even more preferably 0.01 to 1 part by weight, per 100 parts by weight of the aqueous phase.

[0132] In addition to the components described above, the aqueous phase may contain any other suitable components as long as they do not impair the effects of the present invention.

[0133] As for the method of mixing the oil phase and the aqueous phase, any suitable method can be employed as long as suspension polymerization can be carried out, provided that it does not impair the effects of the present invention.

[0134] The suspension is prepared by mixing and stirring the oil phase and the aqueous phase. Typically, this is done by dispersing the oil phase in the aqueous phase. Any suitable dispersion method can be used for dispersing the oil phase in the aqueous phase, as long as the oil phase can be present in droplet form in the aqueous phase, without impairing the effects of the present invention. Typical dispersion methods include dispersion using a homogenizer, such as an ultrasonic homogenizer or a high-pressure homogenizer.

[0135] Any suitable suspension polymerization method can be employed, as long as it does not impair the effects of the present invention.

[0136] The polymerization temperature can be any suitable temperature within a range that does not impair the effects of the present invention, as long as it is suitable for suspension polymerization. For example, such polymerization temperatures are 30°C to 95°C.

[0137] The polymerization time can be any appropriate time, as long as it is suitable for suspension polymerization and does not impair the effects of the present invention. Such a polymerization time is preferably 1 to 20 hours.

[0138] Post-heating, which is preferably performed after polymerization, is a suitable treatment for obtaining high-quality hollow resin particles.

[0139] The temperature of the post-heating, which is preferably performed after polymerization, can be any appropriate temperature within a range that does not impair the effects of the present invention. The temperature of such post-heating is preferably 50°C to 120°C.

[0140] The duration of the post-heating, which is preferably performed after polymerization, can be any appropriate duration as long as it does not impair the effects of the present invention. Such post-heating is preferably 1 to 10 hours.

[0141] The polymerization described above yields a slurry, which is a dispersion containing microcapsule particles encapsulating the organic solvent used in the oil phase.

[0142] Hollow resin particles can be obtained from the slurry obtained by suspension polymerization by performing distillation, solvent removal, washing, drying, classification, etc., as needed.

[0143] In the method for producing hollow resin particles according to embodiments of the present invention, washing is preferable. That is, it is preferable to wash the hollow resin particles to obtain the hollow resin particles according to embodiments of the present invention. By washing, hollow resin particles with reduced amounts of metal residue and eluted ions can be obtained. For example, a slurry obtained by suspension polymerization can be washed and dried after removing the organic solvent by distillation to obtain hollow resin particles. For washing, an aqueous medium such as water may be used, or an organic solvent such as alcohol may be used, but it is preferable to use an organic solvent. This allows for the production of hollow resin particles with further reduced amounts of metal residue and eluted ions. The alcohol may be a lower alcohol such as methyl alcohol, ethyl alcohol, or isopropyl alcohol.

[0144] ≪≪3. Dispersions≫≫ The hollow resin particles according to the embodiments of the present invention may be used as a dispersion as needed. Such a dispersion includes the hollow resin particles according to the embodiments of the present invention and a dispersion medium, wherein the hollow resin particles according to the embodiments of the present invention are dispersed in the dispersion medium as a dispersed phase. For example, it may be used as a dispersion of microcapsule particles containing an organic solvent, obtained after the polymerization step in the above manufacturing method, or it may be used as a solvent dispersion substituted with another dispersion medium.

[0145] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0146] <Average Particle Diameter> The Z-average particle diameter of the hollow resin particles was measured using dynamic light scattering, and the measured Z-average particle diameter was taken as the average particle diameter of the obtained hollow resin particles. Specifically, first, the obtained slurry-like hollow resin particles or particles were diluted with deionized water, and a laser beam was irradiated onto the aqueous dispersion adjusted to 0.1% by weight, and the scattered light intensity scattered from the hollow resin particles was measured over time in microseconds. Then, the Z-average particle diameter of the hollow resin particles was determined by fitting the detected scattering intensity distribution due to the hollow resin particles to a normal distribution and calculating the average particle diameter using the cumulant analysis method. This measurement of the Z-average particle diameter can be easily performed using a commercially available particle diameter analyzer. In the following examples and comparative examples, the Z-average particle diameter was measured using a particle diameter analyzer (Malvern Zetasizer Nano ZS). Typically, commercially available particle diameter analyzers are equipped with data analysis software, which automatically analyzes the measurement data to calculate the Z-average particle diameter.

[0147] <Hollow Ratio> The hollow ratio of the hollow resin particles was obtained from the apparent density of the hollow resin particles. The apparent density of the hollow resin particles was measured using a vibrating densimeter (Anton Paar, product name "DMA1001"). Specifically, the hollow resin particles were mixed with a dispersion medium (Toagosei Co., Ltd., product name "ARUFON UP-1020", density 1.027 g / cm³) so that the proportion of hollow resin particles was 2% by weight. 3 The mixture was defoamed and stirred (at 25°C) using a defoaming agitator (manufactured by Thinky Co., Ltd., product name "Awatori Rentaro ARE-100") to prepare an evaluation mixture. The evaluation mixture was filled into the measurement cell of a vibrating densimeter, and the density of the mixture was calculated from the following formula (4) by measuring the vibration frequency of the mixture in the measurement cell. The apparent density of the air-encompassing hollow resin particles was calculated from the densities of the mixture and dispersion medium and their respective weight percentages in the mixture using the following formula (5). In equation (4), f is the frequency [Hz], M is the weight of the measuring cell [g], and V is the volume of the measuring cell [cm³]. 3 ], ρ is the sample density [g / cm³] filled in the measurement cell. 3 ], c represents the spring constant [N / mm]. In formula (5), ρ pThis is the apparent density of hollow resin particles [g / cm³]. 3 ],ρ d The density of the dispersion medium [g / cm³] 3 ], x p x is the weight percentage of hollow resin particles in the sample. d This represents the weight percentage of the dispersion medium in the sample. The hollowness ratio of the hollow resin particles was calculated from the apparent density and shell density using the following formula: Hollowness ratio [%] = 100 - (100 × apparent density [g / cm³] 3 ]) / shell density [g / cm³] 3 ]

[0148] <Observation of the presence and shape of hollow portions> Hollow resin particles, as dry powder, were surface-treated (10 Pa, 5 mA, 10 seconds) using a "Neoc-Pro" osmium coater coating device manufactured by Meiwa Forsis Co., Ltd. Next, the hollow resin particles were observed using a TEM (transmission electron microscope, Hitachi High-Technologies Corporation H-7600) to confirm the presence or absence of hollow portions and the shape of the hollow resin particles. At this time, the acceleration voltage was set to 80 kV and the magnification was set to 5000x or 10,000x for imaging.

[0149] <Measurement of Metal Residue Amount> The amount of metal residue was measured as follows. (Measurement Sample) 0.5 g of hollow resin particles were accurately weighed into a cleaned 50 mL poly container. 1 mL of washing ethanol was added and thoroughly mixed and dispersed. 50 mL of deionized water was then added and thoroughly mixed. Ultrasonic cleaning and extraction was performed for approximately 10 min, and then the sample was left to stand in a 60°C constant temperature bath for 60 min. The slurry after standing was filtered through an aqueous 0.20 μm chromatographic disc and used as the measurement sample. (Measurement Method) The amount of metal residue in the measurement sample was measured under the following conditions. The amount of metal residue was determined from a calibration curve prepared in advance. The amount of metal residue was calculated using the following formula. The lower limit of quantification was 1 ppm. Amount of metal residue (ppm) = concentration of measured metal element (μg / mL) × 51 (mL) ÷ sample amount (g) The total amount of metal residue for each measured element was calculated from the amount of metal residue for each measured element. The limit of quantification was 3 ppm. When the amount of metal residue for all measured elements was below the limit of quantification, the amount of metal residue was considered to be below the limit of quantification. (ICP measurement conditions) Measurement device = Shimadzu Corporation "ICPE-9000" multi-type ICP emission spectrometer Measured elements = Ca, K, Li, Mg, Na Observation direction = Axial direction High frequency output = 1.20 kW Carrier flow rate = 0.7 L / min Plasma flow rate = 10.0 L / min Auxiliary flow rate = 0.6 L / min Exposure time = 30 seconds Calibration standard solution = SPEX Corporation "XSTC-13" general-purpose mixed standard solution 31-element mixture (base 5% HNO3): approx. 10 mg / L each, "XSTC-8" general-purpose mixed standard solution 13-element mixture (base H2O / trace HF): approx. 10 mg / L each

[0150] <Measurement of Eluted Ion Amount> The amount of eluted ions was measured as follows. A 50 mL container was prepared, approximately 50 mL of deionized water was added, and the container was washed three times. Approximately 0.2 g of the sample was accurately weighed into the washed 50 mL container. 1 mL of washing ethanol (Clinsolve P) was added and mixed well, and then 50 mL of deionized water was added and mixed well. The resulting mixture was subjected to ultrasonic cleaning and extraction for approximately 10 min, and then filtered through an aqueous 0.20 μm chromatographic disk to be used as the test solution for ion chromatography measurement. A calibration curve was created by measuring the standard solution under the following measurement conditions. Next, the test solution was measured under the same conditions. The concentration of each measured ion in the sample was determined from the calibration curve using the peak area values ​​of each ion obtained from the chromatogram. The standard solution used for the calibration curve was "Anion Mixed Standard Solution 1" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. The amount of eluted ions in each sample was calculated using the following formula. The limit of quantification was 2 ppm. Elution amount (ppm) = Measured ion concentration (μg / mL) × 51 (mL) ÷ Sample amount (g) The total elution amount of each measured ion (eluted ion amount) was calculated from the elution amount of each measured ion. Here, in calculating the total elution amount of each measured ion, ions whose measurement result was below the limit of quantification were not taken into consideration. That is, the sum of the elution amounts of ions above the limit of quantification was taken as the eluted ion amount. Also, when the elution amount of all measured ions was below the limit of quantification, the eluted ion amount was considered to be below the limit of quantification. (Ion chromatograph measurement conditions) Measurement device: Tosoh Corporation "IC-2001" Measured ion: F - , Cl - NO2 - , Br - NO3 - , PO4 3- SO4 2- Column: TSKGEL superIC-AZ (manufactured by TOSOH Corporation) Mobile phase: 3.2 mM Na2CO3 + 1.9 mM NaHCO3 Flow rate: 0.8 mL / min Column temperature: 40°C Injection volume: 30 μL

[0151] <Dielectric Properties of Hollow Resin Particles> The dielectric properties of hollow resin particles were measured using a dielectric constant measuring device (ADMS01Nc series) manufactured by AET. The measurements were performed at a frequency of 10 GHz, in a measurement environment of 23°C, and with a relative humidity of 51 ± 1%. The relative permittivity and dielectric loss tangent of the hollow resin particles were calculated based on perturbation theory using a resonator.

[0152] <Ingredients Used> The ingredients used are as follows:

[0153] [Aromatic monofunctional monomers] ・Styrene

[0154] [Aromatic Crosslinkable Monomers] ・Divinylbenzene (DVB) 810 (Nippon Steel Chemical & Material Co., Ltd., 81% by weight content, 19% by weight is ethyl vinylbenzene (EVB))

[0155] [Hydrophilic monofunctional monomers] ・Methacrylic acid ・2-Methacryloyloxyethyl succinate (manufactured by Kyoeisha Chemical Co., Ltd., product name "Light Ester HO-MS(N)") ・Polyethylene glycol propylene glycol monomethacrylate (manufactured by NOF Corporation, product name "Bremmer 50PEP-300")

[0156] [Non-crosslinked polymers] - Aliphatic / aromatic hydrocarbon resin (manufactured by Tosoh Corporation, trade name "Petrotac 90", number average molecular weight 900) - Paraffin wax (manufactured by Nucera Solutions, trade name "VYBAR260", number average molecular weight 2,600-4,000)

[0157] [Organic solvents] ・Heptane

[0158] [Polymerization initiator] ・Lauroyl peroxide (manufactured by NOF Corporation, trade name "Perloyl L")

[0159] [Aqueous media] ・Ion-exchanged water

[0160] [Surfactants] ・Polyoxyethylene styrene-propenylphenyl ether sulfate ammonium salt (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name "Aqualon AR-10") ・Bis(polyoxyethylene phenyl ether) methacrylate sulfate ammonium salt (manufactured by Nippon Emulsifier Co., Ltd., product name "Antox MS-60") ・Polyoxyethylene styrene-propenylphenyl ether (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name "Aqualon AN-5065") ・Polyoxyethylene polycyclic phenyl ether sulfate ammonium salt (manufactured by Nippon Emulsifier Co., Ltd., product name "Newcol 707-SF")

[0161] <SP Value of Monomer Component (M)> The solubility parameter δ of each aromatic monofunctional monomer, aromatic crosslinkable monomer, and hydrophilic monofunctional monomer was calculated using the method described above, using the values ​​of ΔF (molar attractive force constant) and Δv (molar volume) for various atomic groups by Okitsu, as described in Toshinao Okitsu, "Adhesion," Polymer Publishing Association, Vol. 40, No. 8 (1996), pp. 342-350. The specific values ​​of ΔF and Δv for various atomic groups by Okitsu are shown in Table 1 below. The sum of the products of the calculated δ value of each monomer and the mole fraction in the monomer component (M) was taken as the SP value of the monomer component (M).

[0162]

[0163] In Table 1, (Poly) means Polymer. (Arom) means Aromatic. (mean) means average; for example, for a group of -F atoms, the value of "-F (mean)" can be used except for "-F (Poly)". (Link) means Link; for example, "-NH- (Link)" means -NH- that constitutes the ring. Also, "X Member 1 in" (X = 3 to 6) means a substituent that is a cycloalkane of an X-membered ring in a single aromatic ring.

[0164] Specifically, for example, the SP value of styrene was determined as follows. Styrene has one CH2=, one -CH=, and one -C6H5 (Arom) atom as its atomic group. Therefore, the solubility parameter δ of styrene is st δ can be calculated as follows: st=ΣΔF / ΣΔv = (195 + 116 + 731) / (31 + 13.7 + 72) = 8.98 Similarly, δ for each monomer was determined, and the sum of the products of the mole fraction of each monomer and δ was taken as the SP value of the monomer component (M).

[0165] [Example 1] After preparing the oil phase and aqueous phase with the compositions shown in Table 2, the oil phase and aqueous phase were mixed and dispersed for 5 minutes at a rotation speed of 7,000 rpm using a Polytron homogenizer "PT10-35" (manufactured by Central Science Trading Co., Ltd.). Then, the mixture was emulsified at a processing pressure of 20 MPa using a high-pressure emulsifier NVL-AS200 (manufactured by Yoshida Machinery Industry Co., Ltd.) to prepare a suspension. The obtained suspension was heated at 70°C for 5 hours, and then polymerized by raising the temperature to 90°C and heating for 2 hours. After removing the organic solvent from the slurry obtained by polymerization by distillation, large-diameter particles were sorted and removed using a 500-mesh (25 μm opening) wire mesh to obtain a slurry containing hollow resin particles. The obtained slurry was heated and dried, and the dried powder was redispersed in 10 times the amount of isopropyl alcohol and washed by centrifugation. The supernatant was discarded and heated and dried to obtain hollow resin particles (1) as a dried powder. TEM measurement confirmed that the hollow resin particles (1) were hollow particles with a single hollow structure. The amount of metal residue in the hollow resin particles (1) was below the limit of quantification. The amount of eluted ions in the hollow resin particles (1) was also below the limit of quantification. The results of various measurements are shown in Table 2.

[0166] [Examples 2-4] Hollow resin particles (2) to (4) were obtained in the same manner as in Example 1, except that the composition of the oil phase and the aqueous phase were changed as shown in Table 2. It was confirmed by TEM measurement that the hollow resin particles (2) to (4) were hollow particles with a single hollow structure. The amount of metal residue in the hollow resin particles (2) to (4) was below the limit of quantification. The amount of eluted ions in the hollow resin particles (2) to (4) was below the limit of quantification. The results of various measurements are shown in Table 2.

[0167] [Example 5] Suspension polymerization was carried out in the same manner as in Example 1, except that the composition of the oil phase and the aqueous phase were changed as shown in Table 2, to obtain a slurry. After removing the organic solvent from the slurry obtained by polymerization by distillation, large-diameter particles were classified and removed using a 500-mesh (25 μm opening) wire mesh to obtain a slurry containing hollow resin particles. The obtained slurry was washed with 10 times the amount of ion-exchanged water using an ultrafiltration module ACP-0053D (manufactured by Asahi Kasei Corporation, nominal fractionation molecular weight 13,000) to remove impurities. Hollow resin particles (5) as a dried powder were obtained by heating and drying the obtained washed slurry. It was confirmed by TEM measurement that the hollow resin particles (5) were hollow particles with a single hollow structure. The amount of metal residue in the hollow resin particles (5) was below the limit of quantification. The amount of various ions eluted from the hollow resin particles (5) was SO4 2- Except for one, the levels were below the limit of quantification. SO4 2- The amount of elution was 19 ppm. That is, the amount of eluted ions from the hollow resin particles (5) was 19 ppm. The results of various measurements are shown in Table 2.

[0168] [Example 6] Hollow resin particles (6) were obtained in the same manner as in Example 1, except that the composition of the oil phase and the aqueous phase were changed as shown in Table 2. It was confirmed by TEM measurement that the hollow resin particles (6) were hollow particles with a single hollow structure. The amount of metal residue in the hollow resin particles (6) was below the limit of quantification. The amount of eluted ions in the hollow resin particles (6) was below the limit of quantification. The results of various measurements are shown in Table 2.

[0169] [Example 7] Hollow resin particles (7) were obtained in the same manner as in Example 5, except that the composition of the oil phase and the aqueous phase were changed as shown in Table 2. It was confirmed by TEM measurement that the hollow resin particles (7) were hollow particles with a single hollow structure. The amount of metal residue in the hollow resin particles (7) was below the limit of quantification. The amount of eluted ions in the hollow resin particles (7) was 20 ppm. The results of various measurements are shown in Table 2.

[0170] [Comparative Examples 1-2] Hollow resin particles (C1) and hollow resin particles (C2) were obtained in the same manner as in Example 1, except that the composition of the oil phase and the water phase were changed as shown in Table 2. TEM measurements confirmed that the hollow resin particles (C1) and hollow resin particles (C2) were single-hollow structures. The results are shown in Table 2.

[0171]

[0172] <Performance Evaluation: Evaluation of Relative Permittivity and Dielectric Loss Tangent of Particle-Added Film> 0.425 g of particles (2) obtained in Example 2, 8.3 g of ethyl acetate, and 1.7 g of solvent-soluble polyimide KPI-MX300F (manufactured by Kawamura Sangyo Co., Ltd.) were defoamed and stirred using a planetary stirring defoamer (KURABO Co., Ltd., "Mazelstar KK-250") to prepare an evaluation mixture. The evaluation mixture was coated onto a 5 mm thick glass plate using an applicator set to a wet thickness of 250 μm. The ethyl acetate was removed by heating at 60°C for 30 minutes, 90°C for 10 minutes, 150°C for 30 minutes, and 200°C for 30 minutes, and then cooled to room temperature to obtain a film containing particles. The relative permittivity and dielectric loss tangent of the obtained film were evaluated using the cavity resonance method (measurement frequency: 5.8 GHz). The reduction rate (%) for relative permittivity and dielectric loss tangent compared to the measured value of the film without particles was calculated using the following formulas. The results are shown in Table 3. Reduction rate of relative permittivity [%] = 100 - (Relative permittivity of film containing particle (2)) / (Relative permittivity of film without particles) × 100 Reduction rate of dielectric loss tangent [%] = 100 - (Dielectric loss tangent of film containing particle (2)) / (Dielectric loss tangent of film without particles) × 100

[0173]

[0174] The hollow resin particles according to the embodiments of the present invention, and the hollow resin particles obtained by the manufacturing method according to the embodiments of the present invention, can be applied to various uses such as resin compositions for semiconductor components, paint compositions, heat-insulating resin compositions, light-diffusing resin compositions, and light-diffusing films.

Claims

1. Hollow resin particles having a shell portion and a hollow portion surrounded by the shell portion, wherein the shell portion contains a polymer (P1) obtained by the reaction of a monomer component (M), the average particle diameter is 0.1 μm to 1 μm, the dielectric loss tangent at a measurement frequency of 10 GHz is less than 0.0050, and the SP value of the monomer component (M) is 8.80 or less.

2. The hollow resin particle according to claim 1, wherein the monomer component (M) contains a crosslinkable monomer (a), and when the monomer component (M) is 100 parts by weight, the crosslinkable monomer (a) is 40 parts by weight to 100 parts by weight.

3. The hollow resin particle according to claim 1, wherein the monomer component (M) contains a monofunctional monomer (b), and when the monomer component (M) is 100 parts by weight, the amount of the monofunctional monomer (b) is 60 parts by weight or less.

4. Hollow resin particles according to claim 1, wherein the hollowness ratio is 20% or more.

5. The hollow resin particle according to claim 1, wherein the relative permittivity at a measurement frequency of 10 GHz is less than 2.

00.

6. Hollow resin particles according to claim 1, wherein the total amount of metal residues of Ca, K, Li, Mg, and Na is 20 ppm or less.

7. The hollow resin particle according to claim 1, wherein the SP value of the monomer component (M) is less than 8.

70.

8. F - , Cl - NO2 - , Br - NO3 - , PO4 3- , and SO4 2- The hollow resin particles according to claim 1, wherein the total amount of eluted substances is 200 ppm or less.

9. The hollow resin particle according to claim 1, wherein the dielectric loss tangent at a measurement frequency of 10 GHz is less than 0.0030.

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

11. A resin composition for semiconductor components containing hollow resin particles as described in claim 10.

12. A dispersion containing hollow resin particles as described in claim 1.

Images