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

Abstract

Provided are hollow resin particles capable of exhibiting excellent low dielectric characteristics and exhibiting uniform low dielectric characteristics. In addition, provided is a use of the hollow resin particles. Also, provided is a method for producing the hollow resin particles.　Hollow resin particles according to an embodiment of the present invention each have a shell portion and a hollow portion surrounded by the shell portion, wherein the amount of metal residue is 30 ppm or less, the dielectric loss tangent Df at a frequency of 10 GHz is 0.0050 or less, and the F value, which is an index of the uniformity of the dielectric loss tangent Df, is 0.30 or less.

Description

Hollow resin particles, their uses, and their manufacturing method

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

[0002] In recent years, with the increase in the amount of information processed and the communication speed of various electronic devices, there has been rapid progress in packaging technologies, such as higher integration of the semiconductor devices, higher density wiring, and multi-layering. Insulating resin materials used in semiconductor components used in semiconductor devices are required to have low relative permittivity and dielectric loss tangent in order to increase the transmission speed of high-frequency signals and reduce loss during signal transmission.

[0003] In response to such demands, a technology has been reported in which hollow resin particles, each having a shell portion and a hollow portion surrounded by the shell portion, are mixed into the insulating resin to introduce air space into the insulating resin, thereby achieving a low dielectric constant and a low dielectric loss tangent.

[0004] Acrylic hollow resin particles are known as one type of hollow resin particles.

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

[0006] However, acrylic resins have high relative permittivity and dielectric loss tangent, which deteriorate low dielectric properties. For this reason, the acrylic hollow resin particles described in Patent Document 1 cannot be applied to recent semiconductor devices that process high-frequency signals.

[0007] On the other hand, styrene-based hollow resin particles are known as hollow resin particles having lower dielectric properties than acrylic-based hollow resin particles.

[0008] As an example of styrene-based hollow resin particles having low dielectric properties, hollow particles have been reported that include a shell containing a resin and a hollow portion surrounded by the shell, in which the resin in the shell is a polymer containing 70 to 100 parts by mass of crosslinkable monomer units per 100 parts by mass of all monomer units, and that have a porosity of 60% or more, a surfactant content present on the hollow particle surface of 200 ppm or less, and a relative dielectric constant at a frequency of 1 MHz of 1.6 or less (Patent Document 2).

[0009] The hollow particles reported in Patent Document 2 do not use a surfactant to achieve their intended effect, thereby reducing surfactant residue. However, when hollow particles are produced without using a surfactant, aggregation and coalescence of particles occur during production, resulting in the by-production of non-standard particles. The by-production of such non-standard particles results in variations in low dielectric properties among particles, making it difficult to achieve uniform low dielectric properties.

[0010] Furthermore, the hollow particles reported in Patent Document 2 do not use surfactants, but instead use magnesium hydroxide colloid as a dispersion stabilizer. However, when such metal compounds are used, the resulting hollow particles tend to contain a large amount of metal residue. Hollow particles with a large amount of metal residue have the problem of failing to exhibit low dielectric properties or uniform low dielectric properties. Furthermore, a large amount of metal residue can cause corrosion.

[0011] Furthermore, the hollow particles reported in Patent Document 2 are produced using a large amount of crosslinkable monomer, i.e., 70 to 100 parts by mass of crosslinkable monomer units (95.2 parts by mass or 91.9 parts by mass in the examples) per 100 parts by mass of all monomer units, thereby improving the strength of the shell. However, using a large amount of crosslinkable monomer results in the problem that unreacted crosslinkable reactive sites remain, which adversely affects the development of low dielectric properties.

[0012] Another example of a styrene-based hollow resin particle having low dielectric properties is a hollow resin particle having a shell portion and a hollow portion surrounded by the shell portion, in which the total concentration of specific metal elements contained in the hollow resin particle is 200 mg / kg (200 ppm) or less (Patent Document 3).

[0013] The hollow resin particles reported in Patent Document 3 can exhibit excellent low dielectric properties. However, it has been found that the hollow resin particles reported in Patent Document 3, unlike the hollow particles reported in Patent Document 2, are unable to exhibit uniform low dielectric properties despite being produced using a surfactant.

[0014] Patent No. 6513273 International Publication No. 2022 / 107674 Japanese Patent Application Laid-Open No. 2022-96298

[0015] An object of the present invention is to provide hollow resin particles that can exhibit excellent and uniform low dielectric properties, to provide uses for such hollow resin particles, and to provide a method for producing such hollow resin particles.

[0016] [1] A hollow resin particle according to an embodiment of the present invention has a shell portion and a hollow portion surrounded by the shell portion, and has a metal residue content of 30 ppm or less, a dielectric loss tangent Df of 0.0050 or less at a frequency of 10 GHz, and an F value, which is an index of uniformity of the dielectric loss tangent Df, of 0.30 or less. [2] The hollow resin particle described in [1] above may have a dielectric loss tangent Df of 0.0030 or less. [3] The hollow resin particle described in [1] or [2] above may have an F value of 0.15 or less. [4] The hollow resin particle described in any of [1] to [3] above may have an average particle diameter of 0.1 μm to 10.0 μm. [5] The hollow resin particle described in any of [1] to [4] above may have an aromatic polymer (P1) obtained by reacting a monomer component (M) containing an aromatic monofunctional monomer (a) and an aromatic crosslinkable monomer (b). [6] In the hollow resin particles described in [5] above, the content of the aromatic polymer (P1) in the shell may be 60% by weight to 100% by weight. [7] In the hollow resin particles described in [5] or [6] above, the content of the aromatic crosslinkable monomer (b) in the monomer component (M) may be 60% by weight or less. [8] In the hollow resin particles described in any of [5] to [7] above, the monomer component (M) may contain a hydrophilic monofunctional monomer (c). [9] In the hollow resin particles described in [8] above, the hydrophilic monofunctional monomer (c) may be represented by general formula (1) or general formula (2). In general formula (1), R 1 represents H or CH3, R 2 represents H, an alkyl group, or a phenyl group, and R 3 represents an alkanediyl group having 2 to 18 carbon atoms, and m is R 3 the average number of moles of oxyalkylene groups represented by —O is 1 to 100, and m R 3 are independent of each other. In general formula (2), R 4 represents H or CH3, R 5represents an alkanediyl group having 1 to 10 carbon atoms or an alkenediyl group having 2 to 10 carbon atoms, R 6 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; 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 5 , X, R 6are independent of each other.

[10] In the hollow resin particle according to any one of [5] to [9] above, the monomer component (M) may contain a reactive surfactant (d) having a vinyl group.

[11] In the hollow resin particle according to

[10] above, the content of the reactive surfactant (d) having a vinyl group in the monomer component (M) may be 0.10 wt % to 1.0 wt %.

[12] In the hollow resin particle according to

[11] above, the content of the reactive surfactant (d) having a vinyl group in the monomer component (M) may be 0.10 wt % to 0.50 wt %.

[13] In the hollow resin particle according to any one of

[10] to

[12] above, the reactive surfactant (d) having a vinyl group may be polyoxyethylene styrenated propenyl phenyl ether sulfate ester ammonium.

[14] In the hollow resin particle according to any one of [1] to

[13] above, the shell portion may contain a non-crosslinkable polymer (P2).

[15] In the hollow resin particles described in

[14] above, the content of the non-crosslinkable polymer (P2) in the shell may be 0% by weight to 40% by weight.

[16] The hollow resin particles described in any of [1] to

[15] above may be used in a resin composition for a semiconductor member.

[17] The hollow resin particles described in any of [1] to

[15] above may be used in a coating composition.

[18] The hollow resin particles described in any of [1] to

[15] above may be used in a heat insulating resin composition.

[19] The hollow resin particles described in any of [1] to

[15] above may be used in a light diffusing resin composition.

[20] The hollow resin particles described in any of [1] to

[15] above may be used in a light diffusing film.

[21] A resin composition for a semiconductor member according to an embodiment of the present invention comprises the hollow resin particles described in any of [1] to

[15] above.

[22] A coating composition according to an embodiment of the present invention comprises the hollow resin particles described in any one of [1] to

[15] above.

[23] A heat insulating resin composition according to an embodiment of the present invention comprises the hollow resin particles described in any one of [1] to

[15] above.

[24] A light diffusing resin composition according to an embodiment of the present invention comprises the hollow resin particles described in any one of [1] to

[15] above.

[25] A light diffusion film according to an embodiment of the present invention comprises the hollow resin particles according to any one of [1] to

[15] above.

[26] A method for producing hollow resin particles according to an embodiment of the present invention is a method for producing hollow resin particles having a shell portion and a hollow portion surrounded by the shell portion, the method comprising mixing and stirring an oil phase and an aqueous phase to prepare a suspension, and performing suspension polymerization of a monomer component (M) contained in the suspension, the oil phase comprising an aromatic monofunctional monomer (a) and an aromatic crosslinkable monomer (b), the aqueous phase comprising a reactive surfactant having a vinyl group (d), the content of the aromatic monofunctional monomer (a) in the monomer component (M) being 30% by weight or more, the content of the aromatic crosslinkable monomer (b) in the monomer component (M) being 60% by weight or less, and the content of the reactive surfactant having a vinyl group (d) in the monomer component (M) being 0.10% by weight to 1.0% by weight.

[0017] According to an embodiment of the present invention, hollow resin particles that can exhibit excellent and uniform low dielectric properties can be provided. Furthermore, uses of such hollow resin particles can be provided. Furthermore, a method for producing such hollow resin particles can be provided.

[0018] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these embodiments.

[0019] In this specification, the expression "(meth)acrylic" means "acrylic and / or methacrylic", and the expression "(meth)acrylate" means "acrylate and / or methacrylate".

[0020] <<Hollow resin particles>>

[0021] 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. Here, "hollow" means that the interior is filled with a substance other than resin, such as a gas or liquid, and preferably means that the interior is filled with a gas, in order to further exhibit the effects of the present invention.

[0022] In the hollow resin particles according to the embodiment of the present invention, the hollow portion may consist of one hollow region or multiple hollow regions, but it is preferable that the hollow portion consist of one hollow region, from the viewpoint of preventing the resin component constituting the shell from being relatively large and penetrating into the hollow portion of the substrate or the like.

[0023] The average particle diameter of the hollow resin particles according to an embodiment of the present invention is preferably 0.1 μm to 10.0 μm, more preferably 0.1 μm to 5.0 μm, and even more preferably 0.2 μm to 4.0 μm. Depending on the application of the hollow resin particles (particularly semiconductor component applications), the average particle diameter of the hollow resin particles according to an embodiment of the present invention is more preferably 0.2 μm to 3.0 μm, even more preferably 0.2 μm to 2.0 μm, even more preferably 0.2 μm to 1.0 μm, particularly preferably 0.2 μm to 0.8 μm, and most preferably 0.2 μm to 0.6 μm. If the average particle diameter of the hollow resin particles is less than 0.1 μm, the thickness of the shell portion will be relatively thin, and the hollow resin particles may not have sufficient strength. If the average particle diameter of the hollow resin particles is greater than 10.0 μm, phase separation between the polymer and the solvent produced by polymerization of the monomer component during suspension polymerization may be difficult to occur, which may make it difficult to form the shell portion.

[0024] The hollow resin particles according to an embodiment of the present invention typically have a metal residue content of 30 ppm or less. If the metal residue content of the hollow resin particles exceeds 30 ppm, there is a risk that excellent low dielectric properties or uniform low dielectric properties may not be achieved. Furthermore, if the metal residue content of the hollow resin particles exceeds 30 ppm, it may cause corrosion.

[0025] The hollow resin particles according to the embodiment of the present invention have a dielectric loss tangent Df at a frequency of 10 GHz of typically 0.0050 or less, preferably 0.0045 or less, more preferably 0.0040 or less, even more preferably 0.0035 or less, and particularly preferably 0.0030 or less. If the dielectric loss tangent Df at a frequency of 10 GHz is within the above range, the hollow resin particles according to the embodiment of the present invention can exhibit excellent low dielectric properties.

[0026] The hollow resin particles according to the embodiment of the present invention have an F value, which is an index of uniformity of the dielectric loss tangent Df, of typically 0.30 or less, preferably 0.25 or less, more preferably 0.20 or less, even more preferably 0.15 or less, and particularly preferably 0.13 or less. If the F value, which is an index of uniformity of the dielectric loss tangent Df, is within the above range, the hollow resin particles according to the embodiment of the present invention can exhibit uniform low dielectric properties.

[0027] The F value is an index of the uniformity of the dielectric loss tangent Df. The dielectric loss tangent Df of the hollow resin particles is measured at five measurement points, and the maximum value of Df (Df max ) and the minimum value of Df (Df min ) and the average value of Df (Df av ) is calculated, and the F value = (Df max -Df min ) / Df av The smaller this F value is, the less the variation in the dielectric loss tangent Df is, and the more uniform the low dielectric characteristic can be achieved.

[0028] <Shell Portion> The shell portion preferably contains an aromatic polymer (P1).

[0029] The content of the aromatic polymer (P1) in the shell is preferably 60% by weight to 100% by weight, more preferably 70% by weight to 100% by weight, and even more preferably 80% by weight to 100% by weight, in order to further exhibit the effects of the present invention.

[0030] The aromatic polymer (P1) is typically obtained by the reaction of a monomer component (M) containing an aromatic monofunctional monomer (a) and an aromatic crosslinkable monomer (b). When the shell portion contains the aromatic polymer (P1) obtained by the reaction of the monomer component containing the aromatic monofunctional monomer (a) and the aromatic crosslinkable monomer (b), the effects of the present invention can be more effectively exhibited.

[0031] The aromatic polymer (P1) can be defined as one obtained by the reaction of the monomer component (M) in this way. This is because the aromatic polymer (P1) is obtained by the reaction of the monomer component (M), and therefore it is impossible and almost impractical to directly identify the aromatic polymer (P1) by its structure ("impossible / impractical circumstances"). Therefore, the aromatic polymer (P1) is appropriately defined as a "product" by the definition that it is "obtained by the reaction of the monomer component (M)."

[0032] The content of the aromatic monofunctional monomer (a) in the monomer component (M) is preferably 30% by weight or more, more preferably 30% by weight to 80% by weight, even more preferably 35% by weight to 70% by weight, and particularly preferably 40% by weight to 60% by weight, in order to further exhibit the effects of the present invention. When the content of the aromatic monofunctional monomer (a) in the monomer component (M) is within the above range, the effects of the present invention can be further exhibited.

[0033] The content of the aromatic crosslinkable monomer (b) in the monomer component (M) is preferably 60% by weight or less, more preferably 10% to 60% by weight, even more preferably 20% to 55% by weight, and particularly preferably 30% to 50% by weight, in order to further demonstrate the effects of the present invention. When the content of the aromatic crosslinkable monomer (b) in the monomer component (M) is within the above range, the effects of the present invention can be further demonstrated. If the content of the aromatic crosslinkable monomer (b) in the monomer component (M) is too high, unreacted reactive sites may remain, which may adversely affect the sufficient development of low dielectric properties. If the content of the aromatic crosslinkable monomer (b) in the monomer component (M) is too low, the crosslink density may be low, which may reduce the strength of the shell portion.

[0034] The aromatic monofunctional monomer (a) may be of one type only, or of two or more types.

[0035] Any appropriate aromatic monofunctional monomer can be used as the aromatic monofunctional monomer (a) as long as it is a monofunctional aromatic monomer and does not impair the effects of the present invention. Examples of such aromatic monofunctional monomers (a) include styrene, ethylvinylbenzene, α-methylstyrene, vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, vinylbiphenyl, and vinylnaphthalene, from the viewpoint of being able to further exhibit the effects of the present invention and from the viewpoint of reactivity. The aromatic monofunctional monomer (a) is preferably at least one selected from the group consisting of styrene and ethylvinylbenzene.

[0036] The aromatic crosslinkable monomer (b) may be used alone or in combination of two or more kinds.

[0037] As the aromatic crosslinkable monomer (b), any appropriate aromatic crosslinkable monomer can be used as long as it is an aromatic monomer having crosslinkability, as long as it does not impair the effects of the present invention. Examples of such aromatic crosslinkable monomer (b) include divinylbenzene, divinylnaphthalene, and diallyl phthalate, which can further demonstrate the effects of the present invention. Divinylbenzene is preferred as the aromatic crosslinkable monomer (b) because it can further demonstrate the effects of the present invention and has good reactivity.

[0038] The monomer component (M) may contain a hydrophilic monofunctional monomer (c). The hydrophilic monofunctional monomer (c) may be one type only, or two or more types.

[0039] As the hydrophilic monofunctional monomer (c), any appropriate hydrophilic monofunctional monomer can be adopted as long as it does not impair the effects of the present invention. In terms of being able to further exhibit the effects of the present invention, the hydrophilic monofunctional monomer (c) is preferably represented by general formula (1) or general formula (2).

[0040]

[0041]

[0042] In general formula (1), R1 represents H or CH3.

[0043] In general formula (1), R 2 represents H, an alkyl group, or a phenyl group.

[0044] In general formula (1), R 3 represents an alkanediyl group having 2 to 18 carbon atoms, preferably an alkanediyl group having 2 to 8 carbon atoms, and more preferably an alkanediyl group having 2 to 4 carbon atoms. The alkanediyl group may be linear, branched, or cyclic.

[0045] Examples of the alkanediyl group include a methylene group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a propane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a butane-1,3-diyl group, a butane-2,3-diyl group, and a butane-1,4-diyl group.

[0046] In general formula (1), R 3 -O is an oxyalkylene group having 2 to 18 carbon atoms, preferably an oxyalkylene group having 2 to 8 carbon atoms, and more preferably an oxyalkylene group having 2 to 4 carbon atoms. 3 When —O is at least two or more selected from an oxyethylene group, an oxypropylene group, and an oxybutylene group, R 3 The addition form of -O may be any of random addition, block addition, and alternating addition. Note that the addition form referred to here means the form itself, and does not mean that it must be obtained by an addition reaction.

[0047] In general formula (1), R 3 —O is at least one selected from the group consisting of an oxyethylene group, an oxypropylene group, and an oxybutylene group (typically, an oxytetramethylene group), in that the effects of the present invention can be more effectively exhibited.

[0048] In the general formula (1), m is R 3represents the average number of moles added (sometimes referred to as "chain length") of oxyalkylene groups represented by -O. m is a number from 1 to 100, preferably a number from 1 to 40, more preferably a number from 2 to 30, even more preferably a number from 3 to 20, particularly preferably a number from 4 to 18, and most preferably a number from 5 to 15. When m is within the above range, the effects of the present invention can be more effectively exhibited.

[0049] In the general formula (1), m R 3 are independent of each other. In general formula (1), R 3 When there are two or more types of —O, for example, when it consists of an oxyethylene group (C2H4O) and an oxypropylene group (C3H6O), m is the sum of the average number of moles of the oxyalkylene groups added. 3 -O) m - is - [(C2H4O) p (C3H6O) q ]- (as mentioned above, the addition may be in the form of random addition, block addition, or alternating addition), then m=p+q.

[0050] Examples of the hydrophilic monofunctional monomer (c) represented by general formula (1) include methoxypolyethylene glycol methacrylate, ethoxypolyethylene glycol methacrylate, propoxypolyethylene glycol methacrylate, butoxypolyethylene glycol methacrylate, hexaoxypolyethylene glycol methacrylate, octoxypolyethylene glycol polypropylene glycol methacrylate, lauroxypolyethylene glycol methacrylate, stearoxypolyethylene glycol methacrylate, phenoxypolyethylene glycol polypropylene glycol methacrylate, methoxypolyethylene glycol acrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, polyethylene glycol propylene glycol monomethacrylate, polyethylene glycol tetramethylene glycol monomethacrylate, propylene glycol polybutylene glycol monomethacrylate, monoethylene glycol monoacrylate, and polypropylene glycol monoacrylate.

[0051] The hydrophilic monofunctional monomer (c) represented by the general formula (1) may be a commercially available product, such as the "Blenmer" series manufactured by NOF Corporation.

[0052] In general formula (2), R 4 represents H or CH3.

[0053] In general formula (2), R 5 represents an alkanediyl group having 1 to 10 carbon atoms or an alkenediyl group having 2 to 10 carbon atoms. The alkanediyl group preferably has 2 to 6 carbon atoms, and more preferably has 2 to 4 carbon atoms. The alkanediyl group may be linear, branched, or cyclic. The alkenediyl group preferably has 2 to 6 carbon atoms, and more preferably has 2 to 4 carbon atoms. The alkenediyl group may be linear, branched, or cyclic.

[0054] R 5 With regard to R, examples of the alkanediyl group include those mentioned above. 5 In this regard, examples of the alkenediyl group include an ethene-1,2-diyl group, a 1-propene-1,3-diyl group, a 2-butene-1,4-diyl group, a 1-methyl-1-butene-1,4-diyl group, and a 2-cyclohexene-1,4-diyl group.

[0055] In general formula (2), R 6 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 alkanediyl group preferably has 2 to 6 carbon atoms, and more preferably has 2 to 4 carbon atoms. The alkanediyl group may be linear, branched, or cyclic. The alkenediyl group preferably has 2 to 6 carbon atoms, and more preferably has 2 to 4 carbon atoms. The alkenediyl group may be linear, branched, or cyclic.

[0056] R 6 With regard to R, examples of the alkanediyl group include those mentioned above. 6 With regard to the above, examples of the alkenediyl group include those mentioned above.

[0057] In general formula (2), X represents a single bond, an ester bond, an ether bond, or a carbonyl group. 5 -O-CO-R 6 or R 5 -CO-O-R 6 The structure may be:

[0058] In the general formula (2), n represents a number from 1 to 5, and n R 5 , X, R 6 are independent of each other.

[0059] Examples of the hydrophilic monofunctional monomer (c) represented by general formula (2) 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.

[0060] The hydrophilic monofunctional monomer (c) represented by the general formula (2) may be a commercially available product, such as "Light Ester HO-MS (N)" manufactured by Kyoeisha Chemical Co., Ltd.

[0061] The hydrophilic monofunctional monomer (c) preferably has an SP value of 9.0 to 13.0, more preferably 9.5 to 12.5, and even more preferably 10.0 to 12.0. By using a hydrophilic monofunctional monomer (c) having an SP value within the above range, it is possible to suppress the occurrence of particle aggregation and coalescence during production, reduce the by-production of non-standard particles, and achieve more uniform low dielectric properties.

[0062] The SP value of the hydrophilic monofunctional monomer (c) can be calculated by the following formula (A) using the ΔF and Δv values ​​of various atomic groups by Okitsu listed in Table 1 of "Adhesion" (Okitsu Toshinao, Polymer Publishing Association, Vol. 40, No. 8 (1996), pp. 342-350). In the case of a mixed solvent or a copolymer, the SP value means the solubility parameter δ calculated by the following formula (B): δ=ΣΔF / ΣΔv (A) δ mix =φ1δ1+φ2δ2+・・・+φ n δ n (B) In formula (A), ΔF represents ΔF in Table 1 of "Adhesion", Δv represents the molar volume Δv in Table 1 of "Adhesion", φ represents the molar fraction, φ1 + φ2 + ... + φ n = 1. For example, the SP value of heptane as a solvent is calculated as follows. Heptane has two -CH3 and five -CH2- atomic groups. For each atomic group, the ΔF and Δv values ​​are calculated from Table 1 under "Adhesion". ΣΔF = 205 x 2 + 132 x 5 = 1070 ΣΔv = 31.8 x 2 + 16.5 x 5 = 146.1 Therefore, from the above formula (A), the δ of heptane is hep is calculated as follows: δ hep =ΣΔF / ΣΔv=1070 / 146.1=7.32 When a plurality of types of hydrophilic monomers (c) are used, the SP value (δ) of the entire mixed hydrophilic monomers (c) is calculated based on the SP value (solubility parameter δ) and the molar fraction in the manner described above. mix ) is calculated.

[0063] The content of the hydrophilic monofunctional monomer (c) in the monomer component (M) is preferably 10% by weight or less, more preferably 9.0% by weight or less, even more preferably 8.0% by weight or less, even more preferably 7.0% by weight or less, even more preferably 1.0% by weight to 7.0% by weight, even more preferably 1.5% by weight to 7.0% by weight, and even more preferably 2.0% by weight to 7.0% by weight, in order to further exhibit the effects of the present invention. When the content of the hydrophilic monofunctional monomer (c) in the monomer component (M) is within the above range, the effects of the present invention can be further exhibited.

[0064] The monomer component (M) preferably contains a reactive surfactant (d) having a vinyl group. The reactive surfactant (d) having a vinyl group may be one type or two or more types. When the monomer component (M) contains a reactive surfactant (d) having a vinyl group, the reactive surfactant (d) having a vinyl group is incorporated into the aromatic polymer (P1) as a monomer component. Therefore, the surfactant can be reliably distributed unevenly on the particle surface during suspension polymerization, and the surfactant effect can be improved. Therefore, compared to when a non-reactive surfactant without a vinyl group is used, even if the amount used is reduced, an excellent surfactant effect can be obtained, particle aggregation and coalescence during production can be suppressed, the by-production of non-standard particles can be reduced, and more uniform low dielectric properties can be achieved.

[0065] When the vinyl group-containing reactive surfactant (d) is incorporated as a monomer component into the aromatic polymer (P1), the aromatic polymer (P1) contains structural units derived from the vinyl group-containing reactive surfactant (d). That is, when the vinyl group-containing reactive surfactant (d) is represented by CH═C(R)-Z (R is H or CH), the aromatic polymer (P1) has a -Z group derived from the vinyl group-containing reactive surfactant (d).

[0066] In the production of hollow resin particles according to an embodiment of the present invention, it is preferable to use a reactive surfactant (d) having a vinyl group as a surfactant and to minimize the amount of non-reactive surfactant without a vinyl group. That is, in hollow resin particles according to an embodiment of the present invention, the content of the reactive surfactant (d) having a vinyl group relative to the total amount of surfactant used in the production is preferably 50% to 100% by weight, more preferably 70% to 100% by weight, even more preferably 90% to 100% by weight, particularly preferably 95% to 100% by weight, and most preferably 98% to 100% by weight. In hollow resin particles according to an embodiment of the present invention, as long as the content of the reactive surfactant (d) having a vinyl group in the surfactant used in the production falls within the above range, excellent surfactant activity can be obtained even when the amount used is reduced, particle aggregation and coalescence during production can be suppressed, off-specification particle by-production can be reduced, and more uniform low dielectric properties can be achieved.

[0067] The content of the vinyl group-containing reactive surfactant (d) in the monomer component (M) is preferably 0.05 wt % to 1.0 wt %, more preferably 0.10 wt % to 0.50 wt %, and even more preferably 0.15 wt % to 0.45 wt %, in order to further enhance the effects of the present invention. When the content of the vinyl group-containing reactive surfactant (d) in the monomer component (M) is within the above range, the effects of the present invention can be further enhanced. If the content of the vinyl group-containing reactive surfactant (d) in the monomer component (M) is too high and outside the above range, uniform low dielectric properties may not be achieved. One reason for this is thought to be that the vinyl group-containing reactive surfactant (d) contains a non-negligible amount of metal residue, not only when the structure itself contains a metal element, but also when the structure itself does not contain a metal element. The presence of such metal residue is a new finding discovered by the inventors during the completion of this invention. On the other hand, if the content of the reactive surfactant (d) having a vinyl group in the monomer component (M) is too small outside the above range, the surfactant effect will not be fully exerted, particle aggregation and coalescence will occur during production, non-standard particles will be by-produced, and the low dielectric properties will vary depending on the particles, which may prevent the expression of uniform low dielectric properties. Thus, in the present invention, by appropriately adjusting the content of the reactive surfactant (d) having a vinyl group in the monomer component (M) within the above range, the effects of the present invention can be more effectively expressed, and in particular, more uniform low dielectric properties can be expressed.

[0068] As the reactive surfactant (d) having a vinyl group, any suitable compound can be used as long as it has a vinyl group and can exhibit a surfactant effect, as long as it does not impair the effects of the present invention. Examples of such reactive surfactant (d) having a vinyl group include anionic surfactants having a vinyl group and nonionic surfactants having a vinyl group.

[0069] Examples of anionic surfactants having a vinyl group include polyoxyethylene-1-(allyloxymethyl) alkyl ether sulfate ammonium, polyoxyethylene styrenated propenyl phenyl ether sulfate ammonium, polyoxyalkylene alkenyl ether sulfate, 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.

[0070] Commercially available polyoxyethylene-1-(allyloxymethyl) alkyl ether sulfate ester ammonium products include, for example, trade name "Aqualon KH-10" and trade name "Aqualon KH-1025" (a 25 wt % aqueous solution of "Aqualon KH-10") manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.

[0071] Commercially available polyoxyethylene styrenated propenyl phenyl ether ammonium sulfate products include, for example, trade names "Aqualon AR-10," "Aqualon AR-20," and "Aqualon AR-1025" (a 25 wt % aqueous solution of "Aqualon AR-10") manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.

[0072] An example of a commercially available polyoxyalkylene alkenyl ether ammonium sulfate is "Latemul PD-104" manufactured by Kao Corporation.

[0073] Commercially available α-sulfo-ω-(1-alkoxymethyl-2-(2-propenyloxy)ethoxy)-poly(oxy-1,2-ethanediyl)ammonium products include, for example, trade names "ADEKA REASOAP SR-10" and "ADEKA REASOAP SR-20" manufactured by ADEKA Corporation.

[0074] An example of a commercially available polyoxypropylene allyl ether phosphate ester is "ADEKA REASOAP PP-70" manufactured by ADEKA Corporation.

[0075] An example of a commercially available product of bis(polyoxyethylene phenyl ether) methacrylate sulfate is "Antox MS-60" manufactured by Nippon Nyukazai Co., Ltd.

[0076] Examples of nonionic surfactants having a vinyl group include polyoxyethylene styrenated propenyl phenyl ether, polyoxyethylene-1-(allyloxymethyl) alkyl ether, and polyoxyalkylene alkenyl ether.

[0077] Commercially available polyoxyethylene styrenated propenyl phenyl ethers include, for example, trade names "Aqualon AN-10," "Aqualon AN-20," "Aqualon AN-30," and "Aqualon AN-5065" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.

[0078] Examples of commercially available polyoxyethylene-1-(allyloxymethyl) alkyl ethers include products manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. under the trade names "Aqualon KN-10," "Aqualon KN-20," "Aqualon KN-30," and "Aqualon KN-5065," and products manufactured by ADEKA Corporation under the trade names "ADEKA REASOAP ER-10," "ADEKA REASOAP ER-20," "ADEKA REASOAP ER-30," and "ADEKA REASOAP ER-40."

[0079] Commercially available polyoxyalkylene alkenyl ethers include, for example, those available under the trade names "Latemul PD-420," "Latemul PD-430," and "Latemul PD-450" manufactured by Kao Corporation.

[0080] In terms of being able to further exhibit the effects of the present invention, the reactive surfactant (d) having a vinyl group is preferably polyoxyethylene styrenated propenyl phenyl ether sulfate ammonium ester.

[0081] The total content of the aromatic monofunctional monomer (a), the aromatic crosslinkable monomer (b), the hydrophilic monofunctional monomer (c) represented by general formula (1) or general formula (2), and the reactive surfactant having a vinyl group (d) in the monomer component (M) is preferably 80% by weight to 100% by weight, more preferably 85% by weight to 100% by weight, even more preferably 90% by weight to 100% by weight, and particularly preferably 95% by weight to 100% by weight, in terms of being able to further exhibit the effects of the present invention.

[0082] The monomer component (M) may contain any other appropriate monomer as long as the effects of the present invention are not impaired. The other monomer may be one type only, or two or more types.

[0083] The shell portion may contain a non-crosslinkable polymer (P2) in addition to the aromatic polymer (P1). The non-crosslinkable polymer (P2) may be one type or two or more types. The non-crosslinkable polymer (P2) may be contained, and the non-crosslinkable polymer (P2) may promote phase separation of polymerized oil droplets during suspension polymerization, making it easier to form uniform particles, resulting in the development of excellent low dielectric properties and uniform low dielectric properties.

[0084] As the non-crosslinkable polymer (P2), any suitable non-crosslinkable polymer (P2) can be used as long as it does not impair the effects of the present invention. As such a non-crosslinkable polymer (P2), a non-crosslinkable polymer having no carboxyl group is preferable, and examples thereof include at least one selected from the group consisting of paraffin, polyolefin, styrene-based polymer, and (meth)acrylic acid ester-based polymer.

[0085] The content of the non-crosslinkable polymer (P2) in the shell portion is preferably 0 to 40% by weight, more preferably 3 to 30% by weight, and even more preferably 5 to 20% by weight, in order to further exhibit the effects of the present invention. If the content of the non-crosslinkable polymer (P2) in the shell portion is too high, there is a risk that excellent low dielectric properties may not be exhibited or that uniform low dielectric properties may not be exhibited.

[0086] Examples of paraffin include paraffin wax and liquid paraffin.

[0087] Examples of polyolefins include polyethylene, polypropylene, and poly-α-olefins.

[0088] Examples of styrene polymers include polystyrene, styrene-acrylonitrile copolymers, and acrylonitrile-butadiene-styrene copolymers.

[0089] Examples of the (meth)acrylic acid ester polymer include polymethyl(meth)acrylate, polyethyl(meth)acrylate, polybutyl(meth)acrylate, polypropyl(meth)acrylate, styrene-methyl(meth)acrylate copolymer, styrene-ethyl(meth)acrylate copolymer, styrene-butyl(meth)acrylate copolymer, and styrene-propyl(meth)acrylate copolymer.

[0090] <<Method for producing hollow resin particles>> The hollow resin particles according to an embodiment of the present invention may be produced by any appropriate method as long as the effects of the present invention are not impaired. In terms of being able to further exhibit the effects of the present invention, the hollow resin particles according to an embodiment of the present invention may be preferably produced by the method for producing hollow resin particles according to an embodiment of the present invention.

[0091] The method for producing hollow resin particles according to an embodiment of the present invention is a method for producing hollow resin particles having a shell portion and a hollow portion surrounded by the shell portion.

[0092] In a method for producing hollow resin particles according to an embodiment of the present invention, an oil phase and an aqueous phase are mixed and stirred to prepare a suspension, and the monomer component (M) contained in the suspension is subjected to suspension polymerization. The monomer component (M) here has the same meaning as the monomer component (M) in the above-mentioned section "Shell Portion," and means that an aromatic polymer (P1) is obtained by the reaction of the monomer component (M). That is, in a method for producing hollow resin particles according to an embodiment of the present invention, the monomer component (M) refers to all the monomer components contained in the suspension, i.e., the sum of the monomer components in the oil phase and the monomer components in the aqueous phase subjected to suspension polymerization.

[0093] The oil phase typically contains an aromatic monofunctional monomer (a) and an aromatic crosslinking monomer (b). The aromatic monofunctional monomer (a) and the aromatic crosslinking monomer (b) are similar to those described in the "Shell Portion" section.

[0094] In the method for producing hollow resin particles according to an embodiment of the present invention, the content of the aromatic monofunctional monomer (a) in the monomer component (M) is 30% by weight or more, preferably 30 to 80% by weight, more preferably 35 to 70% by weight, and even more preferably 40 to 60% by weight. When the content of the aromatic monofunctional monomer (a) in the monomer component (M) is within the above range, the effects of the present invention can be more effectively exhibited.

[0095] In the method for producing hollow resin particles according to an embodiment of the present invention, the content of aromatic crosslinkable monomer (b) in monomer component (M) is 60% by weight or less, preferably 10% to 60% by weight, more preferably 20% to 55% by weight, and even more preferably 30% to 50% by weight. When the content of aromatic crosslinkable monomer (b) in monomer component (M) is within the above range, the effects of the present invention can be more effectively exhibited. If the content of aromatic crosslinkable monomer (b) in monomer component (M) is too high, unreacted reactive sites may remain, which may adversely affect the sufficient exhibiting of low dielectric properties. If the content of aromatic crosslinkable monomer (b) in monomer component (M) is too low, the crosslink density may be low, which may reduce the strength of the shell portion.

[0096] The oil phase may contain a hydrophilic monofunctional monomer (c). For the hydrophilic monofunctional monomer (c), the explanation in the section "Shell portion" above may be applied.

[0097] In the method for producing hollow resin particles according to an embodiment of the present invention, the content of the hydrophilic monofunctional monomer (c) in the monomer component (M) is preferably 10% by weight or less, more preferably 9.0% by weight or less, even more preferably 8.0% by weight or less, even more preferably 7.0% by weight or less, even more preferably 1.0% by weight to 7.0% by weight, even more preferably 1.5% by weight to 7.0% by weight, and even more preferably 2.0% by weight to 7.0% by weight, in order to further exhibit the effects of the present invention. When the content of the hydrophilic monofunctional monomer (c) in the monomer component (M) is within the above range, the effects of the present invention can be further exhibited.

[0098] The oil phase may contain an organic solvent. The organic solvent may be one type only, or two or more types. Any appropriate organic solvent may be used as the organic solvent as long as it does not impair the effects of the present invention. As such an organic solvent, an organic solvent having a boiling point of less than 100°C is preferably used. By using an organic solvent having a boiling point of less than 100°C as the organic solvent, it becomes easy to remove the solvent from the hollow portion of the obtained hollow resin particles, and it becomes possible to reduce production costs.

[0099] Examples of organic solvents having a boiling point of less than 100° C. include heptane, hexane, cyclohexane, methyl acetate, ethyl acetate, methyl ethyl ketone, chloroform, and carbon tetrachloride.

[0100] The amount of the organic solvent used may be any appropriate amount as long as it does not impair the effects of the present invention, for example, 10 to 300 parts by weight per 100 parts by weight of the monomer components in the oil phase.

[0101] The oil phase may contain a polymerization initiator. The polymerization initiator may be one type or two or more types. Any appropriate polymerization initiator may be used as the polymerization initiator as long as it does not impair the effects of the present invention.

[0102] The polymerization initiator preferably has a 10-hour half-life temperature of 90° C. or less. If such a polymerization initiator is used, the polymerization initiator remaining in the hollow resin particles can be completely decomposed.

[0103] Examples of the polymerization initiator include organic peroxides such as lauroyl peroxide, benzoyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, t-butylperoxy-2-ethylhexanoate, and di-t-butyl peroxide; and azo compounds such as 2,2'-azobisisobutyronitrile, 1,1'-azobiscyclohexanecarbonitrile, and 2,2'-azobis(2,4-dimethylvaleronitrile).

[0104] The amount of the polymerization initiator used may be any appropriate amount as long as the effects of the present invention are not impaired. Such an amount is, for example, 0.1 to 5 parts by weight per 100 parts by weight of the monomer component (M) contained in the suspension (the total of the monomer components in the oil phase and the aqueous phase to be subjected to suspension polymerization).

[0105] The oil phase may contain a non-crosslinkable polymer (P2). The non-crosslinkable polymer (P2) may be one type or two or more types. For the non-crosslinkable polymer (P2), the explanation in the section "Shell Portion" above may be used.

[0106] The amount of the non-crosslinkable polymer (P2) used may be any appropriate amount as long as it does not impair the effects of the present invention. Such an amount is, for example, 0 to 67 parts by weight, more preferably 3 to 43 parts by weight, and even more preferably 5 to 25 parts by weight, relative to 100 parts by weight of the monomer component (M) contained in the suspension (the total of the monomer components in the oil phase and the aqueous phase subjected to suspension polymerization). If the amount of the non-crosslinkable polymer (P2) used is too large, there is a risk that excellent low dielectric properties may not be achieved, or that uniform low dielectric properties may not be achieved.

[0107] The oil phase may contain any other appropriate components in addition to the above-mentioned components, as long as the effects of the present invention are not impaired.

[0108] The aqueous phase typically contains a reactive surfactant (d) having a vinyl group. The explanation in the section "Shell portion" above can be applied to the reactive surfactant (d) having a vinyl group.

[0109] In the method for producing hollow resin particles according to an embodiment of the present invention, the content of the vinyl group-containing reactive surfactant (d) in the monomer component (M) is 0.05 wt % to 1.0 wt %, preferably 0.10 wt % to 0.50 wt %, and more preferably 0.15 wt % to 0.45 wt %. When the content of the vinyl group-containing reactive surfactant (d) in the monomer component (M) is within the above range, the effects of the present invention can be more effectively achieved. If the content of the vinyl group-containing reactive surfactant (d) in the monomer component (M) is too high and outside the above range, uniform low dielectric properties may not be achieved. One of the reasons for this, as explained in the section on "Shell Portion," is thought to be that the vinyl group-containing reactive surfactant (d) contains a non-negligible amount of metal residue, not only when the structure itself contains a metal element, but also when the structure itself does not contain a metal element. The presence of such metal residue is a new finding discovered by the inventors during the completion of the present invention. On the other hand, if the content of the reactive surfactant (d) having a vinyl group in the monomer component (M) is too small outside the above range, the surfactant effect will not be fully exerted, particle aggregation and coalescence will occur during production, non-standard particles will be by-produced, and the low dielectric properties will vary depending on the particles, which may prevent the expression of uniform low dielectric properties. Thus, in the present invention, by appropriately adjusting the content of the reactive surfactant (d) having a vinyl group in the monomer component (M) within the above range, the effects of the present invention can be more effectively expressed, and in particular, more uniform low dielectric properties can be expressed.

[0110] The aqueous phase typically contains an aqueous medium. Examples of the aqueous medium include water and a mixture of water and a lower alcohol (e.g., methanol, ethanol, etc.). The water is preferably at least one selected from the group consisting of ion-exchanged water and distilled water.

[0111] In the method for producing hollow resin particles according to an embodiment of the present invention, the oil phase and the aqueous phase are mixed and stirred to prepare a suspension, and the monomer component (M) contained in the suspension is subjected to suspension polymerization.

[0112] As a method for mixing the oil phase and the aqueous phase, any appropriate method can be adopted as long as it can carry out suspension polymerization and does not impair the effects of the present invention.

[0113] The suspension is prepared by mixing an oil phase and an aqueous phase and stirring the mixture to disperse the oil phase in the aqueous phase. Any suitable dispersion method can be used to disperse the oil phase in the aqueous phase, as long as it allows the oil phase to exist in droplet form in the aqueous phase, as long as it does not impair the effects of the present invention. A typical dispersion method is a dispersion method using a homogenizer, such as an ultrasonic homogenizer or a high-pressure homogenizer.

[0114] Any appropriate method can be adopted as the suspension polymerization method as long as it does not impair the effects of the present invention.

[0115] The polymerization temperature may be any suitable temperature suitable for suspension polymerization within a range that does not impair the effects of the present invention, such as 30°C to 95°C.

[0116] The polymerization time may be any suitable time suitable for suspension polymerization as long as it does not impair the effects of the present invention. Such a polymerization time is preferably 1 hour to 20 hours.

[0117] Post-heating, which is preferably carried out after polymerization, is a treatment suitable for obtaining hollow resin particles with a high degree of perfection.

[0118] The temperature for post-heating preferably carried out after polymerization can be any appropriate temperature within a range that does not impair the effects of the present invention. The temperature for such post-heating is preferably 50°C to 120°C.

[0119] The time for post-heating preferably carried out after polymerization can be any appropriate time within the range that does not impair the effects of the present invention, and the time for such post-heating is preferably 1 hour to 10 hours.

[0120] The slurry obtained by suspension polymerization is subjected to distillation, solvent removal, classification, washing, drying, etc., as required, to obtain hollow resin particles.

[0121] <<Uses of Hollow Resin Particles>> The hollow resin particles according to an embodiment of the present invention can be used in a variety of applications. Because the effects of the present invention can be more effectively utilized, the hollow resin particles according to an embodiment of the present invention are suitable for semiconductor components, and can be typically used in resin compositions for semiconductor components. Furthermore, in addition to the use in the resin compositions for semiconductor components described above, the hollow resin particles according to an embodiment of the present invention can also be used in applications in which the effects of the present invention can be utilized, such as paint compositions, heat-insulating resin compositions, light-diffusing resin compositions, and light-diffusing films.

[0122] <<Resin Composition for Semiconductor Member>> The hollow resin particles according to an embodiment of the present invention can achieve low dielectric constant and low dielectric loss tangent and exhibit excellent heat resistance, and therefore can be suitably used in resin compositions for semiconductor members.

[0123] The resin composition for a semiconductor member according to an embodiment of the present invention contains hollow resin particles according to an embodiment of the present invention.

[0124] The term "semiconductor member" refers to a member that constitutes a semiconductor, such as a semiconductor package or a semiconductor module. In this specification, the term "resin composition for a semiconductor member" refers to a resin composition used for a semiconductor member.

[0125] A semiconductor package is constructed using an IC chip as an essential component and at least one member selected from a mold resin, an underfill material, a mold underfill material, a die bond material, a prepreg for a semiconductor package substrate, a metal-clad laminate for a semiconductor package substrate, and a build-up material for a printed circuit board for a semiconductor package.

[0126] A semiconductor module is constructed using a semiconductor package as an essential component and at least one member selected from a prepreg for a printed circuit board, a metal-clad laminate for a printed circuit board, a build-up material for a printed circuit board, a solder resist material, a coverlay film, an electromagnetic wave shielding film, and an adhesive sheet for a printed circuit board.

[0127] <<Coating Composition>> The hollow resin particles according to an embodiment of the present invention can impart an excellent appearance to a coating film containing the hollow resin particles, and therefore can be suitably used in a coating composition.

[0128] A coating composition according to an embodiment of the present invention includes hollow resin particles according to an embodiment of the present invention.

[0129] The coating composition according to an 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 of only one type or may contain two or more types. The UV-curable resin may be of only one type or may contain two or more types.

[0130] Any suitable binder resin can be used 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. Specific examples of binder resins include acrylic resins, alkyd resins, polyester resins, polyurethane resins, chlorinated polyolefin resins, and amorphous polyolefin resins.

[0131] As the UV-curable resin, any appropriate 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. 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 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-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.

[0132] When the coating composition according to an embodiment of the present invention contains at least one selected from a binder resin and a UV-curable resin, any appropriate content ratio can be adopted depending on the purpose. Typically, the hollow resin particles according to an embodiment of the present invention are preferably contained in an amount of 5 to 50% by weight, more preferably 10 to 50% by weight, and even more preferably 20 to 40% by weight of the total amount of the binder resin (in terms of solids content in the case of an emulsion-type aqueous resin), the at least one selected from the UV-curable resin, and the hollow resin particles according to an embodiment of the present invention.

[0133] When a UV-curable resin is used, a photopolymerization initiator is preferably used in combination. Any appropriate photopolymerization initiator can be used as long as it does not impair the effects of the present invention. Examples of such photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, α-hydroxyalkylphenones, α-aminoalkylphenones, anthraquinones, thioxanthones, azo compounds, peroxides (described in JP 2001-139663 A, etc.), 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfonium compounds, onium salts, borate salts, active halogen compounds, and α-acyloxime esters.

[0134] The coating composition according to the embodiment of the present invention may contain a solvent. The solvent may be one kind or two or more kinds. When the coating composition according to the embodiment of the present invention contains a solvent, any appropriate content ratio can be adopted depending on the purpose.

[0135] As the solvent, any appropriate solvent can be used as long as it does not impair the effects of the present invention. Such a solvent is preferably a solvent that can dissolve or disperse a binder resin or a 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; and ether solvents such as dioxane, ethylene glycol diethyl ether, and ethylene glycol monobutyl ether. For water-based paints, examples of such solvents include water and alcohols.

[0136] The coating composition according to the embodiment of the present invention may be diluted to adjust the viscosity as needed. Any appropriate diluent may be used depending on the purpose. Examples of such diluents include the solvents mentioned above. The diluent may be one type or two or more types.

[0137] The coating composition according to an embodiment of the present invention may contain other components, such as a coating surface conditioner, a flowability conditioner, an ultraviolet absorber, a light stabilizer, a curing catalyst, an extender pigment, a color pigment, a metallic pigment, a mica powder pigment, or a dye, as needed.

[0138] When forming a coating film using the coating composition according to an embodiment of the present invention, any appropriate coating method can be adopted depending on the purpose, such as spray coating, roll coating, brush coating, coating reverse roll coating, gravure coating, die coating, comma coating, and spray coating.

[0139] When forming a coating film using the coating composition according to an embodiment of the present invention, any suitable method can be adopted depending on the purpose. For example, a coating film can be formed by applying the composition to any surface of a substrate, drying the coating film, and then curing the coating film as needed. Examples of substrates include metal, wood, glass, and plastics (PET (polyethylene terephthalate), PC (polycarbonate), acrylic resin, TAC (triacetyl cellulose), etc.).

[0140] The hollow resin particles according to an embodiment of the present invention can impart excellent heat insulating properties to a coating film containing the hollow resin particles, and therefore can be suitably used in a heat insulating resin composition. 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.

[0141] The heat insulating resin composition according to an embodiment of the present invention includes hollow resin particles according to an embodiment of the present invention.

[0142] 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. The above-mentioned explanations regarding the coating composition can be applied to the binder resin and the UV-curable resin.

[0143] The heat insulating resin composition according to the embodiment of the present invention may contain a solvent. Regarding the solvent, the above explanation regarding the coating composition may be cited.

[0144] The heat insulating resin composition according to the embodiment of the present invention may be diluted to adjust the viscosity as needed. The above description of the coating composition can be used as the diluent.

[0145] The heat insulating resin composition according to an embodiment of the present invention may contain other components, such as a coating surface conditioner, a flowability conditioner, an ultraviolet absorber, a light stabilizer, a curing catalyst, an extender pigment, a color pigment, a metal pigment, a mica powder pigment, or a dye, as needed.

[0146] When a coating film is formed using the heat insulating resin composition according to an embodiment of the present invention, the coating method and formation method can be applied as described above for the coating composition.

[0147] <Light-diffusing resin composition> The hollow resin particles according to an embodiment of the present invention can impart excellent light-diffusing properties to a coating film containing the hollow resin particles, and therefore can be suitably used in a light-diffusing resin composition.

[0148] The light-diffusing resin composition according to an embodiment of the present invention includes hollow resin particles according to an embodiment of the present invention.

[0149] 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. The above-mentioned explanations regarding the coating composition can be applied to the binder resin and the UV-curable resin.

[0150] The light-diffusing resin composition according to the embodiment of the present invention may contain a solvent. Regarding the solvent, the above explanation regarding the coating composition may be cited.

[0151] The light-diffusing resin composition according to the embodiment of the present invention may be diluted to adjust the viscosity as needed. The above-mentioned description of the coating composition may be applied to the diluent.

[0152] The light-diffusing resin composition according to an embodiment of the present invention may contain other components, such as a coating surface conditioner, a flowability conditioner, an ultraviolet absorber, a light stabilizer, a curing catalyst, an extender pigment, a color pigment, a metal pigment, a mica powder pigment, or a dye, as needed.

[0153] When forming a coating film using the light-diffusing resin composition according to an embodiment of the present invention, the coating method and formation method can be applied as described above for the coating composition.

[0154] <Light Diffusion Film> The hollow resin particles according to an embodiment of the present invention can impart excellent light diffusibility to a film having a coating film containing the hollow resin particles, and therefore can also be suitably used for a light diffusing film.

[0155] The light diffusion film according to an embodiment of the present invention includes hollow resin particles according to an embodiment of the present invention.

[0156] The light diffusion film according to an embodiment of the present invention includes a light diffusion layer formed from the light-diffusing resin composition according to an embodiment of the present invention and a substrate. The light diffusion layer may or may not be the outermost layer of the light diffusion film. The light diffusion film according to an embodiment of the present invention may include any appropriate other 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 fine particle layer, a conductive metal oxide fine particle layer, and a primer layer.

[0157] Examples of the substrate 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 that constitutes the plastic film, plastic sheet, plastic lens, and plastic panel include polyethylene terephthalate (PET), polycarbonate (PC), acrylic resin, and triacetyl cellulose (TAC).

[0158] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means "parts by weight" and "%" means "% by weight."

[0159] <Average Particle Diameter> The Z-average particle diameter of hollow resin particles or particles was measured using dynamic light scattering, and the measured Z-average particle diameter was used as the average particle diameter of the obtained hollow resin particles or particles. Specifically, the obtained hollow resin particles or particles were first diluted with ion-exchange water to a concentration of 0.1 wt %. The aqueous dispersion was then irradiated with laser light, and the scattered light intensity from the hollow resin particles or particles was measured over time in microseconds. The detected scattering intensity distribution due to the hollow resin particles or particles was then fitted to a normal distribution, and the Z-average particle diameter of the hollow resin particles or particles was calculated using cumulant analysis. This Z-average particle diameter measurement can be easily performed using a commercially available particle size measurement device. In the following examples and comparative examples, the Z-average particle diameter was measured using a particle size measurement device (Malvern Zetasizer Nano ZS). Typically, commercially available particle size measurement devices are equipped with data analysis software, which automatically analyzes the measurement data to calculate the Z-average particle diameter.

[0160] <TEM Measurement: Observation of the Presence or Absence of Hollowness and Shape of Hollow Resin Particles> Hollow resin particles or particles as a dry powder were subjected to surface treatment (10 Pa, 5 mA, 10 seconds) using an "Osmium Coater Neoc-Pro" coating device manufactured by Meiwafosis Co., Ltd. The hollow resin particles or particles were then 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. Images were taken at an acceleration voltage of 80 kV and a magnification of 5,000x or 10,000x. The hollow ratio can be calculated as the average value of 100 particles based on the length measurement results observed by TEM.

[0161] <Metal Residue Amount Measurement> The amount of metal residue was measured as follows. (Measurement Sample) 0.5 g of hollow resin particles was precisely weighed into a cleaned 50 mL plastic container. 1 mL of cleaning ethanol was added, and the mixture was thoroughly mixed and dispersed. 50 mL of ion-exchanged water was then added and thoroughly mixed. Ultrasonic cleaning and extraction was performed for approximately 10 minutes, and the mixture was then left to stand for 60 minutes in a 60°C thermostatic chamber. After standing, the slurry was filtered through an aqueous 0.20 μm chromatographic disc to obtain 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 previously prepared calibration curve. The amount of metal residue was calculated using the following formula: Metal residue amount (ppm) = measured metal element concentration (μg / mL) × 51 (mL) ÷ sample amount (g). The lower limit of quantitation was 1 ppm, and if the measurement result was below this lower limit of quantitation, the lower limit of quantitation of 1 ppm was used as the measurement result. (ICP measurement conditions) Measuring device = Shimadzu Corporation's "ICPE-9000" multi-type ICP optical emission spectrometer; Measurement elements = Ca, K, Li, Mg, Na; Observation direction = axial; 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; Standard solutions for calibration curve = SPEX, USA's "XSTC-13" general-purpose mixed standard solution, 31-element mixture (base 5% HNO3): approximately 10 mg / L each; "XSTC-8" general-purpose mixed standard solution, 13-element mixture (base HO / trace HF): approximately 10 mg / L each

[0162] <Evaluation of Dielectric Properties> [Evaluation of Dielectric Properties of Hollow Resin Particles] The dielectric properties of the hollow resin particles were measured using a dielectric constant measuring device (ADMS01Nc series) manufactured by AET Corporation. The dielectric loss tangent (Df) of the hollow resin particles was calculated based on perturbation theory using a resonator at a frequency of 10 GHz, in a measurement environment of 23°C and a relative humidity of 51±1%. Furthermore, the F value, which is an index of the uniformity of the dielectric loss tangent Df, was calculated. The F value was calculated by measuring the dielectric loss tangent Df of the hollow resin particles at five measurement points and finding the maximum value of Df (Df max ) and the minimum value of Df (Df min ) and the average value of Df (Df av ) is calculated, and the F value = (Df max -Df min ) / Df avThe dielectric loss tangent (Df) was calculated using the formula: A smaller F value indicates less variation in the dielectric loss tangent (Df), which means that uniform low dielectric properties can be achieved. Based on the obtained F value, evaluation was performed using the following criteria: F value less than 0.15: Excellent; F value 0.15 or greater but less than 0.25: Excellent; F value 0.25 or greater but less than 0.35: Fair; F value 0.35 or greater: Bad. [Evaluation of Film Dielectric Properties] The dielectric properties of the film were measured using a dielectric constant measuring device (ADMS01Nc series) manufactured by AET Corporation. The dielectric loss tangent (Df) of the film was calculated based on perturbation theory using a resonator at a frequency of 10 GHz, under a measurement environment of 23°C and a relative humidity of 51±1%. The measurement results of the dielectric loss tangent were expressed as a relative percentage (%), with the measurement value for a particle-free film being taken as 100%. This relative percentage is preferably less than 85%, more preferably 80% or less, even more preferably 75% or less, and particularly preferably 70% or less. Furthermore, the F value, which is an index of the uniformity of the dielectric loss tangent Df, was calculated. The F value was calculated by measuring the dielectric loss tangent Df of the film at five measurement points and finding the maximum value of Df (Df max ) and the minimum value of Df (Df min ) and the average value of Df (Df av ) is calculated, and the F value = (Df max -Df min ) / Df av The F value was calculated using the following formula. A smaller F value means less variation in the dielectric loss tangent Df, and that uniform low dielectric properties can be achieved. Based on the obtained F value, the evaluation was made according to the following criteria. F value less than 0.15: Excellent F value 0.15 or more but less than 0.25: Good F value 0.25 or more but less than 0.35: Fair F value 0.35 or more: Bad

[0163] <Raw materials used> The raw materials used are as follows.

[0164] [Aromatic Monofunctional Monomer (a)] Styrene

[0165] [Aromatic crosslinkable monomer (b)] Divinylbenzene (DVB) 810 (Nippon Steel Chemical & Material Co., Ltd., 81% by weight content, 19% by weight is ethylvinylbenzene (EVB))

[0166] [Hydrophilic monofunctional monomer (c)] Compound corresponding to general formula (1): polyethylene glycol propylene glycol monomethacrylate (manufactured by NOF Corporation, trade name "BLEMMER 50PEP-300"; in general formula (1), R 1 = CH3, R 2 = H, (R 3 -O) m = [(C2H4O) 3.5 (C3H6O) 2.5 ], random addition form, SP value = 10.5) Compound corresponding to general formula (1): methoxypolyethylene glycol monomethacrylate (manufactured by NOF Corporation, trade name "BLEMMER PME-100", in general formula (1), R 1 = CH3, R 2 = CH3, (R 3 -O) m = [(C2H4O)2], SP value = 9.3) Compound corresponding to general formula (1): polyethylene glycol monoacrylate (manufactured by NOF Corporation, trade name "BLEMMER AE-90U", in general formula (1), R 1 = H, R 2 = H, (R 3 -O) m = [(CHO) ], SP value = 12.8) Compound corresponding to general formula (2): 2-methacryloyloxyethyl succinic acid (manufactured by Kyoeisha Chemical Co., Ltd., trade name "Light Ester HO-MS (N)"); in general formula (2), R 4 = CH3, R 5 = CH2CH2, R 6 =CHCH, X = -O-C(=O)-, n = 1, SP value = 10.2)

[0167] [Reactive surfactants (d) having a vinyl group] Polyoxyethylene styrenated propenylphenyl ether sulfate ester ammonium salt (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name "Aqualon AR-10") α-sulfo-ω-(1-alkoxymethyl-2-(2-propenyloxy)ethoxy)-poly(oxy-1,2-ethanediyl)ammonium (manufactured by ADEKA Corporation, trade name "ADEKA REASOAP SR-10")

[0168] [Non-reactive surfactants having no vinyl group] Sodium di-2-ethylhexyl sulfosuccinate (manufactured by NOF Corporation, trade name "Rapisol A-80", pure content 80% by weight)

[0169] [Non-crosslinkable polymer (P2)] Paraffin wax (manufactured by Nucera Solutions, trade name "VYBAR260")

[0170] [Organic solvent] Heptane

[0171] [Polymerization initiator] Lauroyl peroxide (manufactured by NOF Corporation, trade name "Perloyl L")

[0172] [Aqueous medium] Ion-exchanged water

[0173] Example 1 After preparing the oil and aqueous phases according to the compositions shown in Table 1, the oil and aqueous phases were mixed and processed using a homomixer (manufactured by Primix Corporation, trade name "T.K. Homomixer MARK II 2.5 Type") at a rotation speed of 8,000 rpm for 10 minutes to obtain an emulsion (mixed liquid). Subsequently, using a high-pressure emulsifier NVR (manufactured by Yoshida Kikai Kogyo Co., Ltd., model "EM055-P20-0600-Exp"), emulsification was performed under conditions of an inlet processing pressure of 20 MPa and an outlet pressure of 10 MPa to produce a suspension. The resulting suspension was heated at 60°C for 10 hours, then heated to 90°C and heated for 3 hours to perform suspension polymerization. The organic solvent was removed from the slurry obtained by suspension polymerization by distillation, and large particles were then classified and removed using a 500-mesh (25 μm mesh) wire net to obtain a slurry containing hollow resin particles. The slurry containing hollow resin particles was spray-dried using a spray dryer (manufactured by Sakamoto Giken Co., Ltd., machine name "Spray Dryer", model "Atomizer Take-Up Method", model number "TRS-3WK") under the following apparatus conditions to obtain hollow resin particles (1). TEM measurement confirmed that the hollow resin particles (1) were hollow particles with a single hollow structure. <Apparatus conditions> Slurry supply rate containing hollow resin particles: 25 mL / min Atomizer rotation speed: 12,000 rpm Air volume: 2 m 3 / min Inlet temperature (inlet temperature of the inlet port provided in the spray dryer through which the slurry containing hollow resin particles is sprayed and introduced): 185°C Outlet temperature (outlet temperature of the outlet port provided in the spray dryer through which the hollow resin particles are discharged): 70°C The results are shown in Table 1.

[0174] [Example 2] Hollow resin particles (2) were obtained in the same manner as in Example 1, except that sodium nitrite was added to the aqueous phase of Example 1 in the composition shown in Table 1. TEM measurement confirmed that the hollow resin particles (2) were hollow particles with a monohollow structure. The results are shown in Table 1.

[0175] Example 3 Hollow resin particles (3) were obtained in the same manner as in Example 1, except that, as shown in Table 1, "Light Ester HO-MS (N)" was used instead of "Blenmer 50PEP-300" as the hydrophilic monofunctional monomer (c). TEM measurement confirmed that the hollow resin particles (3) were hollow particles with a monohollow structure. The results are shown in Table 1.

[0176] Example 4 Hollow resin particles (4) were obtained in the same manner as in Example 1, except that the amount of "Aqualon AR-10" used was changed to 1.5 parts by weight as shown in Table 1. TEM measurement confirmed that the hollow resin particles (4) were hollow particles with a monohollow structure. The results are shown in Table 1.

[0177] [Example 5] Hollow resin particles (5) were obtained in the same manner as in Example 1, except that the amount of "Aqualon AR-10" used was changed to 5.0 parts by weight as shown in Table 1. TEM measurement confirmed that the hollow resin particles (5) were hollow particles with a monohollow structure. The results are shown in Table 1.

[0178] Example 6 Hollow resin particles (6) were obtained in the same manner as in Example 1, except that, as shown in Table 1, 3.5 parts by weight of "ADEKA REASOAP SR-10" was used instead of 3.0 parts by weight of "AQUALON AR-10" as the reactive surfactant (d). TEM measurement confirmed that the hollow resin particles (6) were hollow particles with a monohollow structure. The results are shown in Table 1.

[0179] Example 7 Hollow resin particles (7) were obtained in the same manner as in Example 1, except that, as shown in Table 1, "BLEMMER PME-100" was used instead of "BLEMMER 50PEP-300" as the hydrophilic monofunctional monomer (c). TEM measurement confirmed that the hollow resin particles (7) were hollow particles with a monohollow structure. The results are shown in Table 1.

[0180] Example 8 Hollow resin particles (8) were obtained in the same manner as in Example 1, except that, as shown in Table 1, "BLEMMER AE-90U" was used instead of "BLEMMER 50PEP-300" as the hydrophilic monofunctional monomer (c). TEM measurement confirmed that the hollow resin particles (8) were hollow particles with a monohollow structure. The results are shown in Table 1.

[0181] Comparative Example 1 Hollow resin particles (C1) were obtained in the same manner as in Example 1, except that sodium nitrite was added to the aqueous phase in the composition shown in Table 2. TEM measurement confirmed that the hollow resin particles (C1) were hollow particles with a monohollow structure. The results are shown in Table 2.

[0182] Comparative Example 2 Hollow resin particles (C2) were obtained in the same manner as in Example 1, except that sodium nitrite was added to the aqueous phase of Example 1 in the composition shown in Table 2. TEM measurement confirmed that the hollow resin particles (C2) were hollow particles with a monohollow structure. The results are shown in Table 2.

[0183] Comparative Example 3 As shown in Table 2, hollow resin particles (C3) were obtained in the same manner as in Example 1, except that the same amount (3.75 g used, 3.0 g as a pure content since the pure content was 80% by weight) of the non-reactive surfactant "Rapisol A-80" having no vinyl group was used instead of the reactive surfactant (d) having a vinyl group "Aqualon AR-10." TEM measurement confirmed that the hollow resin particles (C3) were hollow particles with a monohollow structure. The results are shown in Table 2.

[0184] Comparative Example 4 Hollow resin particles (C4) were obtained in the same manner as in Example 1, except that the amount of "Aqualon AR-10," a reactive surfactant (d) having a vinyl group, used was increased as shown in Table 2. TEM measurement confirmed that the hollow resin particles (C4) were hollow particles with a monohollow structure. The results are shown in Table 2.

[0185] Comparative Example 5 Hollow resin particles (C5) were obtained in the same manner as in Example 1, except that the amount of hydrophilic monofunctional monomer (c) "BLEMMER 50PEP-300" used was increased and the amounts of aromatic monofunctional monomer (a) and aromatic crosslinkable monomer (b) were reduced, as shown in Table 2. TEM measurement confirmed that the hollow resin particles (C5) were hollow particles with a monohollow structure. The results are shown in Table 2.

[0186]

[0187]

[0188] Example 9 A film containing the hollow resin particles (1) obtained in Example 1 was prepared as follows, and the dielectric properties of the resulting film were evaluated. 0.6 g of the hollow resin particles (1) obtained in Example 1 and 10 g of ultra-high heat-resistant polyimide varnish SPIXAREA HR002 (manufactured by Somar Co., Ltd.) were degassed and stirred using a planetary stirring defoamer (manufactured by KURABO Corporation, "Mazerustar KK-250") to prepare a mixture for evaluation. The mixture for evaluation was applied to a 5 mm-thick glass plate using an applicator set to a wet thickness of 250 μm. The solvent was then removed by heating at 120°C for 10 minutes, 180°C for 180 minutes, and 270°C for 60 minutes, and then cooled to room temperature to obtain a film containing the particles. The results are shown in Table 3.

[0189] [Example 10] A film containing the particles was obtained in the same manner as in Example 9, except that the hollow resin particles (2) obtained in Example 2 were used instead of the hollow resin particles (1) obtained in Example 1. The results are shown in Table 3.

[0190] Comparative Example 6 The hollow resin particles (C1) obtained in Comparative Example 1 were used instead of the hollow resin particles (1) obtained in Example 1, and the procedure was carried out in the same manner as in Example 9 to obtain a film containing the particles. The results are shown in Table 3.

[0191] Comparative Example 7 A film containing the particles was obtained in the same manner as in Example 9, except that the hollow resin particles (C2) obtained in Comparative Example 2 were used instead of the hollow resin particles (1) obtained in Example 1. The results are shown in Table 3.

[0192]

[0193] The hollow resin particles according to an embodiment of the present invention and the hollow resin particles obtained by the production method according to an embodiment of the present invention can be used in various applications such as resin compositions for semiconductor members, coating compositions, heat insulating resin compositions, light diffusing resin 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 amount of metal residue being 30 ppm or less, a dielectric loss tangent Df at a frequency of 10 GHz being 0.0050 or less, and an F value, which is an index of the uniformity of the dielectric loss tangent Df, being 0.30 or less.

2. The hollow resin particle according to claim 1, wherein the dielectric loss tangent Df is 0.0030 or less.

3. The hollow resin particle according to claim 1, wherein the F value is 0.15 or less.

4. The hollow resin particles according to claim 1, having an average particle size of 0.1 μm to 10.0 μm.

5. The hollow resin particle according to claim 1, wherein the shell portion comprises an aromatic polymer (P1) obtained by the reaction of a monomer component (M) comprising an aromatic monofunctional monomer (a) and an aromatic crosslinkable monomer (b).

6. The hollow resin particle according to claim 5, wherein the content of the aromatic polymer (P1) in the shell portion is 60% by weight to 100% by weight.

7. The hollow resin particle according to claim 5, wherein the content of said aromatic crosslinkable monomer (b) in said monomer component (M) is 60% by weight or less.

8. The hollow resin particle according to claim 5, wherein the monomer component (M) contains a hydrophilic monofunctional monomer (c).

9. The hollow resin particle according to claim 8, wherein the hydrophilic monofunctional monomer (c) is represented by general formula (1) or general formula (2). In the general formula (1), R 1 represents H or CH3, R 2 represents H, an alkyl group, or a phenyl group; R 3 represents an alkanediyl group having 2 to 18 carbon atoms, and m is R 3 The average number of moles of oxyalkylene groups represented by —O is 1 to 100, and m R 3 are independent of each other. In the general formula (2), R 4 represents H or CH3, R 5 represents an alkanediyl group having 1 to 10 carbon atoms or an alkenediyl group having 2 to 10 carbon atoms; R 6 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; 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 5 , X, R 6 are independent of each other.

10. The hollow resin particle according to claim 5, wherein the monomer component (M) contains a reactive surfactant (d) having a vinyl group.

11. The hollow resin particle according to claim 10, wherein the content of the reactive surfactant (d) having a vinyl group in the monomer component (M) is 0.10% by weight to 1.0% by weight.

12. The hollow resin particle according to claim 11, wherein the content of the reactive surfactant (d) having a vinyl group in the monomer component (M) is 0.10% by weight to 0.50% by weight.

13. The hollow resin particle according to claim 10, wherein the reactive surfactant (d) having a vinyl group is ammonium polyoxyethylene styrenated propenyl phenyl ether sulfate.

14. The hollow resin particle according to claim 1, wherein the shell portion comprises a non-crosslinkable polymer (P2).

15. The hollow resin particle according to claim 14, wherein the content of the non-crosslinkable polymer (P2) in the shell portion is 0% by weight to 40% by weight.

16. The hollow resin particles according to any one of claims 1 to 15, which are used in a resin composition for semiconductor members.

17. The hollow resin particles according to any one of claims 1 to 15, for use in a coating composition.

18. The hollow resin particles according to any one of claims 1 to 15, which are used in a heat insulating resin composition.

19. The hollow resin particles according to any one of claims 1 to 15, which are used in a light-diffusing resin composition.

20. The hollow resin particles according to any one of claims 1 to 15, which are used in a light diffusing film.

21. A resin composition for semiconductor members, comprising the hollow resin particles according to any one of claims 1 to 15.

22. A coating composition comprising the hollow resin particles according to any one of claims 1 to 15.

23. A heat insulating resin composition comprising the hollow resin particles according to any one of claims 1 to 15.

24. A light-diffusing resin composition comprising the hollow resin particles according to any one of claims 1 to 15.

25. A light-diffusing film comprising the hollow resin particles according to any one of claims 1 to 15.

26. A method for producing hollow resin particles having a shell portion and a hollow portion surrounded by the shell portion, comprising mixing and stirring an oil phase and an aqueous phase to prepare a suspension, and carrying out suspension polymerization of a monomer component (M) contained in the suspension, wherein the oil phase contains an aromatic monofunctional monomer (a) and an aromatic crosslinkable monomer (b), and the aqueous phase contains a reactive surfactant having a vinyl group (d), the content of the aromatic monofunctional monomer (a) in the monomer component (M) is 30% by weight or more, the content of the aromatic crosslinkable monomer (b) in the monomer component (M) is 60% by weight or less, and the content of the reactive surfactant having a vinyl group (d) in the monomer component (M) is 0.10% by weight to 1.0% by weight.

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