Hollow resin particles and method for producing the same

Abstract

To provide a hollow resin particle that can reduce a dielectricity and dielectric loss tangent of a resin layer by introducing an empty area thereinto, and can be obtained by forming a hollow portion in a simple manner, and to also provide a method of producing such a hollow resin particle in a simple manner.SOLUTION: A hollow resin particle according to an embodiment of the present invention is a hollow resin particle including a shell portion and a hollow portion surrounded by the shell portion, wherein the shell portion contains an aromatic polymer (P1) obtained by polymerizing a monomer composition containing an aromatic crosslinkable monomer (a), an aromatic monofunctional monomer (b), and a (meth)acrylic acid ester-based monomer (c) having a specific structure.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to hollow resin particles and a method for producing the same. [Background technology]

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

[0003] It has been reported that hollow particles such as 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).

[0004] Generally, acrylic resins are known to have high relative permittivity and dielectric loss tangent, and for this reason, the acrylic hollow resin particles described in Patent Document 1 are unsuitable for achieving low dielectric constant and low dielectric loss tangent of a resin layer.

[0005] It has also been reported that hollow particles, for example, can be obtained by suspension polymerization of divinylbenzene together with saturated hydrocarbons having 8 to 18 carbon atoms (specifically, hexadecane) to produce styrene-based hollow resin particles (Patent Document 2).

[0006] The styrene-based hollow resin particles described in Patent Document 2 are made of a material (crosslinked polystyrene) that has a lower dielectric constant and dielectric loss tangent than acrylic-based hollow resin particles. Therefore, they are effective particles for achieving low dielectric constant and low dielectric loss tangent of the resin layer. However, because saturated hydrocarbons with 8 to 18 carbon atoms (specifically, hexadecane) are used in their production, removing the solvent from the hollow portions by distillation or other methods is difficult. As a result, saturated hydrocarbons with 8 to 18 carbon atoms remain in the resulting styrene-based hollow resin particles, making it difficult to obtain styrene-based hollow resin particles whose hollow portions are completely filled with air. Furthermore, in order to obtain styrene-based hollow resin particles whose hollow portions are completely filled with air, the production costs are high due to the solvent removal described above. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Patent No. 6513273 [Patent Document 2] Japanese Patent Application Laid-Open No. 2002-080503 Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention has been made to solve the above-mentioned problems of the prior art, and its main object is to provide hollow resin particles that can be obtained by simply forming hollow portions by introducing air spaces into a resin layer, thereby enabling a reduction in dielectric constant and a reduction in dielectric loss tangent, and also to provide a method for easily producing such hollow resin particles. [Means for solving the problem]

[0009] The hollow resin particles according to an embodiment of the present invention are A hollow resin particle having a shell portion and a hollow portion surrounded by the shell portion, The shell portion contains an aromatic polymer (P1) obtained by polymerizing a monomer composition containing an aromatic crosslinkable monomer (a), an aromatic monofunctional monomer (b), and a (meth)acrylic acid ester monomer (c) represented by formula (1). [ka] (R 1 represents H or CH3, and R 2 represents H, an alkyl group, or a phenyl group, and R 3 -O represents an oxyalkylene group having 2 to 18 carbon atoms, and m is the average number of moles of the oxyalkylene group added, which is a number from 1 to 100.

[0010] In one embodiment, the oxyalkylene group is at least one selected from the group consisting of an oxyethylene group, an oxypropylene group, and an oxybutylene group.

[0011] In one embodiment, the monomer composition contains 10% by weight to 70% by weight of an aromatic crosslinkable monomer (a), 10% by weight to 70% by weight of an aromatic monofunctional monomer (b), and 0.5% by weight to 30% by weight of a (meth)acrylic acid ester monomer (c) represented by general formula (1).

[0012] In one embodiment, the shell portion contains the aromatic polymer (P1) and further contains a non-crosslinkable polymer (P2) which is at least one selected from the group consisting of polyolefins, styrene-based polymers, (meth)acrylic acid-based polymers, and styrene-(meth)acrylic acid-based polymers.

[0013] In one embodiment, the aromatic crosslinking monomer (a) is divinylbenzene.

[0014] In one embodiment, the aromatic monofunctional monomer (b) is at least one selected from the group consisting of styrene and ethylvinylbenzene.

[0015] A method for producing hollow resin particles according to an embodiment of the present invention includes: A method for producing hollow resin particles according to an embodiment of the present invention, comprising: A monomer composition containing an aromatic crosslinkable monomer (a), an aromatic monofunctional monomer (b), and a (meth)acrylic acid ester monomer (c) represented by formula (1), a polymerization initiator, and an organic mixed solution containing an organic solvent having a boiling point of less than 100°C are dispersed in an aqueous solution containing at least one selected from the group consisting of dispersion stabilizers and surfactants, and suspension polymerization is carried out. [ka] (R 1 represents H or CH3, and R 2 represents H, an alkyl group, or a phenyl group, and R 3 -O represents an oxyalkylene group having 2 to 18 carbon atoms, and m is the average number of moles of the oxyalkylene group added, which is a number from 1 to 100.

[0016] Semiconductor materials according to embodiments of the present invention include hollow resin particles according to embodiments of the present invention. [Effects of the Invention]

[0017] According to an embodiment of the present invention, hollow resin particles can be provided that can have low dielectric constant and low dielectric loss tangent by introducing air spaces into a resin layer, and that can be obtained by simply forming hollow portions. Also, a method for easily producing such hollow resin particles can be provided. [Brief explanation of the drawings]

[0018] [Figure 1] FIG. 1 is a TEM photograph of hollow resin particles (1) obtained in Example 1. [Figure 2] FIG. 2 is a TEM photograph of hollow resin particles (2) obtained in Example 2. [Figure 3] FIG. 2 is a TEM photograph of hollow resin particles (3) obtained in Example 3. [Figure 4]FIG. 2 is a TEM photograph of hollow resin particles (4) obtained in Example 4. [Figure 5] FIG. 1 is a TEM photograph of hollow resin particles (5) obtained in Example 5. [Figure 6] FIG. 1 is a TEM photograph of hollow resin particles (6) obtained in Example 6. [Figure 7] FIG. 1 is a TEM photograph of hollow resin particles (7) obtained in Example 7. [Figure 8] FIG. 1 is a TEM photograph of hollow resin particles (8) obtained in Example 8. [Figure 9] FIG. 1 is a TEM photograph of hollow resin particles (9) obtained in Example 9. [Figure 10] FIG. 1 is a TEM photograph of hollow resin particles (10) obtained in Example 10. [Figure 11] FIG. 1 is a TEM photograph of hollow resin particles (11) obtained in Example 11. [Figure 12] FIG. 1 is a TEM photograph of hollow resin particles (12) obtained in Example 12. [Figure 13] FIG. 2 is a TEM photograph of particles (C1) obtained in Comparative Example 1. [Figure 14] FIG. 2 is a TEM photograph of particles (C2) obtained in Comparative Example 2. [Figure 15] FIG. 1 is a TEM photograph of particles (C3) obtained in Comparative Example 3. DETAILED DESCRIPTION OF THE INVENTION

[0019] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these embodiments.

[0020] ≪≪1. Hollow resin particles≫≫ 1-1. Structure 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. 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.

[0021] 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, since the resin component constituting the shell portion is relatively large and can be prevented from penetrating into the hollow portion of the substrate or the like.

[0022] The average particle diameter of the hollow resin particles is preferably 0.1 μm to 5.0 μm, more preferably 0.15 μm to 1.0 μm, even more preferably 0.2 μm to 0.8 μm, and particularly preferably 0.3 μm to 0.6 μm. When the average particle diameter of the hollow resin particles is within the above range, the effects of the present invention can be more effectively achieved. If 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 the hollow resin particles may not have sufficient strength. If the average particle diameter of the hollow resin particles is greater than 5.0 μm, phase separation between the polymer and the solvent, which occurs when the monomer component is polymerized during suspension polymerization, may be difficult to occur, which may make it difficult to form the shell portion.

[0023] ≪1-2. Shell part≫ The shell portion includes an aromatic polymer (P1) obtained by polymerizing a monomer composition containing an aromatic crosslinkable monomer (a), an aromatic monofunctional monomer (b), and a (meth)acrylic acid ester monomer (c). The effects of the present invention can be realized when the shell portion includes an aromatic polymer (P1) obtained by polymerizing a monomer composition containing an aromatic crosslinkable monomer (a), an aromatic monofunctional monomer (b), and a (meth)acrylic acid ester monomer (c). In particular, the effects of the present invention can be realized when a (meth)acrylic acid ester monomer (c) having a specific structure is used as the monomer constituting the aromatic polymer (P1).

[0024] 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, even more preferably 80% by weight to 100% by weight, and particularly preferably 90% by weight to 100% by weight, in order to further exert the effects of the present invention.

[0025] <Aromatic polymer (P1)> The aromatic polymer (P1) is obtained by polymerizing a monomer composition containing an aromatic crosslinkable monomer (a), an aromatic monofunctional monomer (b), and a (meth)acrylic acid ester monomer (c). That is, the aromatic polymer (P1) has structural units derived from the aromatic crosslinkable monomer (a), structural units derived from the aromatic monofunctional monomer (b), and structural units derived from the (meth)acrylic acid ester monomer (c).

[0026] In order to further exhibit the effects of the present invention, the monomer composition preferably contains 10% by weight to 70% by weight of the aromatic crosslinkable monomer (a), 10% by weight to 70% by weight of the aromatic monofunctional monomer (b), and 0.5% by weight to 30% by weight of the (meth)acrylic acid ester monomer (c), and more preferably contains 20% by weight to 65% by weight of the aromatic crosslinkable monomer (a), 20% by weight to 65% by weight of the aromatic monofunctional monomer (b), and 10% by weight of the (meth)acrylic acid ester monomer (c). The composition preferably contains 30% to 25% by weight of aromatic crosslinkable monomer (a), 30% to 60% by weight of aromatic monofunctional monomer (b), and 1.5% to 20% by weight of (meth)acrylic acid ester monomer (c), and particularly preferably contains 40% to 50% by weight of aromatic crosslinkable monomer (a), 40% to 50% by weight of aromatic monofunctional monomer (b), and 2% to 15% by weight of (meth)acrylic acid ester monomer (c).

[0027] The monomer composition contains an aromatic crosslinkable monomer (a), an aromatic monofunctional monomer (b), and a (meth)acrylic acid ester monomer (c). The total content of the aromatic crosslinkable monomer (a), the aromatic monofunctional monomer (b), and the (meth)acrylic acid ester monomer (c) in the monomer composition 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 order to further exhibit the effects of the present invention.

[0028] The monomer composition may contain any appropriate other monomer other than the aromatic crosslinkable monomer (a), the aromatic monofunctional monomer (b), and the (meth)acrylic acid ester monomer (c) within the range that does not impair the effects of the present invention. The other monomer may be one type only or two or more types.

[0029] (Aromatic crosslinking monomer (a)) As the aromatic crosslinkable monomer (a), any suitable 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 (a) include divinylbenzene, divinylnaphthalene, and diallyl phthalate, which can further demonstrate the effects of the present invention. Divinylbenzene is preferred as the aromatic crosslinkable monomer (a) in terms of further demonstrating the effects of the present invention and reactivity.

[0030] The aromatic crosslinkable monomer (a) may be of one type only, or of two or more types.

[0031] (Aromatic monofunctional monomer (b)) As the aromatic monofunctional monomer (b), any suitable aromatic monofunctional monomer can be used 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 (b) include styrene, ethylvinylbenzene, α-methylstyrene, vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, vinylbiphenyl, and vinylnaphthalene, which can further enhance the effects of the present invention. From the viewpoint of further enhancing the effects of the present invention and reactivity, the aromatic monofunctional monomer (b) is preferably at least one selected from the group consisting of styrene and ethylvinylbenzene.

[0032] The aromatic monofunctional monomer (b) may be of one type only, or of two or more types.

[0033] ((Meth)acrylic acid ester monomer (c)) The (meth)acrylic acid ester monomer (c) is represented by formula (1). [ka]

[0034] In formula (1), R 1 represents H or CH3.

[0035] In formula (1), R 2 represents H, an alkyl group, or a phenyl group.

[0036] In formula (1), R 3 -O represents an oxyalkylene group having 2 to 18 carbon atoms. 3 represents an alkylene group having 2 to 18 carbon atoms.

[0037] In 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. 3When -O is any two or more selected from oxyethylene group, oxypropylene group, oxybutylene group, etc., R 3 The addition form of -O may be any of random addition, block addition, alternating addition, etc. The addition form referred to here means the form itself and does not mean that it must be obtained by an addition reaction.

[0038] In 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.

[0039] In formula (1), m represents the average number of moles of oxyalkylene groups added (sometimes referred to as "chain length"). 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.

[0040] In 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. Specifically, for example, -(R 3 -O) m - is -[(C2H4O) p (C3H6O) q ]- (as mentioned above, the addition may be in any form such as random addition, block addition, or alternating addition), then m=p+q.

[0041] Examples of the (meth)acrylic acid ester-based monomer (c), which can further exhibit the effects of the present invention, 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.

[0042] As the (meth)acrylic acid ester-based monomer (c), commercially available products can be used, for example, the "Blenmer" series manufactured by NOF Corporation.

[0043] The (meth)acrylic acid ester-based monomer (c) may be of one type only, or of two or more types.

[0044] <Non-crosslinkable polymer (P2)> The shell portion may contain an aromatic polymer (P1) and further contain a non-crosslinkable polymer (P2) which is at least one selected from the group consisting of polyolefins, styrene-based polymers, (meth)acrylic acid-based polymers, and styrene-(meth)acrylic acid-based polymers.

[0045] The content of the non-crosslinkable polymer (P2) in the shell portion is preferably 0% by weight to 40% by weight, more preferably 0% by weight to 30% by weight, even more preferably 0% by weight to 20% by weight, and particularly preferably 0% by weight to 10% by weight, in order to further exert the effects of the present invention.

[0046] Examples of polyolefins include polyethylene, polypropylene, polyα-olefins, etc. From the viewpoint of solubility in the monomer composition, it is preferable to use a side-chain crystalline polyolefin using a long-chain α-olefin as a raw material, or a low-molecular-weight polyolefin or olefin oligomer produced using a metallocene catalyst.

[0047] Examples of styrene-based polymers include polystyrene, styrene-acrylonitrile copolymers, and acrylonitrile-butadiene-styrene copolymers.

[0048] Examples of the (meth)acrylic acid polymer include polymethyl(meth)acrylate, polyethyl(meth)acrylate, polybutyl(meth)acrylate, and polypropyl(meth)acrylate.

[0049] Examples of styrene-(meth)acrylic acid polymers include styrene-methyl(meth)acrylate copolymer, styrene-ethyl(meth)acrylate copolymer, styrene-butyl(meth)acrylate copolymer, and styrene-propyl(meth)acrylate copolymer.

[0050] 1-3. Dielectric constant of hollow resin particles The dielectric constant of the hollow resin particles according to an embodiment of the present invention is preferably 1.0 to 2.5, more preferably 1.0 to 2.4, and even more preferably 1.0 to 2.3. When the dielectric constant 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. When the dielectric constant of the hollow resin particles according to an embodiment of the present invention exceeds 2.5, a sufficient dielectric reduction effect cannot be obtained even when the hollow resin particles are mixed with, for example, a thermosetting resin.

[0051] The dielectric constant of hollow resin particles according to an embodiment of the present invention can be calculated by referring to, for example, "Dielectric Constant of a Mixed System" (Applied Physics, Vol. 27, No. 8 (1958)). When the dielectric constant of a mixed system of a dispersion medium and hollow resin particles is ε, the dielectric constant of the base material (e.g., a resin composition such as polyimide or epoxy) that serves as the dispersion medium is ε1, the dielectric constant of the hollow resin particles is ε2, and the volume fraction of the hollow resin particles in the mixed system is φ, the following formula holds. That is, if ε, ε1, and φ are experimentally determined, the dielectric constant ε2 of the hollow resin particles can be calculated.

number

[0052] The volume fraction φ of the hollow resin particles in the mixture of the dispersion medium and the hollow resin particles can be determined as follows.

number

[0053] The density of the hollow resin particles was measured using a pycnometer (Cotec Co., Ltd., TQC 50 mL specific gravity bottle) and a liquid polymer, ARUFON UP-1080 (Toa Gosei Co., Ltd., density 1.05 g / cm 3 ) can be experimentally determined. Specifically, hollow resin particles and ARUFON UP-1080 are degassed and stirred using a planetary mixer degasser (KURABO, Mazerustar KK-250) so that the proportion of hollow resin particles is 10% by weight, to prepare a mixture for evaluation. The mixture for evaluation is filled into a 50 mL pycnometer, and the weight of the filled mixture for evaluation is calculated by subtracting the weight of the empty pycnometer from the weight of the pycnometer filled with the mixture. The density of the hollow resin particles can be calculated from this value using the following formula.

number

[0054] ≪1-4. 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, they are suitable for semiconductor materials such as interlayer insulating films, dry film resists, solder resists, bonding wires, magnet wires, semiconductor encapsulants, epoxy encapsulants, mold underfills, underfills, die bond pastes, buffer coating materials, copper-clad laminates, and flexible substrates. Among these, they are particularly suitable for semiconductor materials such as interlayer insulating films, solder resists, magnet wires, epoxy encapsulants, underfills, buffer coating materials, copper-clad laminates, and flexible substrates. Adding hollow resin particles according to an embodiment of the present invention to resins commonly used in such semiconductor materials, such as polyphenylene ether, polyimide, polybismaleimide, and epoxy resins, can reduce dielectric constant and dielectric loss tangent. That is, the semiconductor material according to an embodiment of the present invention includes hollow resin particles according to an embodiment of the present invention. The hollow resin particles according to an embodiment of the present invention can also be used in applications such as coating compositions, cosmetics, paper coating compositions, heat-insulating compositions, light-diffusing compositions, and light-diffusing films.

[0055] 2. Method for producing hollow resin particles A method for producing hollow resin particles according to an embodiment of the present invention comprises dispersing a monomer composition containing an aromatic crosslinkable monomer (a), an aromatic monofunctional monomer (b), and a (meth)acrylic acid ester monomer (c) represented by formula (1), a polymerization initiator, and an organic mixed solution containing an organic solvent having a boiling point of less than 100°C, in an aqueous solution containing at least one selected from the group consisting of a dispersion stabilizer and a surfactant, and then performing suspension polymerization. [ka] (R 1 represents H or CH3, and R 2 represents H, an alkyl group, or a phenyl group, and R 3 -O represents an oxyalkylene group having 2 to 18 carbon atoms, and m is the average number of moles of the oxyalkylene group added, which is a number from 1 to 100.

[0056] Dispersion of the organic mixed solution in the aqueous solution is not particularly limited, and can be carried out by any known method, as long as the organic mixed solution can be present in the aqueous solution in the form of droplets.

[0057] In the method for producing hollow resin particles according to an embodiment of the present invention, the monomer composition contained in the organic mixed solution contains an aromatic crosslinkable monomer (a), an aromatic monofunctional monomer (b), and a (meth)acrylic acid ester monomer (c), and therefore an organic solvent having a boiling point of less than 100°C can be preferably used as the organic solvent used in suspension polymerization, making it easier to remove the solvent from the hollow portions of the obtained hollow resin particles and reducing production costs.

[0058] ≪2-1. Aqueous solution (aqueous phase)≫ The aqueous solution contains an aqueous medium and at least one selected from the group consisting of a dispersion stabilizer and a surfactant.

[0059] Examples of aqueous media include water and mixed media of water and lower alcohols (methanol, ethanol, etc.).

[0060] Examples of dispersion stabilizers include polyvinyl alcohol, polycarboxylic acid, celluloses (e.g., hydroxyethyl cellulose, carboxymethyl cellulose), and polyvinylpyrrolidone. Inorganic water-soluble polymer compounds such as sodium tripolyphosphate can also be used in combination. Other examples include phosphates such as calcium phosphate, magnesium phosphate, aluminum phosphate, and zinc phosphate; pyrophosphates such as calcium pyrophosphate, magnesium pyrophosphate, aluminum pyrophosphate, and zinc pyrophosphate; and poorly water-soluble inorganic compounds such as calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, and colloidal silica.

[0061] The amount of dispersion stabilizer added is preferably 0.5 to 10 parts by weight relative to 100 parts by weight of the organic mixed solution. Only one type of dispersion stabilizer may be used, or two or more types may be used.

[0062] Examples of the surfactant include anionic surfactants, cationic surfactants, zwitterionic surfactants, and nonionic surfactants.

[0063] Examples of the anionic surfactant include non-reactive anionic surfactants such as alkyl sulfate fatty acid salts, alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkanesulfonates, alkyldiphenylethersulfonates, dialkylsulfosuccinates, monoalkylsulfosuccinates, and polyoxyethylene alkylphenylether phosphates; and reactive anionic surfactants such as polyoxyethylene-1-(allyloxymethyl) alkyl ether sulfate ammonium salts, polyoxyethylene alkylpropenylphenyl ether sulfate ammonium salts, and polyoxyalkylene alkenyl ether ammonium sulfate.

[0064] Examples of cationic surfactants include alkyltrimethylammonium salts, alkyltriethylammonium salts, dialkyldimethylammonium salts, dialkyldiethylammonium salts, and N-polyoxyalkylene-N,N,N-trialkylammonium salts.

[0065] Examples of amphoteric surfactants include lauryl dimethylamine oxide, phosphate salts, and phosphite surfactants.

[0066] Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polysorbitan fatty acid esters, polyoxyethylene alkylamines, glycerin fatty acid esters, and oxyethylene-oxypropylene block polymers.

[0067] The amount of surfactant added is preferably 0.01 to 1 part by weight relative to 100 parts by weight of the organic mixed solution. Only one type of surfactant may be used, or two or more types may be used.

[0068] The aqueous solution may contain any other appropriate components as long as the effects of the present invention are not impaired.

[0069] ≪2-2. Organic mixed solution (oil phase)≫ The organic mixed solution contains a monomer composition including an aromatic crosslinkable monomer (a), an aromatic monofunctional monomer (b), and a (meth)acrylic acid ester monomer (c), a polymerization initiator, and an organic solvent having a boiling point of less than 100°C.

[0070] For the monomer composition contained in the organic mixed solution, the explanation in the section <Aromatic polymer (P1)> in <<1-2. Shell portion>> of <<1. Hollow resin particles>> can be directly applied.

[0071] As the polymerization initiator, any suitable polymerization initiator can be used as long as it does not impair the effects of the present invention. Examples of such polymerization initiators include organic peroxides such as lauroyl peroxide, benzoyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, t-butylperoxy-2-ethylhexanoate, and di-t-butyl peroxide; and azo compounds such as 2,2'-azobisisobutyronitrile, 1,1'-azobiscyclohexanecarbonitrile, and 2,2'-azobis(2,4-dimethylvaleronitrile).

[0072] The amount of the polymerization initiator added is preferably in the range of 0.1 to 5 parts by weight based on 100 parts by weight of the monomer composition. The polymerization initiator may be of one kind or two or more kinds.

[0073] Suitable organic solvents having a boiling point of less than 100° C. in the method for producing hollow resin particles according to an embodiment of the present invention include, for example, heptane, hexane, cyclohexane, methyl acetate, ethyl acetate, methyl ethyl ketone, chloroform, and carbon tetrachloride.

[0074] The organic solvent having a boiling point of less than 100° C. may be a mixed solvent.

[0075] The amount of the organic solvent having a boiling point of less than 100° C. to be added is preferably 20 parts by weight to 250 parts by weight based on 100 parts by weight of the monomer composition.

[0076] The organic mixed solution may contain any other appropriate component within the scope of not impairing the effects of the present invention, such as the non-crosslinkable polymer (P2) in 1-2. Shell portion of 1. Hollow resin particles.

[0077] The amount of the non-crosslinkable polymer (P2) added is preferably 0 to 67 parts by weight based on 100 parts by weight of the monomer composition. The non-crosslinkable polymer (P2) may be one type or two or more types.

[0078] <2-3. Suspension Polymerization> The organic mixed solution is dispersed in an aqueous solution, and the resulting suspension is polymerized and preferably post-heated to obtain hollow resin particles.

[0079] Any suitable dispersion method can be adopted for the dispersion, as long as it can cause the organic mixed solution to exist in droplets in the aqueous solution, as long as the effects of the present invention are not impaired. A typical example of such a dispersion method is a dispersion method using a homogenizer, such as an ultrasonic homogenizer or a high-pressure homogenizer.

[0080] 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, and is preferably 30°C to 80°C.

[0081] The polymerization time may be any appropriate 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.

[0082] Post-heating, which is preferably carried out after polymerization, is a treatment suitable for obtaining hollow resin particles with a high degree of perfection.

[0083] 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, and is preferably 70°C to 120°C.

[0084] The post-heating time preferably carried out after polymerization can be any appropriate time within the range that does not impair the effects of the present invention, and is preferably 1 to 10 hours. [Example]

[0085] 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."

[0086] (Average particle size) The Z-average particle diameter of the hollow resin particles or particles was measured using a dynamic light scattering method, and the measured Z-average particle diameter was taken as the average particle diameter of the obtained hollow resin particles or particles. The hollow resin particles or particles were diluted with ion-exchange water to a 0.1 wt% aqueous dispersion, which was then irradiated with laser light to measure the intensity of the scattered light from the hollow resin particles or particles over time in microseconds. The scattering intensity distribution of the detected hollow resin particles or particles was then fitted to a normal distribution, and the Z-average particle size of the hollow resin particles or particles was calculated using cumulant analysis. This Z-average particle size can be easily measured using a commercially available particle size measuring device. In the following examples and comparative examples, the Z-average particle size was measured using a particle size measuring device (Zetasizer Nano ZS manufactured by Malvern Instruments). Typically, commercially available particle size measuring devices are equipped with data analysis software, which automatically analyzes the measurement data to calculate the Z-average particle size.

[0087] (TEM measurement: Observation of hollow resin particles or the presence or absence of hollows in particles and their shapes) The hollow resin particles or particles as dry powder were surface treated (10 Pa, 5 mA, 10 seconds) using a Meiwafosis "Osmium Coater Neoc-Pro" coating device. The hollow resin particles or particles were then observed using a TEM (transmission electron microscope, Hitachi High-Technologies Corporation H-7600) to confirm the presence or absence of hollowness and the shape of the hollow resin particles or particles. Images were taken at an accelerating voltage of 80 kV and a magnification of 5,000x or 10,000x.

[0088] Example 1 Styrene (St) 1.15 g, divinylbenzene (DVB) 810 (Nippon Steel Chemical & Material Co., Ltd., 81% content, 19% is ethylvinylbenzene (EVB)) 1.85 g, heptane 2.4 g, HS Crystal 4100 (side chain crystalline polyolefin, Toyokuni Oil Mills Co., Ltd.) 0.3 g, Blenmar 50PEP-300 (polyethylene glycol propylene glycol monomethacrylate (in formula (1), R 1 =CH3, R 2 =H, (R 3 -O) m =[(C2H4O) 3.5 (C3H6O) 2.5 ], random addition form, NOF Corporation) 0.3 g, and Perloyl L (polymerization initiator, NOF Corporation) 0.099 g were mixed to prepare an oil phase. Next, 34 g of ion-exchanged water and 0.017 g of Rapisol A-80 (surfactant, NOF Corporation) were mixed to prepare an aqueous phase. The oil phase was added to the aqueous phase, and a suspension was prepared using an ultrasonic homogenizer (SONIFIER 450, manufactured by Branson, conditions: Duty Cycle = 50%, Output Control = 5, processing time 3 minutes). The resulting suspension was heated at 70°C for 4 hours to polymerize, yielding a slurry. The resulting slurry was heated at 100°C for 24 hours to obtain hollow resin particles (1) as a dry powder. The resulting hollow resin particles (1) had an average particle diameter of 356 nm and a particle density of 0.65 g / cm. 3 The results of TEM observation of the obtained hollow resin particles (1) are shown in Figure 1. It was confirmed that the hollow resin particles (1) were hollow resin particles with a hollow space surrounded by a shell. The blending amounts and other information are shown in Table 1.

[0089] Example 2 Hollow resin particles (2) were obtained by the same procedure as in Example 1, except that 0.92 g of styrene, 1.48 g of divinylbenzene 810, 3.0 g of heptane, and 0.10 g of Peroyl L were used. The average particle diameter of the obtained hollow resin particles (2) was 382 nm, and the particle density was 0.64 g / cm. 3 The results of TEM observation of the obtained hollow resin particles (2) are shown in Figure 2. It was confirmed that the hollow resin particles (2) were hollow resin particles with a hollow space surrounded by a shell. The blending amounts and other information are shown in Table 1.

[0090] Example 3 Hollow resin particles (3) were obtained by the same procedure as in Example 1, except that 1.49 g of styrene, 2.41 g of divinylbenzene 810, 1.5 g of heptane, and 0.126 g of Peroyl L were used. The average particle diameter of the obtained hollow resin particles (3) was 329 nm, and the particle density was 0.69 g / cm. 3 The results of TEM observation of the obtained hollow resin particles (3) are shown in Figure 3. It was confirmed that the hollow resin particles (3) were hollow resin particles with a hollow space surrounded by a shell. The blending amounts and other information are shown in Table 1.

[0091] Example 4 Hollow resin particles (4) were obtained by the same procedure as in Example 1, except that 1.19 g of styrene, 1.93 g of divinylbenzene 810, 0.10 g of Perloyl L, and 0.18 g of polystyrene (PS) (non-crosslinked, weight-average molecular weight 300,000) were used instead of 0.3 g of HS Crysta 4100 (side-chain crystalline polyolefin, Toyokuni Oil Mills Co., Ltd.). The average particle diameter of the obtained hollow resin particles (4) was 390 nm, and the particle density was 0.67 g / cm. 3 The results of TEM observation of the obtained hollow resin particles (4) are shown in Figure 4. It was confirmed that the hollow resin particles (4) were hollow resin particles with a hollow space surrounded by a shell. The blending amounts and other information are shown in Table 1.

[0092] Example 5 Hollow resin particles (5) were obtained by the same procedure as in Example 1, except that 0.6 g of Blenmar 50PEP-300 was used and HS Crysta 4100 was not used. The average particle diameter of the obtained hollow resin particles (5) was 310 nm. The TEM observation results of the obtained hollow resin particles (5) are shown in FIG. 5. It was confirmed that the hollow resin particles (5) were hollow resin particles having a hollow space surrounded by a shell. The blending amounts and other information are shown in Table 1.

[0093] Example 6 Blemmer 50PEP-300 (polyethylene glycol propylene glycol monomethacrylate (in formula (1), R 1 =CH3, R 2 =H, (R 3 -O) m =[(C2H4O) 3.5 (C3H6O) 2.5 ], random addition form), NOF Corporation) 0.3 g, instead of Blenmar PME-100 (polyethylene glycol methacrylate (in formula (1), R 1 =CH3, R 2 =CH3, (R 3 -O) mHollow resin particles (6) were obtained by the same procedure as in Example 1, except that 0.3 g of PEG-40 (C2H4O) (NOF Corporation) was used. The average particle diameter of the obtained hollow resin particles (6) was 520 nm. The TEM observation results of the obtained hollow resin particles (6) are shown in FIG. 6. It was confirmed that the hollow resin particles (6) were hollow resin particles having a hollow space surrounded by a shell. The blending amounts and other information are shown in Table 1.

[0094] Example 7 Hollow resin particles (7) were obtained by the same procedure as in Example 3, except that 0.3 g of Blenmar PME-100 was used instead of 0.3 g of Blenmar 50PEP-300. The average particle diameter of the obtained hollow resin particles (7) was 501 nm, and the particle density was 0.63 g / cm. 3 The results of TEM observation of the obtained hollow resin particles (7) are shown in Figure 7. It was confirmed that the hollow resin particles (7) were hollow resin particles with a hollow space surrounded by a shell. The blending amounts and other information are shown in Table 1.

[0095] Example 8 Instead of using 0.3 g of Blemmer 50PEP-300, Blemmer 55PET-800 (polyethylene glycol tetramethylene glycol monomethacrylate (R in formula (1))) was used. 1 =CH3, R 2 =H, (R 3 -O) m =[(C2H4O) 10 Hollow resin particles (8) were obtained by the same procedure as in Example 3, except that 0.3 g of [(C4H8O)5], random addition form) was used. The average particle diameter of the obtained hollow resin particles (8) was 325 nm. The TEM observation results of the obtained hollow resin particles (8) are shown in Figure 8. It was confirmed that the hollow resin particles (8) were hollow resin particles having a hollow space surrounded by a shell. The blending amounts and other information are shown in Table 1.

[0096] Example 9 Hollow resin particles (9) were obtained by the same procedure as in Example 3, except that 0.0081 g of Coatamin 86W (surfactant, Kao Corporation) was used instead of 0.017 g of Rapisol A-80. The average particle diameter of the obtained hollow resin particles (9) was 539 nm. The TEM observation results of the obtained hollow resin particles (9) are shown in FIG. 9. It was confirmed that the hollow resin particles (9) were hollow resin particles having a hollow space surrounded by a shell. The blending amounts and other information are shown in Table 1.

[0097] Example 10 Hollow resin particles (10) were obtained by the same procedure as in Example 3, except that 0.034 g of Adekamin 4MAC-30 (surfactant, ADEKA Corporation) was used instead of 0.017 g of Rapisol A-80. The average particle diameter of the obtained hollow resin particles (10) was 430 nm. The TEM observation results of the obtained hollow resin particles (10) are shown in FIG. 10. It was confirmed that the hollow resin particles (10) were hollow resin particles having a hollow space surrounded by a shell. The blending amounts and other information are shown in Table 1.

[0098] Example 11 Hollow resin particles (11) were obtained by the same procedure as in Example 3, except that 0.0076 g of Adekamin 4MAC-30 was used instead of 0.017 g of Rapisol A-80. The average particle diameter of the obtained hollow resin particles (11) was 1270 nm. The TEM observation results of the obtained hollow resin particles (11) are shown in FIG. 11. It was confirmed that the hollow resin particles (11) were hollow resin particles having a hollow space surrounded by a shell. The blending amounts and other information are shown in Table 1.

[0099] Example 12 Hollow resin particles (12) were obtained by the same procedure as in Example 3, except that 1.38 g of styrene, 2.22 g of divinylbenzene 810, 1.5 g of cyclohexane instead of heptane, 0.6 g of HS Crysta 4100, 0.054 g of Perloyl L, and 0.0085 g of Lapisol A-80 were used. The average particle diameter of the obtained hollow resin particles (12) was 416 nm. The TEM observation results of the obtained hollow resin particles (12) are shown in FIG. 12. It was confirmed that the hollow resin particles (12) were hollow resin particles having a hollow center surrounded by a shell. The blending amounts and other information are shown in Table 1.

[0100] Comparative Example 1 An oil phase was prepared by mixing 1.74 g of methyl methacrylate (MMA), 1.74 g of dipentaerythritol hexaacrylate (ADPH) (Shin-Nakamura Chemical Co., Ltd.), 2.4 g of toluene, 0.126 g of polystyrene (non-crosslinked, weight-average molecular weight 300,000), and 0.104 g of Perloyl L (polymerization initiator, NOF Corporation). Next, 34 g of ion-exchanged water and 0.034 g of Rapisol A-80 (surfactant, NOF Corporation) were mixed to prepare an aqueous phase. The oil phase was added to the aqueous phase, and a suspension was prepared using an ultrasonic homogenizer (SONIFIER 450, manufactured by Branson, conditions: Duty Cycle = 50%, Output Control = 5, processing time 3 minutes). The resulting suspension was heated at 70°C for 4 hours to polymerize, yielding a slurry. The resulting slurry was heated at 100°C for 24 hours to obtain particles (C1) as a dry powder. The resulting particles (C1) had an average particle diameter of 478 nm and a particle density of 0.614 g / cm. 3 The results of TEM observation of the obtained particles (C1) are shown in Figure 13. It was confirmed that the particles (C1) were hollow resin particles with a hollow space surrounded by a shell. The blending amounts and other information are shown in Table 1.

[0101] Comparative Example 2 Particles (C2) were obtained by the same procedure as in Example 1, except that 1.31 g of styrene, 2.11 g of divinylbenzene 810, 0.10 g of Perloyl L, and 0.18 g of polystyrene (non-crosslinked, weight-average molecular weight 300,000) were used instead of 0.3 g of HS Crysta 4100 (side-chain crystalline polyolefin, Toyokuni Oil Mills Co., Ltd.), Blenmar 50PEP-300 was not used, and 0.36 g of reactive surfactant RN2025 (Dai-ichi Kogyo Seiyaku Co., Ltd.) was added to the aqueous phase. The average particle diameter of the obtained particles (C2) was 350 nm. The TEM observation results of the obtained particles (C2) are shown in Figure 14. It was confirmed that particles (C2) did not become hollow resin particles with a hollow space surrounded by a shell. The blending amounts and other information are shown in Table 1.

[0102] Comparative Example 3 Particles (C3) were obtained by the same procedure as in Example 1, except that 1.38 g of styrene, 2.22 g of divinylbenzene 810, 0.10 g of Perloyl L, and 0.18 g of polystyrene (non-crosslinked, weight-average molecular weight 300,000) were used, and HS Crysta 4100 and Blenmar 50PEP-300 were not used. The average particle diameter of the obtained particles (C3) was 430 nm. The TEM observation results of the obtained particles (C3) are shown in Figure 15. It was confirmed that particles (C3) did not become hollow resin particles with a hollow space surrounded by a shell. The blending amounts and other information are shown in Table 1.

[0103] [Table 1]

[0104] As shown in Examples 1 to 12, it can be seen that when the shell contains an aromatic polymer (P1) obtained by polymerizing a monomer composition containing an aromatic crosslinkable monomer (a), an aromatic monofunctional monomer (b), and a (meth)acrylic acid ester monomer (c) represented by formula (1), hollow resin particles having a hollow space surrounded by a shell and an average particle size of 0.1 μm to 5.0 μm can be obtained without using a high-boiling point compound such as hexadecane.

[0105] <Performance evaluation 1> To a mixture of 8.3 g of ethyl acetate and 1.7 g of solvent-soluble polyimide KPI-MX300F (Kawamura Sangyo Co., Ltd.), 1.6 g of ethyl acetate in which each particle had been dispersed at a concentration of 10 wt% was added, and the mixture was degassed and stirred using a planetary stirring defoamer (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 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. The film samples containing each particle were then cooled to room temperature. The dielectric constant and dielectric loss tangent of the resulting films were evaluated using the cavity resonance method (measurement frequency: 5.8 GHz). The results are shown in Table 2.

[0106] [Table 2]

[0107] From the results in Table 2, it can be confirmed that the hollow resin particles provided by the present invention have the effect of lowering the relative dielectric constant and dielectric loss tangent of the substrate, and are therefore effective for the purpose of reducing the dielectric constant and dielectric loss tangent of the substrate.

[0108] <Performance evaluation 2> The slurries obtained in each Example and Comparative Example were dried using a Mini Spray Dryer B-290 (Nihon Buchi Co., Ltd.) to obtain hollow resin particles or particles as a dry powder. 0.425 g of the obtained hollow resin particles or particles, 12.1 g of ethyl acetate, and 1.7 g of solvent-soluble polyimide KPI-MX300F (Kawamura Sangyo Co., Ltd.) were mixed and degassed using a planetary mixer defoamer (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 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. The film samples containing each particle were then cooled to room temperature. The dielectric constant and dielectric loss tangent of the resulting films were evaluated using the cavity resonance method (measurement frequency: 5.8 GHz). The results are shown in Table 3.

[0109] [Table 3]

[0110] From the results in Table 3, it can be confirmed that the hollow resin particles provided by the present invention have the effect of lowering the relative dielectric constant of the substrate while suppressing an increase in the dielectric loss tangent compared to the particles (C1) of Comparative Example 1, and are therefore effective in achieving low dielectric constant and low dielectric loss tangent of the substrate. From these results, the relative dielectric constants of the hollow resin particles were calculated to be 1.90 for hollow resin particles (1) of Example 1, 2.20 for hollow resin particles (2) of Example 2, 1.93 for hollow resin particles (3) of Example 3, 1.90 for hollow resin particles (4) of Example 4, 2.20 for hollow resin particles (7) of Example 7, and 2.28 for particles (C1) of Comparative Example 1. The density of the substrate was 1.57 g / cm. 3 It was calculated as:

[0111] <Performance evaluation 3> The slurries obtained in each Example and Comparative Example were dried using a Mini Spray Dryer B-290 (Nihon Buchi Co., Ltd.) to obtain hollow resin particles or particles as a dry powder. 0.4 g of the obtained hollow resin particles or particles and 10 g of ultra-high heat-resistant polyimide varnish (SPIXAREA HR002, Somar Co., Ltd.) were degassed and stirred using a planetary stirring defoamer (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, after which film samples containing each particle were obtained by cooling to room temperature. The dielectric constant and dielectric loss tangent of the resulting films were evaluated using the cavity resonance method (measurement frequency: 5.8 GHz). The results are shown in Table 4.

[0112] [Table 4]

[0113] From the results in Table 4, it can be confirmed that the hollow resin particles provided by the present invention have the effect of lowering the relative dielectric constant and dielectric loss tangent of the substrate, and are therefore effective for the purpose of reducing the dielectric constant and dielectric loss tangent of the substrate. [Industrial Applicability]

[0114] The hollow resin particles according to the embodiment of the present invention and the hollow resin particles obtained by the production method according to the embodiment of the present invention can be used as semiconductor materials and the like.

Claims

1. A hollow resin particle having a shell portion and a hollow portion surrounded by the shell portion, the shell portion comprises an aromatic polymer (P1) obtained by polymerizing a monomer composition comprising an aromatic crosslinkable monomer (a), an aromatic monofunctional monomer (b), and a (meth)acrylic acid ester monomer (c) represented by formula (1), and a non-crosslinkable polymer (P2) which is at least one selected from the group consisting of polyolefins, styrene polymers, (meth)acrylic acid polymers, and styrene-(meth)acrylic acid polymers; Hollow resin particles. 【Chemistry 1】 (R 1 is H or CH 3 represents R 2 represents H, an alkyl group, or a phenyl group, and R 3 -O represents an oxyalkylene group having 2 to 18 carbon atoms, and m represents the average number of moles of the oxyalkylene group added, which is a number from 1 to 100.

2. 2. The hollow resin particle according to claim 1, wherein the oxyalkylene group is at least one selected from the group consisting of an oxyethylene group, an oxypropylene group, and an oxybutylene group.

3. 3. The hollow resin particles according to claim 1, wherein the monomer composition comprises 10% by weight to 70% by weight of an aromatic crosslinkable monomer (a), 10% by weight to 70% by weight of an aromatic monofunctional monomer (b), and 0.5% by weight to 30% by weight of a (meth)acrylic acid ester monomer (c) represented by general formula (1).

4. 4. The hollow resin particle according to claim 1, wherein the aromatic crosslinkable monomer (a) is divinylbenzene.

5. 5. The hollow resin particles according to claim 1, wherein the aromatic monofunctional monomer (b) is at least one selected from the group consisting of styrene and ethylvinylbenzene.

6. A method for producing hollow resin particles according to any one of claims 1 to 5, comprising: a monomer composition including an aromatic crosslinkable monomer (a), an aromatic monofunctional monomer (b), and a (meth)acrylic acid ester-based monomer (c) represented by formula (1), a non-crosslinkable polymer (P2) which is at least one selected from the group consisting of a polyolefin, a styrene-based polymer, a (meth)acrylic acid-based polymer, and a styrene-(meth)acrylic acid-based polymer, a polymerization initiator, and an organic mixed solution including an organic solvent having a boiling point of less than 100°C, are dispersed in an aqueous solution containing at least one selected from the group consisting of a dispersion stabilizer and a surfactant, and suspension polymerization is carried out; A method for producing hollow resin particles. 【Chemistry 2】 (R 1 is H or CH 3 represents R 2 represents H, an alkyl group, or a phenyl group, and R 3 -O represents an oxyalkylene group having 2 to 18 carbon atoms, and m represents the average number of moles of the oxyalkylene group added, which is a number from 1 to 100.

7. A semiconductor material comprising the hollow resin particles according to any one of claims 1 to 5.

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