Hollow resin particles, production method therefor, and use therefor

Abstract

Hollow resin particles according to an embodiment of the present invention each have a shell part and a hollow portion surrounded by the shell part. The shell part contains a polymer (P1) having a specific ether structure and a non-crosslinkable polymer (P2). A 1.0 mm-thick cured product obtained by curing a mixture of the hollow resin particles at 10 wt%, a polyphenylene ether resin, a crosslinking agent, and a polymerization initiator demonstrates a total light transmittance in the thickness direction of 20.00% or less.

Description

Hollow resin particles, methods for producing the same, and their applications

[0001] This invention relates to hollow resin particles, a method for producing the same, and applications thereof.

[0002] To accelerate information processing using electronic devices, attempts are being made to reduce the dielectric constant and dielectric loss tangent of the insulating layer of multilayer printed circuit boards. As part of this effort, studies are being conducted to introduce voids into the resin layer by mixing hollow particles, which have a shell portion and a hollow portion surrounded by the shell portion, into thermosetting resins, thereby reducing the dielectric constant and dielectric loss tangent.

[0003] Hollow particles used in such applications require high heat resistance so that, for example, they do not undergo substantial changes even when heated during molding processes of thermosetting resins containing the hollow particles or when using solder.

[0004] Furthermore, when hollow particles are mixed with thermosetting resins to form a resin composition, in conventional hollow particles, the thermosetting resin penetrates into the interior of the hollow particles during kneading. As a result, the voids inside the hollow particles cannot be maintained, and the low dielectric properties expected of the resin composition do not materialize.

[0005] Patent Document 1 describes using a resin composition containing hollow silica particles in the prepreg. However, the hollow particles described in Patent Document 1 are unsuitable for the purpose of reducing the dielectric loss tangent of the resin layer due to their composition, and thermosetting resins and the like tend to penetrate into the hollow particles.

[0006] Patent Document 2 describes hollow resin particles aimed at low dielectric strength and low dielectric loss tangent. However, the hollow resin particles described in Patent Document 2 are brittle and easily broken, making it easy for thermosetting resins and the like to penetrate into the hollow particles. Furthermore, the hollow resin particles described in Patent Document 2 have insufficient heat resistance due to their composition.

[0007] Japanese Patent Publication No. 2024-081140, International Publication No. 2024 / 048093

[0008] The present invention was made to solve the above-mentioned conventional problems, and its main objective is to provide hollow resin particles having a shell portion and a hollow portion surrounded by the shell portion, which suppress the penetration of thermosetting resins and other materials into the particle interior, and which have excellent heat resistance and excellent dielectric properties. Furthermore, it aims to provide applications for such hollow resin particles. Moreover, it aims to provide a method for producing such hollow resin particles.

[0009] [1] Hollow resin particles according to embodiments of the present invention are hollow resin particles having a shell portion and a hollow portion surrounded by the shell portion, wherein the shell portion comprises a polymer (P1) having an ether structure represented by formula (1) and a non-crosslinkable polymer (P2), and the total light transmittance in the thickness direction of a cured product with a thickness of 1.0 mm obtained by mixing 10 wt% of the hollow resin particles, a polyphenylene ether resin, a crosslinking agent, and a polymerization initiator and curing it is 20.00% or less. [2] In the hollow resin particles described in [1] above, the polymer (P1) is a polymer obtained by reacting a composition containing a compound (A) having an ether structure and a radical reactive group represented by formula (1) and a monomer (M) that reacts with the compound (A), and the monomer (M) may contain an aromatic crosslinkable monomer. [3] In the hollow resin particles described in [2] above, the monomer (M) may contain an aromatic monofunctional monomer. [4] In the hollow resin particles described in [2] or [3] above, the composition contains the non-crosslinkable polymer (P2), and when the total of the compound (A), the monomer (M), and the non-crosslinkable polymer (P2) is 100 parts by weight, the compound (A) may be 1 part by weight to 50 parts by weight. [5] In the hollow resin particles described in any one of [2] to [4] above, the composition contains the non-crosslinkable polymer (P2), and when the total of the compound (A), the monomer (M), and the non-crosslinkable polymer (P2) is 100 parts by weight, the non-crosslinkable polymer (P2) may be 0.1 part by weight to 20 parts by weight. [6] The hollow resin particles described in any one of [1] to [5] above may have a single hollow structure in which the hollow portion consists of one hollow region. [7] The hollow resin particles described in any one of [1] to [6] above may have a 5% thermal weight loss temperature of 300 °C or higher when heated at 10 °C / min in an air atmosphere. [8] The hollow resin particles described in any one of [1] to [7] above, when 10 wt% of the hollow resin particles, a polyphenylene ether resin, a crosslinking agent, and a polymerization initiator are mixed and cured, the lightness L in the CIE 1976 L * a * b * brightness L1 based on the color space * chromaticity a1 * and chromaticity b1 * and the L on the surface of a 1.0 mm thick first cured product obtained by mixing and curing the polyphenylene ether resin, the crosslinking agent, and the polymerization initiator * a * b * brightness L2 based on the color space * chromaticity a2* , and chromaticity b2 * And may satisfy equation (2). 20.0 ≤ ΔE * ab = [(L1 * -L2 * ) 2 + (a1 * -a2 * ) 2 + (b1 * -b2 * ) 2 ] 1 / 2 ... (2) [9] The hollow resin particles described in any one of [1] to [8] above may have a relative permittivity of 2.00 or less at a measurement frequency of 10 GHz.

[10] The hollow resin particles described in any one of [1] to [9] above may have a dielectric loss tangent of 0.00200 or less at a measurement frequency of 10 GHz.

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

[10] above may be used in a resin composition for semiconductor components.

[12] The resin composition for semiconductor components of the present invention includes the hollow resin particles described in any one of [1] to

[11] above.

[13] 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, comprising reacting a composition containing a compound (A) having an ether structure and radical reactive groups represented by formula (1) and a non-crosslinkable polymer (P2) in an aqueous medium in the presence of a non-reactive solvent.

[14] In the method for producing hollow resin particles described in

[13] above, the composition may include a monomer (M) that reacts with the compound (A), and the compound (A) and the monomer (M) may be suspended polymerized by the reaction.

[15] In the method for producing hollow resin particles described in

[14] above, the monomer (M) may include an aromatic crosslinkable monomer and an aromatic monofunctional monomer.

[0010] According to embodiments of the present invention, it is possible to provide hollow resin particles that suppress penetration into the interior of thermosetting resins and other particles, and that have excellent heat resistance and excellent dielectric properties. Furthermore, applications for such hollow resin particles can be provided. Moreover, a method for producing such hollow resin particles can be provided.

[0011] This is a schematic cross-sectional view illustrating the structure of the hollow portion. This is an SEM image of the appearance of particle (A1) obtained in Example 1. This is an SEM image of the cross-section of particle (A1) obtained in Example 1. This is an SEM image of the appearance of particle (A2) obtained in Example 2. This is an SEM image of the cross-section of particle (A2) obtained in Example 2. This is an SEM image of the appearance of particle (A3) obtained in Example 3. This is an SEM image of the cross-section of particle (A3) obtained in Example 3. This is an SEM image of the appearance of particle (A4) obtained in Example 4. This is an SEM image of the cross-section of particle (A4) obtained in Example 4. This is an SEM image of the appearance of particle (A5) obtained in Example 5. This is an SEM image of the cross-section of particle (A5) obtained in Example 5. This is an SEM image of the appearance of particle (A6) obtained in Example 6. This is an SEM image of the cross-section of particle (A6) obtained in Example 6. This is an SEM image of the appearance of particle (A7) obtained in Example 7. This is an SEM image of the cross-section of the particle (A7) obtained in Example 7. This is an SEM image of the appearance of the particle (A8) obtained in Example 8. This is an SEM image of the cross-section of the particle (A8) obtained in Example 8. This is an SEM image of the appearance of the particle (A9) obtained in Example 9. This is an SEM image of the cross-section of the particle (A9) obtained in Example 9. This is an SEM image of the appearance of the particle (CA1) obtained in Comparative Example 1. This is an SEM image of the cross-section of the particle (CA1) obtained in Comparative Example 1. This is an SEM image of the appearance of the particle (CA2) obtained in Comparative Example 2. This is an SEM image of the cross-section of the particle (CA2) obtained in Comparative Example 2. This is an SEM image of the appearance of the particle (CA3) obtained in Comparative Example 3. This is an SEM image of the cross-section of the particle (CA3) obtained in Comparative Example 3.

[0012] The following describes embodiments of the present invention, but the present invention is not limited to these embodiments.

[0013] In this specification, the expression "(meth)acrylic" means "acrylic and / or methacrylic," the expression "(meth)acrylate" means "acrylate and / or methacrylate," and the expression "(meth)acrylonitrile" means "acrylonitrile and / or methacrylonitrile."

[0014] ≪≪1. Hollow Resin Particles≫≫ ≪1-1. Structure and Characteristics of Hollow Resin Particles≫ The hollow resin particles according to the embodiment of the present invention have a shell portion and a hollow portion surrounded by the shell portion. The hollow resin particles according to the embodiment of the present invention have a total light transmittance in the thickness direction of a cured product with a thickness of 1.0 mm obtained by mixing 10 wt% of the hollow resin particles, polyphenylene ether resin, a crosslinking agent, and a polymerization initiator and curing it, which is 20.00% or less.

[0015] In this context, "hollow" refers to a state in which the interior is filled with a substance other than resin, such as a gas or liquid. Preferably, it refers to a state in which the interior is filled with gas, as this allows the effects of the present invention to be more fully realized.

[0016] The hollow portion may consist of a single hollow region, or it may consist of multiple hollow regions or a porous structure. Figure 1(a) is a schematic cross-sectional view of a hollow resin particle having a single hollow structure, where the hollow portion consists of a single hollow region. Figure 1(b) is a schematic cross-sectional view of a hollow resin particle having multiple hollow regions. Figure 1(c) is a schematic cross-sectional view of a hollow resin particle having a porous structure for the hollow portion. In the embodiments of the present invention, it is preferable that the hollow resin particle has a single hollow structure, where the hollow portion consists of a single hollow region. Having a single hollow portion results in a relatively larger amount of resin components constituting the shell, making the particle less prone to cracking. Such hollow resin particles may be less prone to crushing of the shell even when kneaded in a resin composition. Therefore, having a single hollow portion effectively prevents penetration into the hollow portion of the substrate, etc.

[0017] In this specification, the total light transmittance in the thickness direction of a 1.0 mm thick cured product obtained by mixing 10 wt% hollow resin particles, polyphenylene ether resin, a crosslinking agent, and a polymerization initiator according to embodiments of the present invention may be described as "total light transmittance of a cured product of a 10 wt% hollow resin particle resin composition." In this specification, a 1.0 mm thick cured product obtained by mixing 10 wt% hollow resin particles, polyphenylene ether resin, a crosslinking agent, and a polymerization initiator may be described as "cured product of a 10 wt% hollow resin particle resin composition." The method for producing the cured product and the method for measuring the total light transmittance of the cured product of a 10 wt% hollow resin particle resin composition will be described later.

[0018] The total light transmittance of a cured product of a 10 wt% resin composition containing hollow resin particles can serve as an indicator of the degree to which the resin penetrates into the interior of the hollow resin particles. Specifically, a cured product of a resin composition without particles has a high total light transmittance because no light diffusion occurs due to the particles. In contrast, a cured product of a resin composition containing hollow resin particles in which a sufficient air layer is maintained inside the hollow resin particles has a low total light transmittance because light diffusion occurs due to the air layer. Here, if the base resin constituting the resin composition penetrates into the interior of the hollow resin particles, the air layer is lost, reducing the occurrence of light diffusion and increasing the total light transmittance (i.e., approaching the total light transmittance when no particles are added).

[0019] The hollow resin particles according to the embodiments of the present invention have a low total light transmittance of 20.00% or less for the cured product of a 10 wt% resin composition of hollow resin particles. When hollow resin particles are kneaded with thermosetting resins or the like to form a resin composition, the penetration of resin into the interior of the particles can be suppressed, and the voids inside the particles can be maintained. As a result, the resin composition using the hollow resin particles according to the embodiments of the present invention can exhibit excellent dielectric properties, particularly low dielectric constant.

[0020] The hollow resin particles according to the embodiments of the present invention have a total light transmittance of the cured product of the 10 wt% resin composition of the hollow resin particles preferably of 15.00% or less, more preferably of 10.00% or less, more preferably of 5.00% or less, and even more preferably of 3.00% or less. With the above configuration, the hollow resin particles can suppress the penetration of resin into the interior of the particles and exhibit better dielectric properties. The lower limit of the total light transmittance of the cured product of the 10 wt% resin composition of the hollow resin particles is not particularly limited, and may be, for example, 0.00% or more, 0.01% or more, and even 0.10% or more.

[0021] The polyphenylene ether resin in the cured product of a 10 wt% resin composition of hollow resin particles is the main component of the resin composition. The polyphenylene ether resin is a reactive polyphenylene ether that reacts with the above-mentioned crosslinking agent by a polymerization initiator, and is typically a modified polyphenylene ether having a polymerizable double bond at at least one end. The modified polyphenylene ether preferably has polymerizable double bonds at both ends, and more preferably is a modified oligomer having a low molecular weight difunctional group based on polyphenylene ether. Here, "having a difunctional group" means that a functional group having a double bond, or a functional group having a substituent having a double bond, is located at both ends of the oligomer. The number average molecular weight Mn of the above oligomer is preferably 500 to 3500.

[0022] A preferred example of such a modified polyphenylene ether is the compound represented by the following formula (3).

[0023] In equation (3), n1 and n2 represent integers from 0 to 300 independently of each other, provided that at least one of them is an integer of 1 or more. 3 L represents a divalent linking group. 3The group is preferably selected from the group consisting of alkylene groups, alkenylene groups, -O-, -CO-, -CS-, -SO-, and -SO2-, more preferably an alkylene group, and even more preferably an isopropylidene group (-C(CH3)2-). Examples of commercially available compounds represented by formula (3) include the "Noryl®" series (Noryl® SA9000, etc.) (manufactured by SABIC). As described above, it is preferable that the modified polyphenylene ether has (meth)acryloyl groups at both ends.

[0024] Another preferred example of a modified polyphenylene ether is the compound represented by the following formula (4).

[0025] In formula (4), n1 and n2 represent integers from 0 to 300, independent of each other, provided that at least one of them is an integer of 1 or more. A commercially available example of the compound represented by formula (4) is the "OPE-2St" series (manufactured by Mitsubishi Gas Chemical).

[0026] The crosslinking agent in the cured product of a 10 wt% resin composition of hollow resin particles is a so-called curing agent added to the resin composition during the production of the cured product, and is typically triallyl isocyanurate (TAIC).

[0027] The hollow resin particles according to the embodiment of the present invention are obtained by mixing 10 wt% hollow resin particles, polyphenylene ether resin, a crosslinking agent, and a polymerization initiator, and curing a first cured product with a thickness of 1.0 mm (i.e., a cured product of a 10 wt% resin composition of hollow resin particles) on the surface of the product conforming to CIE 1976 L * a * b * Lightness L1 based on color space * , chromaticity a1 * , and chromaticity b1 * The surface of the 1.0 mm thick second cured product (i.e., a cured product of a resin composition that does not contain hollow resin particles) obtained by mixing and curing polyphenylene ether resin, a crosslinking agent, and a polymerization initiator, conforms to CIE 1976 L * a * b * Lightness L2 based on color space* , chromaticity a2 * , and chromaticity b2 * Preferably, the following equation (2) is satisfied: 20.0 ≤ ΔE * ab = [(L1 * -L2 * ) 2 + (a1 * -a2 * ) 2 + (b1 * -b2 * ) 2 ] 1 / 2 ... (2)

[0028] In other words, the hollow resin particles according to the embodiment of the present invention are L1 * a1 * , b1 * , L2 * a2 * , and b2 * CIE 1976 L calculated from * a * b * Color difference ΔE in color space * It is preferable that ab is 20.0 or higher.

[0029] The above color difference ΔE * The values ​​of ab can also serve as an indicator of the resin penetration into the interior of hollow resin particles. Cured resin compositions containing hollow resin particles in which a sufficient air layer is maintained inside the hollow resin particles exhibit light diffusion due to the air layer, and are therefore particularly L-diffused compared to cured resin compositions without particles (second cured product). * The value of increases. Here, if the base resin constituting the resin composition penetrates into the interior of the hollow resin particles, the air layer is lost, so the occurrence of light diffusion decreases, and L from the second cured product * Change in the value (ΔL) * ) becomes smaller. Chromatic difference ΔE * The value of ab is ΔL * (That is, L1 * -L2 * ) correlates with the color difference ΔE * A larger value for ab indicates less penetration of the hollow resin particles into the resin interior.

[0030] Therefore, ΔE* When ab satisfies the above numerical range, when hollow resin particles according to the embodiment of the present invention are kneaded with a thermosetting resin or the like to form a resin composition, the penetration of resin into the interior of the particles can be further suppressed, and the voids inside the particles can be better maintained. As a result, the resin composition using hollow resin particles according to the embodiment of the present invention can exhibit superior dielectric properties.

[0031] ΔE * ab is preferably 25.0 or higher, more preferably 30.0 or higher, even more preferably 35.0 or higher, and particularly preferably 40.0 or higher. ΔE * The upper limit of ab is not particularly limited, but for example, it could be 80.0 or less, 60.0 or less, or even 50.0 or less.

[0032] The volume-average particle diameter of the hollow resin particles according to the embodiments of the present invention is, for example, 0.1 μm to 10.0 μm, preferably 0.3 μm to 8.0 μm, and more preferably 0.5 to 7.0 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, which may result in hollow resin particles that do not have sufficient strength, and if the hollow resin particles are kneaded with a thermosetting resin or the like, the thermosetting resin or the like may penetrate into the interior of the hollow resin particles. If the average particle diameter of the hollow resin particles is greater than 10.0 μm, it may become difficult for the polymer and solvent to separate during suspension polymerization, which may make it difficult to form the shell portion.

[0033] The coefficient of variation of the volume-average particle diameter of the hollow resin particles according to the embodiments of the present invention is not particularly limited and can be set appropriately depending on the purpose and application. The coefficient of variation of the volume-average particle diameter of the hollow resin particles according to the embodiments of the present invention is, for example, 40.0% or less, preferably 30.0% or less, more preferably 25.0% or less, even more preferably 23.0% or less, and particularly preferably 20.0% or less. The coefficient of variation of the volume-average particle diameter of the hollow resin particles according to the embodiments of the present invention may be, for example, 1.0% or more, 5.0% or more, and even more preferably 10.0% or more.

[0034] The hollow resin particles according to the embodiments of the present invention have a hollowness ratio of preferably 10% to 80%, more preferably 15% to 75%, even more preferably 20% to 70%, and particularly preferably 20% to 60%. When the hollowness ratio of the hollow resin particles is within the above range, the hollow resin particles have superior particle strength and can suppress the penetration of resin into the interior of the particles. As a result, the resin composition using the hollow resin particles can exhibit superior dielectric properties.

[0035] The hollow resin particles according to the embodiment of the present invention have a 5% thermoweight loss temperature of preferably 300.0°C or higher, and more preferably 303.0°C or higher, when heated at a rate of 10°C / min in an air atmosphere. In practice, the upper limit of the 5% thermoweight loss temperature is preferably 500.0°C or lower. If the 5% thermoweight loss temperature of the hollow resin particles according to the embodiment of the present invention, when heated at a rate of 10°C / min in an air atmosphere, falls within the above range, the hollow resin particles according to the embodiment of the present invention can exhibit excellent heat resistance. If the 5% thermoweight loss temperature of the hollow resin particles according to the embodiment of the present invention, when heated at a rate of 10°C / min in an air atmosphere, falls too low and falls outside the above range, for example, when the hollow resin particles are kneaded with a thermosetting resin to form a resin composition, the particles may deform due to heating for the curing reaction, and the hollow portion may be lost. This may reduce the dielectric properties that should be exhibited in the resin composition by the hollow resin particles, such as the low dielectric constant effect and the low dielectric loss tangent effect.

[0036] The hollow resin particles according to the embodiments of the present invention have a 5% thermoweight loss temperature of preferably 320.0°C or higher, more preferably 340.0°C or higher, even more preferably 360.0°C or higher, and particularly preferably 380°C or higher when heated at a rate of 10°C / min in a nitrogen atmosphere. In practice, the upper limit of the 5% thermoweight loss temperature is preferably 500°C or lower. If the 5% thermoweight loss temperature of the hollow resin particles according to the embodiments of the present invention is within the above range when heated at a rate of 10°C / min in a nitrogen atmosphere, the hollow resin particles according to the embodiments of the present invention can exhibit excellent heat resistance. If the 5% thermoweight loss temperature of hollow resin particles according to an embodiment of the present invention, when heated at 10°C / min in a nitrogen atmosphere, is too small and falls outside the above range, for example, when hollow resin particles are kneaded with a thermosetting resin to form a resin composition, the particles may deform due to heating for the curing reaction, causing the hollow portion to be lost. This may reduce the dielectric properties that should be exhibited in the resin composition by the hollow resin particles, such as the low dielectric constant effect and the low dielectric loss tangent effect.

[0037] The hollow resin particles according to the embodiments of the present invention preferably have a relative permittivity of 2.00 or less at a frequency of 10 GHz, more preferably 1.00 to 1.90, even more preferably 1.00 to 1.85, and particularly preferably 1.10 to 1.80. If the relative permittivity at a frequency of 10 GHz is within the above range, the hollow resin particles according to the embodiments of the present invention can exhibit excellent low dielectric properties.

[0038] The hollow resin particles according to the embodiments of the present invention have a dielectric loss tangent at a frequency of 10 GHz, preferably 0 to 0.00200, more preferably 0 to 0.00170, even more preferably 0 to 0.00150, and particularly preferably 0 to 0.00140. If the dielectric loss tangent at a frequency of 10 GHz is within the above range, the hollow resin particles according to the embodiments of the present invention can exhibit excellent low dielectric properties. The dielectric loss tangent at a frequency of 10 GHz of the hollow resin particles according to the embodiments of the present invention may be 0.00010 or higher.

[0039] ≪1-2. Shell Part≫ The shell part includes a polymer (P1) having an ether structure represented by formula (1), and a non-crosslinkable polymer (P2). The effects of the present invention can be realized by the shell part containing a polymer (P1) having such a structure and a non-crosslinkable polymer (P2).

[0040] The polymer (P1) may be of one type or two or more types.

[0041] The content ratio of the polymer (P1) in the shell portion is preferably 60% to 100% by weight, more preferably 70% to 100% by weight, even more preferably 80% to 100% by weight, and particularly preferably 90% to 100% by weight, in order to better exhibit the effects of the present invention.

[0042] The polymer (P1) can be any suitable polymer as long as it has an ether structure represented by formula (1), provided that it does not impair the effects of the present invention. In terms of being able to better express the effects of the present invention, an example of such a polymer (P1) is a polymer obtained by the reaction of a composition containing a compound (A) having an ether structure and a radical reactive group represented by formula (1) and a monomer (M) that reacts with compound (A).

[0043] The compound (A) having an ether structure and a radical-reactive group represented by formula (1) may be one type or two or more types.

[0044] The monomer (M) that reacts with compound (A) may be just one type or two or more types.

[0045] The monomer (M) preferably contains an aromatic crosslinkable monomer, and more preferably contains both an aromatic crosslinkable monomer and an aromatic monofunctional monomer. Therefore, the polymer (P1) is preferably obtained by polymerizing, for example, compound (A), an aromatic crosslinkable monomer, and a monofunctional monomer, and has an ether structure represented by formula (1), a structural unit derived from the aromatic crosslinkable monomer, and a structural unit derived from the aromatic monofunctional monomer.

[0046] The ratio of compound (A) to monomer (M) is, when the total amount of compound (A) and monomer (M) is 100 parts by weight, preferably (1 to 50 parts by weight):(99 to 50 parts by weight), more preferably (2 to 40 parts by weight):(98 to 60 parts by weight), even more preferably (3 to 30 parts by weight):(97 to 70 parts by weight), and particularly preferably (4 to 20 parts by weight):(96 to 80 parts by weight). If the content of compound (A) is too small and outside the above range, the heat resistance may be insufficient. If the content of compound (A) is too large and outside the above range, it may be difficult to form the shell portion and the hollow portion surrounded by the shell portion. For example, when the total amount of compound (A) and monomer (M) is 100 parts by weight, the amount of compound (A) may be 1 to 50 parts by weight.

[0047] As compound (A), any suitable compound can be used as long as it has an ether structure represented by formula (1) and a radical-reactive group, provided that it does not impair the effects of the present invention. The radical-reactive group preferably includes a double bond. Compound (A) is preferably a compound having an ether structure represented by formula (1) and a polymerizable double bond at at least one end. Compound (A) is preferably a modified polyphenylene ether in that it can better express the effects of the present invention. The modified polyphenylene ether is as described in the description of the polyphenylene ether resin of the cured product of the 10 wt% resin composition of hollow resin particles described above. Examples of commercially available modified polyphenylene ethers include the "Noryl®" series (e.g., Noryl® SA9000) (manufactured by SABIC), the "Yupiace®" series (manufactured by Mitsubishi Chemical), the "Zylon®" series (manufactured by Asahi Kasei), and the "OPE-2St" series (manufactured by Mitsubishi Gas Chemical). Compound (A) may also be a modified polyphenylene ether having (meth)acryloyl groups at both ends.

[0048] From the standpoint of enabling the simpler production of hollow resin particles with excellent heat resistance, the modified polyphenylene ether as compound (A) is preferably an oligomer, and its number average molecular weight Mn is preferably 500 to 3500.

[0049] Examples of monomers (M) include crosslinkable monomers and monofunctional monomers. A monomer that reacts with the terminal group of compound (A) is preferred in that it can better exhibit the effects of the present invention.

[0050] Crosslinkable monomers are monomers having two or more radically polymerizable double bonds in their skeleton, and typically have two or more vinyl groups. Examples of crosslinkable monomers include aromatic crosslinkable monomers such as divinylbenzene, divinylnaphthalene, diallyl phthalate, and divinylbiphenyl; polyfunctional (meth)acrylic acid esters such as ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and glycerin tri(meth)acrylate; polyfunctional acrylamide derivatives such as N,N'-methylenebis(meth)acrylamide and N,N'-ethylenebis(meth)acrylamide; and polyfunctional allyl derivatives such as diallylamine and tetraallyloxyethane. In terms of being able to better express the effects of the present invention, aromatic crosslinkable monomers are preferred as the crosslinkable monomer. Aromatic crosslinkable monomers preferably include divinylbenzene. Crosslinkable monomers may be used individually or in combination of two or more.

[0051] Monofunctional monomers are monomers that have one double bond in their skeleton that is capable of radical polymerization, and typically have one vinyl group. Examples of monofunctional monomers include aromatic monofunctional monomers such as styrene, ethyl vinylbenzene, vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, vinyl biphenyl, and vinylnaphthalene; C1-C16 alkyl (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and cetyl (meth)acrylate; dicarboxylic acid ester monomers such as dimethyl maleate, diethyl fumarate, dimethyl fumarate, and diethyl fumarate; maleic anhydride; N-vinylcarbazole; hydroxyalkyl (meth)acrylate monomers such as hydroxyethyl (meth)acrylate; (meth)acrylic acid; 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl phthalic acid. Examples include carboxyl group-containing hydrophilic monomers such as tacryloyloxyethylhexahydrophthalic acid, 2-methacryloyloxyethyl maleic acid, 2-acryloyloxyethylhexahydrophthalic acid, 2-acryloyloxyethyl succinic acid, and 2-acryloyloxyethyl phthalic acid; polyethylene glycol, propylene glycol, monomethacrylate; glycidyl group-containing monomers such as glycidyl (meth)acrylate, allyl glycidyl ether, and 4-hydroxybutyl (meth)acrylate glycidyl ether; epoxy group-containing monomers such as 1,2-epoxy-4-vinylcyclohexane and (meth)acrylate (3,4-epoxycyclohexyl)methyl; acrylamide derivative monomers such as 4-vinylphenyl glycidyl ether (meth)acrylamide; and (meth)acrylonitrile. In terms of being able to better express the effects of the present invention, the monofunctional monomer is preferably an aromatic monofunctional monomer. The aromatic monofunctional monomer preferably contains styrene, and more preferably contains styrene and ethyl vinylbenzene. Monofunctional monomers may be used individually or in combination of two or more.

[0052] When the total amount of compound (A) and monomer (M) is 100 parts by weight, the crosslinkable monomer is preferably 1 to 80 parts by weight, more preferably 1 to 70 parts by weight, more preferably 5 to 65 parts by weight, even more preferably 10 to 60 parts by weight, and particularly preferably 10 to 55 parts by weight.

[0053] When the total amount of compound (A) and monomer (M) is 100 parts by weight, the monofunctional monomer is preferably 1 to 80 parts by weight, more preferably 1 to 70 parts by weight, more preferably 5 to 65 parts by weight, even more preferably 10 to 60 parts by weight, and particularly preferably 10 to 55 parts by weight.

[0054] The total content of crosslinkable monomers and monofunctional monomers in the monomer component (M) is preferably 50% to 100% by weight, more preferably 80% to 100% by weight, even more preferably 90% to 100% by weight, and particularly preferably 95% to 100% by weight, in order to better express the effects of the present invention.

[0055] The monomer component (M) may include any other suitable monomer that is different from either of the crosslinkable monomers or monofunctional monomers described above, as long as it does not impair the effects of the present invention. The other monomer may be one type or two or more types.

[0056] Other monomers that may be included in monomer component (M) include, for example, vinyl halogenated monomers such as vinyl chloride; vinyl carboxylate monomers such as vinyl acetate; olefin monomers such as ethylene; unsaturated imide monomers; vinyl alcohol; silane coupling agents having a vinyl group; phosphate ester monomers; and the like. Monomer component (M) does not necessarily have to contain other monomers.

[0057] The phosphate ester monomer that may be included in the monomer component (M) may be a compound having a phosphate ester structure and a radical-reactive group. In terms of being able to better express the effects of the present invention, such a compound is preferably a compound represented by formula (5).

[0058] In formula (5), R 3 , R 5 R is a linear or branched alkylene group having 1 to 30 carbon atoms. 4 represents a methyl group or a hydrogen atom. In formula (5), m represents 1 to 300. In formula (5), n represents 1 to 3. In formula (5), a is 0 or 1, b is 0 to 300, and c is 0 or 1.

[0059] In formula (5), R 3 Preferably, the alkylene group is a linear or branched alkylene group having 1 to 20 carbon atoms; more preferably, it is a linear or branched alkylene group having 1 to 10 carbon atoms; even more preferably, it is a linear or branched alkylene group having 1 to 8 carbon atoms; particularly preferably, it is a linear or branched alkylene group having 1 to 6 carbon atoms; and most preferably, it is a linear or branched alkylene group having 1 to 4 carbon atoms.

[0060] In formula (5), R 5 Preferably, the alkylene group is a linear or branched alkylene group having 1 to 20 carbon atoms; more preferably, it is a linear or branched alkylene group having 1 to 10 carbon atoms; even more preferably, it is a linear or branched alkylene group having 1 to 8 carbon atoms; particularly preferably, it is a linear or branched alkylene group having 1 to 6 carbon atoms; and most preferably, it is a linear or branched alkylene group having 1 to 4 carbon atoms.

[0061] In formula (5), m is preferably 1 to 100, more preferably 1 to 50, even more preferably 1 to 40, and particularly preferably 1 to 30.

[0062] In formula (5), b is preferably 0 to 100, more preferably 0 to 50, even more preferably 0 to 10, particularly preferably 0 to 5, and most preferably 0 or 1.

[0063] Such compounds may be those that are commercially available. For example, from the viewpoint of compatibility, one such compound is the product name "KAYAMER (registered trademark) PM-21" (manufactured by Nippon Kayaku Co., Ltd.).

[0064] The content of the phosphate ester monomer is preferably 0 to 10 parts by weight, more preferably 0 to 5 parts by weight, even more preferably 0 to 3 parts by weight, and particularly preferably 0 to 1 part by weight, when the total amount of compound (A) and monomer (M) is 100 parts by weight.

[0065] In a composition containing a compound (A) and a monomer (M) that yield a polymer (P1) by reaction, the content of the monomer component (M) is preferably 50% to 99% by weight, more preferably 60% to 98% by weight, even more preferably 70% to 97% by weight, and particularly preferably 80% to 96% by weight, in order to better express the effects of the present invention. Here, the monomer component (M) does not include polymerization initiators, chain transfer agents, and surfactants used in the polymerization reaction.

[0066] The composition may further contain a chain transfer agent in such a way that the effects of the present invention can be more fully expressed. That is, the polymer (P1) may be a polymer obtained by reacting compound (A) and monomer (M) using a chain transfer agent.

[0067] The chain transfer agent may be at least one selected from the group consisting of mercaptan compounds, styrene dimers, terpenes, halogenated hydrocarbons, and α-methylstyrene. Examples of mercaptan compounds include n-octyl mercaptan (1-octanthiol), n-dodecyl mercaptan (1-dodecanethiol), tert-dodecyl mercaptan, 2-hydroxyethyl mercaptan, n-octadecyl mercaptan (stearyl mercaptan), alkylenedithiol, thiocyanuric acid, etc., with n-octyl mercaptan and n-dodecyl mercaptan being preferred. Examples of styrene dimers include α-methylstyrene dimer. Examples of terpenes include γ-terpinene and dipentene. Examples of halogenated hydrocarbons include halogenated hydrocarbons. Of these chain transfer agents, mercaptan, α-methylstyrene, and styrene-based dimers are preferred, mercaptan and α-methylstyrene are more preferred, and mercaptan is even more preferred. These chain transfer agents may be used individually or in combination of two or more.

[0068] The content of the chain transfer agent (B) is preferably 0 to 10 parts by weight, more preferably 0 to 5 parts by weight, even more preferably 0 to 3 parts by weight, and particularly preferably 0 to 1 part by weight, when the total amount of compound (A) and monomer (M) is 100 parts by weight.

[0069] The shell portion contains a non-crosslinkable polymer (P2).

[0070] For example, the above composition, which yields a polymer (P1) through a reaction, can form a shell portion containing polymer (P1) and non-crosslinkable polymer (P2) by including a non-crosslinkable polymer (P2) in addition to compound (A) and monomer component (M). The inclusion of non-crosslinkable polymer (P2) can promote phase separation of polymerization oil droplets during suspension polymerization, thereby improving the density of the shell portion. This suppresses the penetration of thermosetting resins and the like into the particle interior, and as a result, excellent low dielectric properties can be achieved.

[0071] As the non-crosslinkable polymer (P2), any suitable non-crosslinkable polymer can be used within a range that does not impair the effects of the present invention. Preferably, such a non-crosslinkable polymer has a number average molecular weight of 500 to 200,000. Including a non-crosslinkable polymer with a number average molecular weight of 500 to 200,000 can further promote phase separation of polymerized oil droplets during suspension polymerization, thereby improving the density of the shell portion. This results in superior particle strength, suppression of the penetration of thermosetting resins into the particle interior, and consequently, superior low dielectric properties. Note that if a non-crosslinkable polymer with a number average molecular weight of less than 500 is used, phase separation may be less likely to occur, potentially making shell formation difficult. If a non-crosslinkable polymer with a number average molecular weight greater than 200,000 is used, the viscosity of the oil droplets may increase, potentially leading to larger average particle diameters, particle deformation, or difficulty in shell formation. The number-average molecular weight of the non-crosslinkable polymer is more preferably 500 to 150,000, even more preferably 600 to 100,000, and particularly preferably 700 to 70,000.

[0072] Examples of such non-crosslinkable polymers (P2) include polystyrene, polyethylene, polypropylene, aliphatic olefin polymers having 4 or more carbon atoms (may have a linear or branched side-chain structure), polyphenylene ether, modified polyphenylene ether, polymethyl methacrylate, block copolymer of styrene and butadiene (e.g., styrene-butadiene-styrene block copolymer (SBS)), block copolymer of styrene and isoprene (e.g., styrene-isoprene-styrene block copolymer (SIS)), poly(meth)acrylic acid esters (fatty chains having 1 or more carbon atoms, which may be linear or branched), paraffin, etc. Note that the above-mentioned non-crosslinkable polymers (P2) may undergo hydrogenation reactions to at least some of their unsaturated bonds. The non-crosslinkable polymer (P2) may be a single type or two or more types.

[0073] The non-crosslinkable polymer (P2) may contain a hydrocarbon resin. Any suitable compound can be used as the hydrocarbon resin, as long as it does not impair the effects of the present invention. Examples of hydrocarbon resins include aliphatic / aromatic hydrocarbon resins, aromatic hydrocarbon resins, alicyclic hydrocarbon resins, and aliphatic hydrocarbon resins. Preferably, the hydrocarbon resin is at least one selected from the group consisting of aliphatic / aromatic hydrocarbon resins, aromatic hydrocarbon resins, and aliphatic hydrocarbon resins; more preferably, it is at least one selected from the group consisting of aliphatic / aromatic hydrocarbon resins and aromatic hydrocarbon resins; and even more preferably, it is an aliphatic / aromatic hydrocarbon resin. According to the above, phase separation of polymerization oil droplets during suspension polymerization is promoted, and as a result, better low dielectric properties can be exhibited. These hydrocarbon resins may be used individually or in combination of two or more types.

[0074] Aliphatic / aromatic hydrocarbon resins refer to hydrocarbon resins obtained by copolymerizing aliphatic hydrocarbons and aromatic hydrocarbons. Aliphatic / aromatic hydrocarbon resins are resins polymerized using styrene, vinyltoluene, indene, piperine, etc., as the main raw materials.

[0075] Aromatic hydrocarbon resins are resins polymerized using styrene, vinyltoluene, indene, etc., as the main raw materials.

[0076] Alicyclic hydrocarbon resins are, for example, resins obtained by hydrogenating aliphatic / aromatic hydrocarbon resins or aromatic hydrocarbon resins.

[0077] Aliphatic hydrocarbon resins are hydrocarbon resins obtained by polymerizing one or more aliphatic hydrocarbons having polymerizable unsaturated bonds.

[0078] In order to better express the effects of the present invention, when the total amount of compound (A), monomer (M), and non-crosslinkable polymer (P2) is 100 parts by weight, the non-crosslinkable polymer (P2) is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 20 parts by weight, even more preferably 1 to 15 parts by weight, particularly preferably 2 to 15 parts by weight, and most preferably 2 to 10 parts by weight.

[0079] In order to better express the effects of the present invention, when the total amount of compound (A), monomer (M), and non-crosslinkable polymer (P2) is 100 parts by weight, compound (A) is preferably 1 to 50 parts by weight, more preferably 2 to 40 parts by weight, even more preferably 3 to 30 parts by weight, and particularly preferably 4 to 20 parts by weight.

[0080] Furthermore, when the total of compound (A), monomer (M), and non-crosslinkable polymer (P2) is 100 parts by weight, the amount of crosslinkable monomer is preferably 1 to 80 parts by weight, more preferably 1 to 70 parts by weight, more preferably 5 to 65 parts by weight, even more preferably 10 to 60 parts by weight, and particularly preferably 10 to 55 parts by weight.

[0081] Furthermore, when the total of compound (A), monomer (M), and non-crosslinkable polymer (P2) is 100 parts by weight, the amount of monofunctional monomer is preferably 1 to 80 parts by weight, more preferably 1 to 70 parts by weight, more preferably 5 to 65 parts by weight, even more preferably 10 to 60 parts by weight, and particularly preferably 10 to 55 parts by weight.

[0082] ≪1-3. Applications of Hollow Resin Particles≫ Hollow resin particles according to the embodiments of the present invention can be used in various applications. In terms of making better use of the effects of the present invention, hollow resin particles according to the embodiments of the present invention are suitable as additives for semiconductor components, additives for optical materials such as light diffusers and anti-glare / low-reflection materials, additives for paints, and additives for inks, and are typically suitable for use in resin compositions for semiconductor components. An example of an application of hollow resin particles according to the embodiments of the present invention will be described below in the context of resin compositions for semiconductor components.

[0083] A resin composition for semiconductor components according to an embodiment of the present invention includes hollow resin particles according to an embodiment of the present invention.

[0084] Semiconductor components refer to the components that make up a semiconductor, such as semiconductor packages and semiconductor modules. In this specification, a resin composition for semiconductor components refers to a resin composition used in semiconductor components.

[0085] A semiconductor package is a component in which an IC chip is an essential component, and is constructed using at least one material selected from molding resin, underfill material, molded underfill material, die bonding material, prepreg for semiconductor package substrates, metal-clad laminate for semiconductor package substrates, and build-up material for printed circuit boards for semiconductor packages.

[0086] A semiconductor module is a component in which a semiconductor package is used as an essential component, and at least one component selected from printed circuit board prepregs, printed circuit board metal-clad laminates, printed circuit board build-up materials, solder resist materials, coverlay films, electromagnetic shielding films, and printed circuit board adhesive sheets.

[0087] 2. Method for Producing Hollow Resin Particles The hollow resin particles according to the embodiments of the present invention can be produced by any suitable method, as long as the effects of the present invention are not impaired.

[0088] A method for producing hollow resin particles according to embodiments of the present invention typically involves reacting a composition containing a compound (A) having an ether structure and radical-reactive groups represented by formula (1) and a non-crosslinkable polymer (P2) in an aqueous medium in the presence of a non-reactive solvent.

[0089] The above composition preferably contains a monomer (M) that reacts with compound (A). Monomer (M) typically includes crosslinkable monomers and monofunctional monomers, and preferably includes aromatic crosslinkable monomers and aromatic monofunctional monomers.

[0090] According to the above manufacturing method, hollow resin particles according to embodiments of the present invention can be easily produced.

[0091] The explanations in section 1-2, "Shell," above can be applied to the compound (A), monomer (M), non-crosslinkable polymer (P2), and compositions containing these.

[0092] In the method for producing hollow resin particles according to embodiments of the present invention, compound (A) and monomer (M) are preferably subjected to a suspension polymerization reaction.

[0093] Suspension polymerization is typically a suspension polymerization using an aqueous phase containing an aqueous medium and an oil phase containing the above composition and a non-reactive solvent. Preferably, the oil phase containing the above composition and the non-reactive solvent is added to the aqueous phase containing the aqueous medium, dispersed, and heated to carry out suspension polymerization.

[0094] The non-reactive solvent is a solvent that does not chemically react with either compound (A) or monomer (M), and is preferably an organic solvent. The organic solvent may be one type or two or more types. Any suitable organic solvent can be used as the organic solvent, as long as it does not impair the effects of the present invention. Such organic solvents preferably have a boiling point of less than 100°C. By using an organic solvent with a boiling point of less than 100°C, solvent removal from the hollow portion of the resulting hollow resin particles becomes easier, and manufacturing costs can be reduced.

[0095] Examples of organic solvents with a boiling point below 100°C include heptane, hexane, cyclohexane, methyl acetate, ethyl acetate, methyl ethyl ketone, chloroform, and carbon tetrachloride.

[0096] The amount of nonreactive solvent used can be any appropriate amount, as long as it does not impair the effects of the present invention. For example, when the total amount of compound (A), monomer (M), and non-crosslinkable polymer (P2) is 100 parts by weight, such an amount can be 10 to 250 parts by weight.

[0097] The oil phase preferably contains a polymerization initiator. There may be only one polymerization initiator or two or more. Any suitable polymerization initiator can be used as the polymerization initiator, as long as it does not impair the effects of the present invention.

[0098] As polymerization initiators, radical polymerization initiators, particularly thermal polymerization initiators, are preferred. Examples of such polymerization initiators include organic peroxides, oil-soluble nitrile-azo compounds, water-soluble azo compounds, persulfates (e.g., ammonium persulfate, potassium persulfate, sodium persulfate, etc.), and hydrogen peroxide.

[0099] Polymerization initiators include, for example, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]n hydrate (trade name "VA-057"), 4,4'-azobis(4-cyanovaleric acid) (trade name "V-501"), 2,2'-azobis[2-(2-imidazolin-2-yl)propane] (trade name "VA-061" and its dihydrochloride product "VA-044"), and 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)ionamidine]n hydrate (trade name "VA-061"), and its dihydrochloride product (trade name "VA-044"), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamidine]n hydrate (trade name "VA-057"), 4,4'-azobis(4-cyanovaleric acid) (trade name "VA-501"), 2,2'-azobis[2-(2-carboxyethyl)-2-methylpropionamidine]n hydrate (trade name "VA-06 2,2'-Azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide} (product name "VA-080"), 2,2'-Azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide} (product name "VA-082"), 2,2'-Azobis{2-methyl-N-[2-(1-hydroxybutyl)]-propionamide} (product name " Water-soluble azo compounds such as VA-085 (both manufactured by Fujifilm Wako Pure Chemical Industries); organic peroxides such as cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide (dilauroyl peroxide), dimethylbis(tert-butylperoxy)hexane, dimethylbis(tert-butylperoxy)hexine-3, bis(tert-butylperoxyisopropyl)benzene, bis(tert-butylperoxy)trimethylcyclohexane, butyl-bis(tert-butylperoxy)valerate, tert-butyl 2-ethylhexaneperoxyate, dibenzoyl peroxide, paramentane hydroperoxide, tert-butyl-2-ethylperoxyhexanoate, tert-butyl-2-ethylperoxyacetate, and tert-butylperoxybenzoate;2,2'-Azobisisobutyronitrile, 2,2'-Azobis(2-methylbutyronitrile), 2,2'-Azobis(2-isopropylbutyronitrile), 2,2'-Azobis(2,3-dimethylbutyronitrile), 2,2'-Azobis(2,4-dimethylbutyronitrile), 2,2'-Azobis(2-methylcapronitrile), 2,2'-Azobis(2,3,3-trimethylbutyronitrile), 2,2'-Azobis(2,4,4-trimethylvaleronitrile), 2,2'-Azobis Examples include oil-soluble nitrile-azo compounds such as 2,4-dimethylvaleronitrile, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(4-ethoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(4-n-butoxy-2,4-dimethylvaleronitrile), 1,1'-azobis(cyclohexane-1-carbonitride), 2-(carbamoylazo)isobutyronitrile, and 4,4'-azobis(4-cyanopentanoic acid). From the viewpoint of dielectric properties, the polymerization initiator is preferably an organic peroxide.

[0100] Furthermore, a redox-type initiator may be used as a polymerization initiator, which is a combination of the above-mentioned persulfate and organic peroxide polymerization initiators and a reducing agent such as sodium sulfoxylate formaldehyde, sodium bisulfite, ammonium bisulfite, sodium thiosulfate, ammonium thiosulfate, hydrogen peroxide, sodium hydroxymethanesulfinate, L-ascorbic acid and its salts, cuprous salts, or ferrous salts.

[0101] Among these, the polymerization initiators are 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]n hydrate (trade name "VA-057"), 4,4'-azobis(4-cyanovaleric acid) (trade name "V-501"), 2,2'-azobis[2-(2-imidazolin-2-yl)propane] (trade name "VA-061"), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] (trade name "VA-086"), and 2,2'- Azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide} (trade name "VA-080"), 2,2'-Azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide} (trade name "VA-082"), 2,2'-Azobis{2-methyl-N-[2-(1-hydroxybutyl)]-propionamide} (trade name "VA-085"), (all manufactured by Fujifilm Wako Pure Chemical Industries), 2,2'-A It is preferable that the peroxide is at least one selected from the group consisting of zobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonnitrile), 4,4'-azobis(4-cyanopentanoic acid), cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, benzoyl peroxide, tert-butyl-2-ethylperoxyhexanoate, and lauroyl peroxide. From the viewpoint of dielectric properties, it is more preferable that the peroxide is at least one selected from the group consisting of cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, benzoyl peroxide, tert-butyl-2-ethylperoxyhexanoate, and lauroyl peroxide.

[0102] The amount of polymerization initiator used can be any appropriate amount, as long as it does not impair the effects of the present invention. For example, when the total amount of compound (A) and monomer (M) is 100 parts by weight, the amount of polymerization initiator used can be 0.05 to 5 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.5 to 5 parts by weight, and even more preferably 0.8 to 3 parts by weight.

[0103] In addition to the components described above, the oil phase may contain any other suitable components as long as they do not impair the effects of the present invention. Such other components may be one type or two or more types.

[0104] Examples of aqueous media include water, and mixed media of water and lower alcohols (alcohols with 5 or fewer carbon atoms, such as methanol, ethanol, and isopropyl alcohol). As for water, at least one selected from the group consisting of deionized water and distilled water is preferred.

[0105] The amount of aqueous medium used can be any appropriate amount, as long as it does not impair the effects of the present invention. Such an amount is preferably 100 to 2000 parts by weight, and more preferably 200 to 1000 parts by weight, per 100 parts by weight of the oil phase. By adjusting the amount of aqueous medium to the above range, the dispersion stability of monomers during polymerization is improved, and the formation of aggregates of resin particles during polymerization can be suppressed.

[0106] The aqueous phase preferably contains a dispersion stabilizer. Any suitable dispersion stabilizer can be used as the dispersion stabilizer, as long as it does not impair the effects of the present invention. There may be only one dispersion stabilizer or two or more.

[0107] Examples of dispersion stabilizers include water-soluble polymer compounds such as polyvinyl alcohol, polycarboxylic acid, celluloses (hydroxyethylcellulose, carboxymethylcellulose, etc.), and polyvinylpyrrolidone. Other examples of dispersion stabilizers 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. Among these, magnesium pyrophosphate is preferred because it is relatively easy to remove from hollow resin particles and does not easily remain on the surface of hollow resin particles.

[0108] The amount of dispersion stabilizer used can be any appropriate amount, as long as it does not impair the effects of the present invention. Preferably, the amount of dispersion stabilizer is 0.5 to 10 parts by weight per 100 parts by weight of the aqueous medium.

[0109] The aqueous phase may contain a surfactant. Any suitable surfactant can be used as the surfactant, as long as it does not impair the effects of the present invention. There may be only one surfactant or two or more surfactants. Examples of such surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants.

[0110] Examples of anionic surfactants include sodium oleate; fatty acid soaps such as potassium castor oil soap; polysulfonates; polycarboxylates; alkyl sulfate esters such as sodium lauryl sulfate and ammonium lauryl sulfate; alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate; alkylaryl sulfonates; alkylnaphthalene sulfonates; alkanesulfonates; dialkyl sulfonates; dialkyl sulfosuccinates; alkyl phosphates; alkyl phosphate esters; naphthalene sulfonic acid formalin condensates or salts thereof, such as sodium salt of β-naphthalene sulfonic acid formalin condensate; polyoxyethylene alkylphenyl ether sulfate esters such as polyoxyethylene nonylphenyl ether sulfate; polyoxyethylene styrene-phenyl ether phosphate; polyoxyethylene alkyl ether phosphate; polyoxyethylene alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate and polyoxyethylene lauryl ether ammonium sulfate; polyoxyethylene alkyl sulfate esters; polyoxyethylene alkyl phosphate sulfonates; glycerol borate fatty acid esters; polyoxyethylene glycerol fatty acid esters; phosphate ester surfactants; and phosphite ester surfactants. The anionic surfactant may be one type or two or more types. Furthermore, the countercation of the anionic group is preferably an ammonium salt.

[0111] Examples of cationic surfactants include alkylamine salts such as laurylamine acetate and stearylamine acetate; and quaternary ammonium salts such as lauryltrimethylammonium chloride. There may be only one cationic surfactant or two or more.

[0112] Examples of nonionic surfactants include (meth)acrylate sulfate surfactants (commercial products such as RMA-564, RMA-568, and RMA-1114 from Nippon Emulsifier Co., Ltd.); polyoxyalkylene branched decyl ethers; polyoxyalkylene alkyl ethers such as polyoxyethylene tridecyl ether, polyoxyethylene isodecyl ether, polyoxyethylene lauryl ether, and polyoxyethylene oleyl cetyl ether; polyoxyalkylene aryl ethers such as polyoxyethylene naphthyl ether and polyoxyethylene phenyl ether; polyoxyalkylene alkylaryl ethers; polyether polyols; polyoxyethylene styrene phenyl ether; polyoxyethylene polyoxypropylene glycol; polyoxyethylene glyceryl isostearate; polyoxyethylene fatty acid esters; sorbitan fatty acid esters; polyoxysorbitan fatty acid esters; polyoxyethylene alkylamines; glycerin fatty acid esters; and oxyethylene-oxypropylene block polymers. The nonionic surfactant may be one type or two or more types.

[0113] Examples of amphoteric surfactants include lauryldimethylamine oxide, alkyldiaminoethylglycine hydrochloride, sodium laurylaminopropionate, and alkylbetaine. The amphoteric surfactant may be present in a single form or in two or more forms.

[0114] The amount of surfactant used can be any appropriate amount, as long as it does not impair the effects of the present invention. Such an amount is preferably 0.001 to 5 parts by weight, more preferably 0.005 to 3 parts by weight, and even more preferably 0.01 to 1 part by weight, per 100 parts by weight of the aqueous phase.

[0115] The aqueous phase may contain any other suitable components in addition to the components described above, as long as they do not impair the effects of the present invention.

[0116] The dispersion can be any suitable method, as long as it allows the oil phase to exist in droplet form in the aqueous phase, and does not impair the effects of the present invention. Typical dispersion methods include those using homomixers or homogenizers, such as polytron homogenizers, ultrasonic homogenizers, and high-pressure homogenizers.

[0117] For example, in the manufacturing method according to an embodiment of the present invention, it is preferable that the polymerization step includes a step in which the aqueous phase contains a dispersion stabilizer, and after the oil phase is dispersed in the aqueous phase, an emulsification treatment is performed using a high-pressure emulsifier at a pressure of 1 MPa to 200 MPa.

[0118] The polymerization temperature can be any suitable temperature within a range that does not impair the effects of the present invention, as long as it is suitable for suspension polymerization. For example, such polymerization temperatures are 30°C to 95°C.

[0119] The polymerization time can be any appropriate time, as long as it is suitable for suspension polymerization and does not impair the effects of the present invention. Such a polymerization time is preferably 1 to 20 hours.

[0120] Post-heating, which is preferably performed after polymerization, is a suitable treatment for obtaining high-quality hollow resin particles.

[0121] The temperature of the post-heating, which is preferably performed after polymerization, can be any appropriate temperature within a range that does not impair the effects of the present invention. The temperature of such post-heating is preferably 50°C to 120°C.

[0122] The duration of the post-heating, which is preferably performed after polymerization, can be any appropriate duration as long as it does not impair the effects of the present invention. Such post-heating is preferably 1 to 10 hours.

[0123] The slurry containing particles obtained by the polymerization process can be subjected to distillation, solvent removal, filtering, washing, drying, classification, etc., as needed, to obtain additional particles.

[0124] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0125] <Resin Penetration Evaluation 1: Measurement of Total Light Transmittance of Cured Resin Composition with 10 wt% Hollow Resin Particles> (Preparation of Cured Resin) A cured resin composition containing 10 wt% hollow resin particles was prepared as follows. First, 190 g of reactive low molecular weight polyphenylene ether (trade name "Noryl® SA9000-111 resin", manufactured by SABIC), 47.5 g of triallyl isocyanurate (trade name "TAIC®", manufactured by Mitsubishi Chemical), and 260 g of toluene (manufactured by Fujifilm Wako Pure Chemical Industries) were placed in a beaker containing a stirring bar and stirred for 2 hours. 26.6 g of hollow resin particles were added and stirred for 1 hour, and then 1.9 g of perbutyl P (manufactured by NOF Corporation) was added and stirred for another hour to obtain varnish. The obtained varnish was concentrated using an evaporator set to 40°C. The concentrate was transferred to an aluminum tray and dried overnight in a vacuum dryer set to 40°C. The obtained dried material was crushed to produce a powdered sample (resin composition). Next, copper foil was placed on a mirror plate, and a 100 mm x 100 mm x t1.0 mm mold was placed on the copper foil. The powdered sample was placed inside the mold and sandwiched between copper foil. 20 g of the sample sandwiched between copper foil was sandwiched between a mirror plate, a 500 μm thick Teflon® sheet, and a SUS plate (5 mm thick), and vacuum press molded using a manual hydraulic vacuum heating press IMC-46E2-3 (manufactured by Imoto Seisakusho) under the following molding conditions: Molding conditions Temperature: Heat from room temperature (25°C) to 150°C at a rate of 10°C / min, and held at 150°C for 30 minutes. Heat from 150°C to 175°C at a rate of 10°C / min, and held at 175°C for 30 minutes. The temperature was increased from 175°C to 200°C at a rate of 10°C / min, and held at 200°C for 2 hours. Pressure: 6 MPa. After molding, the copper foil was peeled off to obtain a plate-shaped cured product with a thickness of 1.0 mm. (Measurement of total light transmittance) The total light transmittance in the thickness direction of the obtained cured product was measured using a haze meter (Nippon Denshoku Industries, "NDH4000") in accordance with JIS K 7361-1. Three measurements were taken, and the arithmetic mean of the three obtained measurements was taken as the total light transmittance. The total light transmittance in the thickness direction of a 1.0 mm thick cured product, which was cured by mixing the above polyphenylene ether resin, crosslinking agent, and polymerization initiator without adding hollow resin particles, was 59.0%.

[0126] <Resin Invasiveness Evaluation 2: CIE 1976 L * a * b * Color Space Chromaticity Difference Measurement> (Preparation of Measurement Samples) In the same manner as in (Production of Hardened Products) of <Resin Invasiveness Evaluation 1: Measurement of Total Light Transmittance of Hardened Products of 10 wt% Resin Compositions of Hollow Resin Particles> described above, a hardened product (first hardened product) of a resin composition containing 10 wt% of hollow resin particles was produced. Further, a second hardened product having a thickness of 1.0 mm obtained by mixing and curing a polyphenylene ether resin, a crosslinking agent, and a polymerization initiator was produced in the same manner as the first hardened product except that no hollow resin particles were added. (L * 、a * 、b * Value Measurement) The L * 、a * 、b * values of the surfaces of the first hardened product and the second hardened product were measured using a color difference meter (manufactured by Konica Minolta Optics, "CR-400") and a data processor (manufactured by Konica Minolta Optics, "DP-400"). Specifically, first, the color difference meter and the data processor were connected, and the power supplies of the color difference meter and the data processor were turned on. The "Color System" button of the data processor was pressed to set the display screen to the Yxy color system. Next, the measurement part of the color difference meter was placed on the white calibration plate (X = 84.5, x = 0.3159, y = 0.3227) attached to the color difference meter, and the "Calibration" button of the data processor was pressed to perform calibration. After calibration, the measurement sample was placed on a black plate (plate color difference: L * = 21.97, a * = 0.32, b * = -0.87), and the measurement was performed by placing the measurement part of the color difference meter "CR-400" on the measurement sample. The "Color System" button of the data processor was pressed to switch to the display screen of the L * a * b * color system, and the values of the L * a * b * color system were read. Each sample measurement was performed 3 times, and the average value of the three measurement values was taken as the L * 、a * 、b * of each sample. (Chromaticity Difference ΔE* Calculation of ab) L measured for the first cured product * , a * , b * are respectively denoted as L1 * , a1 * , b1 * and L, a * , a * , b * measured for the second cured product are respectively denoted as L2 * , a2 * , b2 * and the color difference ΔE * ab is calculated by the CIE1976 color difference formula of JIS Z8781-4 shown below. ΔE * ab = [(L1 * − L2 * )<x 2 + (a1 * − a2 * ) 2 + (b1 * − b2 * ) 2 1 / 2 Here, for the second cured product, L2 * = 32.10, a2 * = 3.96, b2 * = 14.46.

[0127] ​<Measurement of Volume-Average Particle Diameter> The volume-average particle diameter of the particles was measured using the Coulter method as follows. The volume-average particle diameter of the particles was measured using the Coulter Multisizer® 4e (a measuring device manufactured by Beckman Coulter). The measurement was performed using an aperture calibrated according to the Multisizer 4e User's Manual issued by Beckman Coulter. The aperture used for the measurement was appropriately selected according to the assumed volume-average particle diameter of the particles being measured. For example, if the assumed volume-average particle diameter was 0.2 μm to 6 μm, an aperture with a size of 10 μm was selected; if the assumed volume-average particle diameter was 0.4 μm to 16 μm, an aperture with a size of 20 μm was selected; if the assumed volume-average particle diameter was 1.0 μm to 40 μm, an aperture with a size of 50 μm was selected; and if the assumed volume-average particle diameter was 2.0 μm to 80 μm, an aperture with a size of 100 μm was selected. If the volume-average particle diameter after measurement differed from the expected volume-average particle diameter, the aperture was changed to one of the appropriate size, and the measurement was repeated. For the measurement sample, 0.1 g of particles was dispersed in 10 mL of a 0.1 wt% nonionic surfactant aqueous solution using a touch mixer (Yamato Scientific, "TOUCHMIXER MT-31") and an ultrasonic cleaner (Velvo-Clear, "ULTRASONIC CLEANER VS-150") to prepare the dispersion. During the measurement, the contents of the beaker were gently stirred to prevent the introduction of air bubbles, and the measurement was terminated when 100,000 particles had been measured. The volume-average particle diameter was calculated as the arithmetic mean of the volume-based particle size distribution of 100,000 particles.

[0128] <Coefficient of Variation of Volume-Average Particle Size> The coefficient of variation (CV value) of the volume-average particle size was calculated using the following formula: Coefficient of Variation [%] = (Standard deviation of particle size distribution based on particle volume ÷ Volume-average particle size of particle) × 100

[0129] <Observation of Particle Appearance> The surface of dried particles was coated using a sputtering apparatus (Hitachi High-Tech, "Ion Sputter MC1000") to create a sample. Next, the appearance of the sample was photographed using the secondary electron detector of a scanning electron microscope (Hitachi High-Tech, "SU3800"). The images were taken at a magnification of 1000x or 3000x.

[0130] <Observation of Particle Cross-Sections> Dried particles were mixed with the curable resin "Epoclear" (manufactured by Konishi Co., Ltd.) and allowed to dry overnight to obtain a cured product. The cured product was then cut with a cutter and coated using a sputtering device (Hitachi High-Tech Corporation, "Ion Sputter MC1000"). Next, the cross-section of the sample was photographed using the secondary electron detector of a scanning electron microscope (Hitachi High-Tech Corporation, "SU3800"). The images were taken at a magnification of 1000x or 3000x.

[0131] <Measurement of 5% Thermogravimetric Loss Temperature when Heating at 10°C / min in an Air Atmosphere> The 5% thermogravimetric loss temperature was measured using a TG / DTA instrument (Seiko Instruments TG / DTA6200). The sampling method and temperature conditions were as follows: 10.5 ± 0.5 mg of the sample was packed into the bottom of a platinum measuring container to create a sample for measurement. Under measurement conditions of an air flow rate of 200 mL / min, a heating rate of 20°C / min in the range of 40°C to 100°C, and a heating rate of 10°C / min in the range of 100°C to 500°C, the weight loss behavior in the range of 40°C to 500°C was measured using alumina as the reference material to obtain a TG / DTA curve. From the obtained curve, the temperature at which a 5% weight loss occurred was calculated using the analysis software attached to the instrument, and this was defined as the 5% thermogravimetric loss temperature.

[0132] <Measurement of 5% thermogravimetric loss temperature when heating at 10°C / min in a nitrogen atmosphere> The 5% thermogravimetric loss temperature when heating at 10°C / min in a nitrogen atmosphere was measured in the same manner as described above in <Measurement of 5% thermogravimetric loss temperature when heating at 10°C / min in an air atmosphere>, except that nitrogen gas (flow rate 200 mL) was used instead of air (flow rate 200 mL).

[0133] <Measurement of Apparent Density> The apparent density of the hollow resin particles was measured as follows. First, hollow resin particles and a polymer ("ARUFON UP-1020", manufactured by Toagosei) as a dispersion medium were prepared, and the weights of each were measured. At this time, the amount of particles was set to 2% by weight of the total amount of particles and dispersion medium. Using a rotation-revolution type mixer ("Awatori Rentaro AR-100", manufactured by Shinky), the particles were dispersed in the dispersion medium to obtain a first particle dispersion with a concentration of 2% by weight. Approximately 5 mL was sampled from the obtained first particle dispersion using a syringe, and 1 to 2 mL of the first particle dispersion was injected from the syringe into the device inlet of a digital densimeter ("DMA-1001", manufactured by Anton Paar), and the density was measured. After measurement, the measuring tube in the device was cleaned, and 1 mL of the first particle dispersion was injected again from the syringe into the device inlet, and the density of the particle dispersion was measured. The average of these two measurements was taken as the density of the first particle dispersion. Next, the density of the dispersion medium was measured using a digital densimeter ("DMA-1001", manufactured by Anton Paar) in the same manner as above. From the density of the first particle dispersion and the density of the dispersion medium, the apparent density of the particles [g / cm³] was calculated using the following formula. 3 The result was calculated.

[0134] <Hollow Ratio> The hollow ratio of the hollow resin particles was calculated from the apparent density and true density of the hollow resin particles. The true density of the hollow resin particles was measured as follows: Crushed hollow resin particles and a polymer ("ARUFON UP-1020", Toagosei) as a dispersion medium were prepared, and the weight of each was measured. At this time, the amount of particles was set to 2% by weight of the total amount of particles and dispersion medium. Using a stirring and defoaming machine ("Mazelstar KK-250", KURABO), the particles were dispersed in the dispersion medium to obtain a second particle dispersion. Approximately 5 mL was sampled from the obtained second particle dispersion using a syringe, and 1 to 2 mL of the second particle dispersion was injected from the syringe into the device inlet of a digital densimeter ("DMA-1001", Anton Paar), and the density was measured. After the measurement, the measuring tube inside the apparatus was cleaned, and 1 mL of the second particle dispersion was injected again into the apparatus inlet from the syringe, and the density of the second particle dispersion was measured. The average of these two measurements was taken as the density of the second particle dispersion. Next, the density of the dispersion medium was measured in the same manner as above using a digital densimeter ("DMA-1001", manufactured by Anton Paar). From the density of the second particle dispersion and the density of the dispersion medium, the true density of the particles [g / cm³] was calculated using the following formula. 3 The result was calculated. The particle hollowness [%] was calculated using the following formula from the true density and the apparent density calculated in <Measurement of Apparent Density>: Hollowness (%) = 100 - 100 × Apparent Density (g / cm³) 3 ) / true density (g / cm 3 )

[0135] <Dielectric Properties of Hollow Resin Particles> The dielectric properties of hollow resin particles were measured using an AET dielectric constant measuring device (ADMS01Nc series). The relative permittivity and dielectric loss tangent of the hollow resin particles were calculated based on perturbation theory using a resonator at a frequency of 10 GHz, a measurement environment of 25 ± 2°C, and a relative humidity of 43 ± 5%.

[0136] <Method for Measuring Number-Average Molecular Weight> The number-average molecular weight (Mn) of non-crosslinked polymers was measured using gel permeation chromatography (GPC). Here, "number-average molecular weight" refers to the number-average molecular weight on a polystyrene basis. 0.003 g of the sample was dissolved in 10 mL of tetrahydrofuran (THF) at room temperature for at least 24 hours. The solution was then filtered through a non-aqueous 0.45 μm chromatographic disk and used as the measurement solution. The number-average molecular weight of the sample was determined from a pre-prepared calibration curve of standard polystyrene. The chromatographic measurement conditions were as follows. • Equipment: High-speed GPC instrument • Product name: Tosoh Corporation HLC-8320GPC EcoSEC-WorkStation (built-in RI detector) • Analytical conditions Column: TSKgel SuperHZM-H x 2 (4.6 mm ID x 15 cm L x 2) Guard column: TSKguardcolumn SuperHZ-H x 1 (4.6 mm ID x 2 cm L) Flow rate: Sample side 0.175 mL / min, Reference side 0.175 mL / min Detector: Built-in RI detector Concentration: 0.3 g / L Injection volume: 50 μL Column temperature: 40°C System temperature: 40°C Eluent: THF (Calibration curve creation) As a standard polystyrene sample for the calibration curve, Tosoh Corporation product name "TSK standard Standard polystyrene samples of "POLYSTYRENE" with number-average molecular weights of 500, 2630, 9100, 37900, 102000, 355000, 3840000, and 5480000 were used, along with a standard polystyrene sample of Showa Denko's product name "Shodex STANDARD" with a number-average molecular weight of 1,030,000. The calibration curve was prepared as follows: First, the above standard polystyrene samples for the calibration curve were grouped into Group A (number-average molecular weight of 1,030,000), Group B (number-average molecular weights of 500, 9100, 102000, and 3480000), and Group C (number-average molecular weights of 2630, 37900, 355000, and 5480000). A standard polystyrene sample belonging to Group A, with a number-average molecular weight of 1,030,000, was weighed out at a dose of 5 mg, dissolved in 20 mL of THF, and 50 μL of the resulting solution was injected into the sample column.Standard polystyrene samples belonging to Group B, with number-average molecular weights of 500, 9100, 102000, and 3480000, were weighed at 10 mg, 5 mg, 5 mg, and 5 mg respectively, dissolved in 50 mL of THF, and 50 μL of the resulting solution was injected into the sample column. Standard polystyrene samples belonging to Group C, with number-average molecular weights of 2630, 37900, 355000, and 5480000, were weighed at 5 mg, 5 mg, 5 mg, and 1 mg respectively, dissolved in 40 mL of THF, and 50 μL of the resulting solution was injected into the sample column. Calibration curves (cubic equations) were created from the retention times of these standard polystyrene samples using the HLC-8320 GPC dedicated data analysis program GPC workstation (EcoSEC-WS), and these were used as calibration curves for measuring the polystyrene-equivalent number-average molecular weight.

[0137] (Example 1) Reactive low molecular weight polyphenylene ether as a compound having an ether structure and radical reactive groups (product name "Noryl® SA9000-111 resin", manufactured by SABIC): 60.0 parts by weight, Divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Material, 81% content, 19% is ethyl vinylbenzene (EVB)): 300.0 parts by weight, Styrene (manufactured by Denka): 204.0 parts by weight, Olefin polymer (product name "VYBAR® 260", NuCera An oil phase was prepared by mixing 36 parts by weight of Solution's magnesium pyrophosphate (Mn: 5,800), 400.0 parts by weight of heptane (Gordo), 3.0 parts by weight of 1-octanthiol (Tokyo Chemical Industries) as a chain transfer agent, 6.0 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) (trade name "V-65", Fujifilm Wako Pure Chemical Industries) as a polymerization initiator, and 3.0 parts by weight of "KAYAMER® PM-21" (Nippon Kayaku) as a phosphate ester monomer. The oil phase was added to 3203 parts by weight of a 2.0% by weight aqueous dispersion of magnesium pyrophosphate as the aqueous phase, and the mixture was stirred at 5000 rpm for 3 minutes using a TK homomixer (Primix) to obtain a preemulsification. The pre-emulsification was further subjected to high-pressure emulsification treatment using a coarse-grain processing system (manufactured by Yoshida Machinery Industry Co., Ltd., model "NVR-EM055-P20-0600-Exp") under processing pressure of 17 MPa and outlet pressure of 1 MPa to obtain a finely milled emulsion. The emulsion was placed in a pressure-resistant polymerizer equipped with a stirring device, thermometer, and cooling mechanism, nitrogen gas was blown in for 3 minutes to create an inert gas atmosphere, and then the temperature was raised to 60°C for 3 hours to carry out polymerization. After that, the temperature was further raised to 90°C for 3 hours to carry out the polymerization reaction. After the polymerization process was completed, hydrochloric acid was added to the obtained slurry to decompose magnesium pyrophosphate, and then dehydration was performed using a centrifuge and washing with ion-exchanged water to obtain a cake containing hollow resin particles. This cake was dried in a vacuum oven under reduced pressure at 80°C for 24 hours to obtain particles (A1). SEM observation of the appearance and cross-section of particles (A1) was performed. A photograph of the appearance of particles (A1) is shown in Figure 2. A cross-sectional photograph of particle (A1) is shown in Figure 3.Particle (A1) was confirmed to be a hollow resin particle with a single hollow structure, where the hollow enclosed by the shell was single. By performing a 10 μm top cut on particle (A1) using an airflow classifier (Nisshin Engineering Co., Ltd., "Turbo Classifier (registered trademark) TC-15NS"), hollow resin particle (1) was obtained. The hollowness ratio of hollow resin particle (1) was 51.6%. The volume-average particle diameter of hollow resin particle (1) was 3.6 μm, and the coefficient of variation was 16.8%. The 5% thermogravimetric loss temperature of hollow resin particle (1) when heated at 10 °C / min in an air atmosphere was 314.7 °C. The relative permittivity of hollow resin particle (1) at a frequency of 10 GHz was 1.52, and the dielectric loss tangent was 0.00107.

[0138] (Example 2) As shown in Table 1, particle (A2) was obtained in the same manner as particle (A1) in Example 1, except that the composition of the oil phase was changed. A photograph of the appearance of particle (A2) is shown in Figure 4. A cross-sectional photograph of particle (A2) is shown in Figure 5. Particle (A2) was a hollow resin particle with a single hollow structure, where the hollow surrounded by the shell was single. A 10 μm top cut was performed on particle (A2) using an airflow classifier in the same manner as in Example 1 to obtain hollow resin particle (2). The various measurement results for hollow resin particle (2) are shown in Table 1.

[0139] (Example 3) As shown in Table 1, particle (A3) was obtained in the same manner as particle (A1) in Example 1, except that an aromatic-aliphatic block copolymer polymer (Kuraray's "Septon-2002", Mn: 51,800) was used instead of an olefin polymer. A photograph of the appearance of particle (A3) is shown in Figure 6. A cross-sectional photograph of particle (A3) is shown in Figure 7. Particle (A3) was a hollow resin particle with a single hollow structure, where the hollow was surrounded by a shell. A 10 μm top cut was performed on particle (A3) using an airflow classifier in the same manner as in Example 1 to obtain hollow resin particle (3). The results of various measurements of hollow resin particle (3) are shown in Table 1.

[0140] (Example 4) As shown in Table 1, particle (A4) was obtained in the same manner as particle (A1) in Example 1, except that 36.0 parts by weight of an olefin polymer and 12.0 parts by weight of a polyphenylene ether polymer (SABIC's "Noryl SA90", Mn: 1,900) were used as non-crosslinkable polymers, and the amount of styrene used was changed to 192.0 parts by weight. A photograph of the appearance of particle (A4) is shown in Figure 8. A photograph of the cross-section of particle (A4) is shown in Figure 9. Particle (A4) was a hollow resin particle with a single hollow structure, where the hollow surrounded by a shell was single. A 10 μm top cut was performed on particle (A4) using an airflow classifier in the same manner as in Example 1 to obtain hollow resin particle (4). The results of various measurements of hollow resin particle (4) are shown in Table 1.

[0141] (Example 5) As shown in Table 1, particle (A5) was obtained in the same manner as particle (A1) in Example 1, except that the composition of the oil phase was changed. A photograph of the appearance of particle (A5) is shown in Figure 10. A cross-sectional photograph of particle (A5) is shown in Figure 11. Particle (A5) was a hollow resin particle with a single hollow structure, where the hollow surrounded by the shell was single. A 10 μm top cut was performed on particle (A5) using an airflow classifier in the same manner as in Example 1 to obtain hollow resin particle (5). Various measurement results for hollow resin particle (5) are shown in Table 1.

[0142] (Example 6) As shown in Table 1, particle (A6) was obtained in the same manner as particle (A1) in Example 1, except that 9.0 parts by weight of dilauroyl peroxide (NOF Corporation, "Perloyl L") was used as the polymerization initiator, and the polymerization reaction was changed from 3 hours at 60°C to 3 hours at 75°C. A photograph of the appearance of particle (A6) is shown in Figure 12. A cross-sectional photograph of particle (A6) is shown in Figure 13. Particle (A6) was a hollow resin particle with a single hollow structure, where the hollow surrounded by a shell was single. A 10 μm top cut was performed on particle (A6) using an airflow classifier in the same manner as in Example 1 to obtain hollow resin particle (6). Various measurement results for hollow resin particle (6) are shown in Table 1.

[0143] (Example 7) As shown in Table 1, particle (A7) was obtained in the same manner as particle (A1) in Example 1, except that 6.0 parts by weight of tert-butyl-2-ethylperoxyhexanoate (manufactured by NOF Corporation, "Perbutyl O") was used as the polymerization initiator, and the polymerization reaction was changed from 3 hours at 60°C to 3 hours at 75°C. A photograph of the appearance of particle (A7) is shown in Figure 14. A cross-sectional photograph of particle (A7) is shown in Figure 15. Particle (A7) was a hollow resin particle with a single hollow structure, where the hollow surrounded by a shell was single. A 10 μm top cut was performed on particle (A7) using an airflow classifier in the same manner as in Example 1 to obtain hollow resin particle (7). Various measurement results for hollow resin particle (7) are shown in Table 1.

[0144] (Example 8) As shown in Table 1, particle (A8) was obtained in the same manner as particle (A1) in Example 1, except that the composition of the oil phase was changed. A photograph of the appearance of particle (A8) is shown in Figure 16. A cross-sectional photograph of particle (A8) is shown in Figure 17. Particle (A8) was a hollow resin particle with a single hollow structure, where the hollow surrounded by a shell was single. A 10 μm top cut was performed on particle (A8) using an airflow classifier in the same manner as in Example 1 to obtain hollow resin particle (8). Various measurement results for hollow resin particle (8) are shown in Table 1.

[0145] (Example 9) As shown in Table 1, particle (A9) was obtained in the same manner as particle (A1) in Example 1, except that the composition of the oil phase was changed. A photograph of the appearance of particle (A9) is shown in Figure 18. A cross-sectional photograph of particle (A9) is shown in Figure 19. Particle (A9) was a hollow resin particle with a porous structure consisting of a hollow surrounded by a shell. A 10 μm top cut was performed on particle (A9) using an airflow classifier in the same manner as in Example 1 to obtain hollow resin particle (9). Various measurement results for hollow resin particle (9) are shown in Table 1.

[0146] (Comparative Example 1) Divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Material, 81% content, 19% is ethyl vinylbenzene (EVB)): 380.8 parts by weight, styrene (manufactured by Denka): 304.6 parts by weight, polyethylene glycol propylene glycol monomethacrylate ("Brenmer 50PEP-300", manufactured by NOF Corporation): 6.9 parts by weight, aromatic polymer (polystyrene, Mn: 86,300): 48.5 parts by weight, heptane (manufactured by Gordo): 464.7 parts by weight, and 2,2'-azobis(2,4-dimethylvaleronitrile) (trade name "V-65", manufactured by Fujifilm Wako Pure Chemical Industries) as a polymerization initiator: 10.4 parts by weight were mixed to prepare an oil phase. A pre-emulsification was obtained by adding 2603.3 parts by weight of a 2.5 wt% aqueous dispersion of magnesium pyrophosphate as the aqueous phase to an oil phase and stirring at 5000 rpm for 3 minutes using a TK homomixer (Primix). The pre-emulsification was further subjected to high-pressure emulsification treatment using a coarse-grain processing system (Yoshida Machinery Industry, model "NVR-EM055-P20-0600-Exp") under processing pressure of 17 MPa and outlet pressure of 1 MPa to obtain a finely milled emulsion. The emulsion was placed in a pressure-resistant polymerization chamber equipped with a stirring device, thermometer, and cooling mechanism, and nitrogen gas was blown in for 3 minutes to create an inert gas atmosphere. The temperature was then raised to 60°C and polymerization was carried out for 3 hours. After that, the temperature was further raised to 90°C and the polymerization reaction was carried out for another 3 hours. After the polymerization process was completed, hydrochloric acid was added to the obtained slurry to decompose the magnesium pyrophosphate, and then dehydration was performed using a centrifuge and washing with ion-exchanged water to obtain a cake containing hollow resin particles. This cake was dried in a vacuum oven under reduced pressure at 80°C for 24 hours to obtain particles (CA1). The appearance and cross-section of particles (CA1) were observed using SEM. A photograph of the appearance of particles (CA1) is shown in Figure 20. A photograph of the cross-section of particles (CA1) is shown in Figure 21. It was confirmed that particles (CA1) are hollow resin particles with a porous structure in the hollow space surrounded by the shell. Particles (CA1) were classified using a JIS test sieve with a mesh opening of 32 μm (manufactured by Okutani Wire Mesh Co., Ltd., standard: JIS Z 8801-1:2000), and the particles that passed through the mesh and fell to the bottom of the sieve were designated as the hollow resin particles (C1) of Comparative Example 1.The results of various measurements for hollow resin particles (C1) are shown in Table 1.

[0147] (Comparative Example 2) As shown in Table 1, particles (CA2) were obtained in the same manner as particles (A1) in Example 1, except that the composition of the oil phase and aqueous phase was changed. A photograph of the appearance of particles (CA2) is shown in Figure 22. A cross-sectional photograph of particles (CA2) is shown in Figure 23. Particles (CA2) were hollow resin particles with a porous structure consisting of a hollow surrounded by a shell. Particles (CA2) were subjected to a 10 μm top cut using an airflow classifier in the same manner as in Example 1 to obtain hollow resin particles (C2). Various measurement results for hollow resin particles (C2) are shown in Table 1.

[0148] (Comparative Example 3) As shown in Table 1, particles (CA3) were obtained in the same manner as particles (A1) in Example 1, except that the composition of the oil phase and aqueous phase was changed. A photograph of the appearance of particles (CA3) is shown in Figure 24. A cross-sectional photograph of particles (CA3) is shown in Figure 25. Particles (CA3) were hollow resin particles with a porous structure consisting of a hollow surrounded by a shell. Particles (CA3) were subjected to a 10 μm top cut using an airflow classifier in the same manner as in Example 1 to obtain hollow resin particles (C3). Various measurement results for hollow resin particles (C3) are shown in Table 1.

[0149]

[0150] The abbreviations in Table 1 are as follows: ADVN: 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, trade name "V-65") LPO: dilauroyl peroxide (manufactured by NOF Corporation, "Perloyl L") t-BuPEHx: tert-butyl-2-ethylperoxyhexanoate (manufactured by NOF Corporation, "Perbutyl O")

[0151] Hollow resin particles according to embodiments of the present invention, and hollow resin particles obtained by the manufacturing method according to embodiments of the present invention, are suitably usable in semiconductor components and the like.

Claims

1. Hollow resin particles having a shell portion and a hollow portion surrounded by the shell portion, wherein the shell portion comprises a polymer (P1) having an ether structure represented by formula (1) and a non-crosslinkable polymer (P2), and the total light transmittance in the thickness direction of a cured product with a thickness of 1.0 mm obtained by mixing 10 wt% of the hollow resin particles, a polyphenylene ether resin, a crosslinking agent, and a polymerization initiator and curing it is 20.00% or less.

2. The hollow resin particle according to claim 1, wherein the polymer (P1) is a polymer obtained by the reaction of a composition comprising a compound (A) having an ether structure and a radical reactive group represented by formula (1), and a monomer (M) that reacts with compound (A), wherein the monomer (M) comprises an aromatic crosslinkable monomer.

3. The hollow resin particle according to claim 2, wherein the monomer (M) comprises an aromatic monofunctional monomer.

4. The hollow resin particles according to claim 2, wherein the composition comprises the non-crosslinkable polymer (P2), and when the total of the compound (A), the monomer (M), and the non-crosslinkable polymer (P2) is 100 parts by weight, the compound (A) is present in an amount of 1 to 50 parts by weight.

5. The hollow resin particles according to claim 2, wherein the composition comprises the non-crosslinkable polymer (P2), and when the total of the compound (A), the monomer (M), and the non-crosslinkable polymer (P2) is 100 parts by weight, the amount of the non-crosslinkable polymer (P2) is 0.1 parts by weight to 20 parts by weight.

6. The hollow resin particle according to claim 1, wherein the hollow portion has a single hollow structure consisting of one hollow region.

7. The hollow resin particles according to claim 1, wherein the 5% thermoweight loss temperature when the hollow resin particles are heated at 10°C / min in an air atmosphere is 300°C or higher.

8. The lightness L * a * b * in the CIE 1976 L * a * b * color space of the surface of the first cured product with a thickness of 1.0 mm obtained by mixing 10 wt% of the hollow resin particles, a polyphenylene ether resin, a crosslinking agent, and a polymerization initiator and curing them * a * b * is L1 * and the chromaticity a1 * and the chromaticity b1 * ; and the lightness L * a * b * in the L * a * b * color space of the surface of the second cured product with a thickness of 1.0 mm obtained by mixing the polyphenylene ether resin, the crosslinking agent, and the polymerization initiator and curing them * a * b * is L2 * and the chromaticity a2 * and the chromaticity b2 * satisfy the formula (2), and the hollow resin particles according to claim 1. 20.0 ≦ ΔE * ab = [(L1 * - L2 * ) 2 +(a1 * - a2 * ) 2 +(b1 * - b2 * ) 2 ] 1 / 2 ...(2) * ab = [[(L1 * - L2 * ) 2 [[ID=三十一]] 2 +(a1 * - a2 * ) 2 * - a2 * ) 2 2 +(b1 * - b2 * ) 2 * - b2 * ) 2 2 1 / 2 1 / 2 ...(2) 9. The hollow resin particle according to claim 1, wherein the relative permittivity at a measurement frequency of 10 GHz is 2.00 or less.

10. The hollow resin particle according to claim 1, wherein the dielectric loss tangent at a measurement frequency of 10 GHz is 0.00200 or less.

11. Hollow resin particles according to claim 1, used in a resin composition for semiconductor components.

12. A resin composition for semiconductor components comprising the hollow resin particles described in claim 11.

13. A method for producing hollow resin particles having a shell portion and a hollow portion surrounded by the shell portion, comprising reacting a composition containing a compound (A) having an ether structure and radical reactive groups represented by formula (1) and a non-crosslinkable polymer (P2) in an aqueous medium in the presence of a non-reactive solvent.

14. The method for producing hollow resin particles according to claim 13, wherein the composition comprises a monomer (M) that reacts with the compound (A), and the compound (A) and the monomer (M) are suspended polymerized by the reaction.

15. The method for producing hollow resin particles according to claim 14, wherein the monomer (M) includes an aromatic crosslinkable monomer and an aromatic monofunctional monomer.

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