Hollow resin particle and resin composition for semiconductor component

Abstract

This invention provides hollow resin particles with reduced coarse particle number and excellent particle strength. Furthermore, this invention provides an application of such hollow resin particles. Also, this invention provides a method for manufacturing such hollow resin particles. The hollow resin particles of the embodiment of the present invention have a shell and a hollow portion surrounded by the shell, and the porosity is 5 to 90%. Under the following measurement conditions A, the number of particles with a diameter of 10 μm or larger among 1,000,000 particles is 45 or less. (Measurement Condition A) Particle size measurement range (sphere conversion volume standard): 0.5 μm to 200.0 μm, sphericity measurement range: 0.97 to 1.00.

Description

[Technical Field]

[0001] This invention relates to a hollow resin particle, its manufacturing method and its use. [Previous Technology]

[0002] Hollow resin particles are materials that can impart properties such as low dielectric or low refractive index to components in the semiconductor component market or display component market.

[0003] In recent years, the semiconductor component market has seen various research efforts aimed at high-performance electronic circuits. For example, in packages, copper-clad laminates (rigid and flexible), interlayer insulating films, and underfill materials, as wafers become smaller, these components also tend to be miniaturized. For instance, in underfill materials, there is a technique that uses an inorganic filler with an average diameter of approximately 2 μm and few coarse particles to achieve a coating process that reduces viscosity and prevents mesh clogging (Patent Document 1). For example, in copper-clad laminates, there is a technique that uses silicon oxide with a top cut of 10 μm as an inorganic filler during prepreg fabrication (Patent Document 2). In the semiconductor component market, where miniaturization is a priority, it is crucial to use fillers with few coarse particles to improve yield and reliability.

[0004] Three patent documents describe a hollow resin particle with a submicron size and few coarse particles, and a method for manufacturing the same. However, this technology is characterized by treating the surface of silicon oxide particles coated with a resin layer with an alkali metal-containing liquid and removing the silicon oxide. When this technology is applied to the semiconductor component market, there are still issues such as residual alkali metal residues that can damage the insulation of the components.

[0005] Patent Document 4 describes hollow particles with low dielectric properties. However, the hollow particles obtained by this technology still have the problem of being weak and easily broken, and the presence of a certain number of coarse particles larger than 10 μm leads to reduced yield or reliability during component fabrication. [Prior Art Documents] [Patent Documents]

[0006] [Patent Document 1] International Publication No. 2024 / 075343 [Patent Document 2] International Publication No. 2020 / 203469 [Patent Document 3] Japanese Patent Application Publication No. 2021-094502 [Patent Document 4] International Publication No. 2024 / 048093 [Summary of the Invention]

[0007] [Problem to be Solved by the Invention] The present invention is constructed to solve the aforementioned problems of conventional resins, and its main objective is to provide hollow resin particles with a reduced number of coarse particles and excellent particle strength. Furthermore, the present invention provides a method for manufacturing such hollow resin particles. Moreover, the present invention provides uses for such hollow resin particles. [Means for Solving the Problem]

[0008] [1] The hollow resin particles of the embodiment of the present invention have a shell and a hollow portion surrounded by the shell, wherein the porosity is 5 to 90%, and the number of particles with a diameter of 10 μm or more in 1,000,000 particles obtained by using a flow particle image analysis device under the following measurement conditions A is 45 or less, (measurement conditions A) particle size measurement range (sphere conversion volume basis): 0.5 μm to 200.0 μm, sphericity measurement range: 0.97 to 1.00. [2] In the hollow resin particles described above [1], the shell is a polymer (P1) that is obtained by polymerizing the free radical polymerizable monomer component (M) by reacting a composition containing a free radical polymerizable monomer component (M), wherein the free radical polymerizable monomer component (M) may contain a crosslinking monomer (a). [3] In the hollow resin particles described in [2] above, the proportion of the aforementioned crosslinking monomer (a) in the aforementioned free radical polymerizable monomer component (M) may be from 20% by weight to 96% by weight. [4] In the hollow resin particles described in [2] or [3] above, the aforementioned free radical polymerizable monomer component (M) may contain a monofunctional monomer (b). [5] In the hollow resin particles described in [4] above, the proportion of the aforementioned monofunctional monomer (b) in the aforementioned free radical polymerizable monomer component (M) is from 4% by weight to 80% by weight. [6] In the hollow resin particles described in any one of [2] to [5] above, the composition contains a polymer component (P2), and the number average molecular weight of the aforementioned polymer component (P2) may be from 500 to 200,000. [7] In the hollow resin particles described in [6] above, when the total amount of the free radical polymerizable monomer component (M) is 100 parts by weight, the polymer component (P2) may be 0.1 parts by weight to 20 parts by weight. [8] In the hollow resin particles described in any one of [1] to [7] above, the volume average particle size may be 0.1 μm to 5.0 μm. [9] In the hollow resin particles described in any one of [1] to [8] above, the coefficient of variation of the volume average particle size may be 25% or less.

[10] The hollow resin particles described in any one of [1] to [9] above can be used as additives for semiconductor components.

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

[10] above.

[12] The hollow resin particles described in any one of [1] to [9] above can be used as additives for optical materials.

[13] The method for manufacturing hollow resin particles according to an embodiment of the present invention is a method for manufacturing hollow resin particles having a shell and a hollow portion surrounded by the shell. The manufacturing method includes a polymerization step of dispersing an oil phase containing a free radical polymerizable monomer component (M), a polymerization initiator, and an organic solvent in an aqueous phase, and then performing polymerization. In this step, when the total amount of the free radical polymerizable monomer component (M) is 100 parts by weight, the polymerization initiator is 2.00 parts by weight or less.

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

[13] above, the oil phase may contain a polymer component (P2). When the total amount of the free radical polymerizable monomer component (M) is 100 parts by weight, the polymer component (P2) may be 0.1 parts by weight to 20 parts by weight.

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

[13] or

[14] above, the number of particles with a diameter of 10 μm or larger out of 1,000,000 particles obtained by means of a flow particle image analyzer under the following measurement conditions A may be 80 or less; (Measurement conditions A) Particle size measurement range (sphere conversion volume basis): 0.5 μm to 200.0 μm, sphericity measurement range: 0.97 to 1.00.

[16] In the method for manufacturing hollow resin particles described in any one of

[13] to

[15] above, the proportion of particles with a diameter of 10 μm or larger out of 1 μm or larger, as determined by means of a Coulter counter method (pore size 50 μm), out of the total number of particles obtained in the above polymerization step may be 1.0% by volume or less.

[17] The method for manufacturing hollow resin particles as described in any of

[13] to

[16] above may include a grading step of grading the particles obtained in the aforementioned polymerization step.

[18] In the method for manufacturing hollow resin particles described in

[17] above, regarding the particles obtained in the aforementioned grading step, the number of particles with a diameter of 10 μm or larger out of 1,000,000 particles, as determined by a flow particle image analysis device under the following measurement conditions A, may be 45 or less; (Measurement conditions A) Particle size measurement range (sphere-to-volume standard): 0.5 μm to 200.0 μm Circularity measurement range: 0.97 to 1.00.

[19] In any of the above-described methods for manufacturing hollow resin particles

[13] to

[18] , the aqueous phase may contain a dispersing stabilizer, and the polymerization step may include dispersing the oil phase in the aqueous phase and then emulsifying it using a high-pressure emulsifier at a pressure of 1 MPa to 200 MPa. [Effects of the Invention].

[0009] According to an embodiment of the present invention, a hollow resin particle with reduced coarse particle number and excellent particle strength can be provided. Furthermore, a method for manufacturing such a hollow resin particle can be provided. Moreover, an application of such a hollow resin particle can be provided.

Implementation Method

[0010] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these embodiments.

[0011] When the term "(meth)acrylic acid" appears in this specification, it means "acrylic acid and / or methacrylic acid"; when the term "(meth)acrylate" appears, it means "acrylate and / or methacrylate"; and when the term "(meth)acrylonitrile" appears, it means "acrylonitrile and / or methacrylonitrile".

[0012] ≪≪1. Hollow Resin Particles≫≫ ≪1-1. Structure and Characteristics of Hollow Resin Particles≫ The hollow resin particles of the embodiments of the present invention have a shell and a hollow portion surrounded by the shell. The hollow resin particles of the embodiments of the present invention have a porosity of 5 to 90%. The hollow resin particles of the embodiments of the present invention, as determined by a flow-through particle imaging analyzer under the following measurement conditions A, have 45 or fewer particles with a diameter of 10 μm or larger out of 1,000,000 particles. (Measurement Condition A) Particle size measurement range (sphere-converted volume basis): 0.5 μm to 200.0 μm Circularity measurement range: 0.97 to 1.00

[0013] In this context, "hollow" means a state in which the interior is filled with substances other than resin, such as gas or liquid. In this respect, it is more preferably a state in which the interior is filled with gas.

[0014] The hollow portion may be composed of a single hollow region, or it may be composed of a plurality of hollow regions or a porous structure. In the hollow resin particles of the embodiments of the present invention, the hollow portion is preferably a single hollow structure composed of a single hollow region. By having a single hollow portion, the resin component constituting the shell is relatively more abundant, and the particles become less prone to breakage. Even if such hollow resin particles coexist and are mixed with inorganic particles in the resin composition, the shell is not prone to collapse. Furthermore, by having a single hollow portion, it is possible to effectively prevent the substrate or the like from penetrating into the hollow portion.

[0015] In this specification, the number of particles with a diameter of 10 μm or larger out of 1,000,000 particles obtained using a flow-through particle image analyzer under measurement condition A is recorded as "the number of coarse particles with a diameter of 10 μm or larger". Examples of flow-through particle image analyzers include: FPIA-3000S (manufactured by SYSMEX) and PARSHE ANALYZER (manufactured by HOSOKAWA MICRON).

[0016] In the hollow resin particles of the embodiments of the present invention, the number of coarse particles with a particle size of 10 μm or more, as obtained by the above method, is 45 or less. That is, the hollow resin particles of the embodiments of the present invention have a roundness of 0.97 or more, and the proportion of coarse particles with a particle size of 10 μm or more, in terms of the number of particles, is 0.0045% or less. The hollow resin particles of the embodiments of the present invention, with such a small number of coarse particles, are less prone to cracking or breakage, and have excellent particle strength. Furthermore, as described above, the hollow resin particles of the embodiments of the present invention, due to the small number of coarse particles, make it possible to form a thin film of resin layer composed of resin composition containing particles. Furthermore, clogging during the manufacturing process of resin composition and various components can be prevented. When the proportion of coarse particles exceeds the above range and is too large, for example, when a resin layer is formed from resin composition containing particles, it may be difficult to form a thin film or uneven thickness may occur. Furthermore, there is a risk of blockage occurring during the manufacturing process of the aforementioned resin composition. Moreover, there is a risk of unevenness forming in the resin layer, leading to a deterioration in the adhesion of the semiconductor component. Based on the above, from the viewpoint of improved reliability and yield, the hollow resin particles of the embodiment of the present invention are suitable for various components such as semiconductor components.

[0017] The hollow resin particle system of the embodiment of the present invention, under the above-mentioned measurement conditions A, preferably has 40 or fewer coarse particles with a particle size of 10 μm or larger, more preferably 30 or fewer, more preferably 20 or fewer, more preferably 10 or fewer, even more preferably 5 or fewer, particularly preferably 3 or fewer, most preferably 1 or fewer, and may have 0. Based on the above configuration, the hollow resin particle system can have superior particle strength.

[0018] The hollow resin particle system of the embodiment of the present invention, under the above-mentioned measurement conditions A, preferably has 55 or fewer particles with a diameter of 8 μm or more but less than 10 μm (hereinafter referred to as "the number of coarse particles with a diameter of 8 μm or more but less than 10 μm") per 1,000,000 particles, more preferably 50 or fewer, more preferably 40 or fewer, more preferably 30 or fewer, even more preferably 20 or fewer, particularly preferably 15 or fewer, and most preferably 10 or fewer. Based on the above configuration, the hollow resin particle system can have superior particle strength. Such a hollow resin particle system is more suitable for various components such as semiconductor components.

[0019] The number of coarse particles with a diameter of 10 μm or more and the number of coarse particles with a diameter of 8 μm or more but less than 10 μm can be determined, for example, as follows.

[0020] First, an aqueous solution of surfactant (dodecylbenzene sulfonate) was prepared by adding 0.01 parts to 4.94 parts of ion-exchanged water. Then, 0.06 parts of hollow resin particles were added to the aqueous solution of surfactant, and the hollow resin particles were dispersed in the aqueous solution of surfactant using a disperser (ultrasonic scrubber (VELVO-CLEAR, VS-150)) and ultrasonic treatment was applied for 10 minutes to obtain an aqueous dispersion of hollow resin particles for testing.

[0021] When using the FPIA-3000S (manufactured by SYSMEX) as a flow-through particle imaging analyzer, the obtained hollow resin particle aqueous dispersion is introduced into the flow-through particle imaging analyzer (SYSMEX, FPIA-3000S; equipped with a standard objective lens (10x)), and measurements are performed under the following conditions. Particle sheath (SYSMEX, PSE-900A) is used as the sheath fluid. Measurement mode: HPF mode. Particle size measurement range (sphere-to-volume standard): 0.5 μm to 200.0 μm. Circularity measurement range: 0.97 to 1.00. During measurement, before the start of the measurement, the automatic focus adjustment of the flow-through particle imaging analyzer is performed using a suspension of standard polymer particle groups (e.g., Thermo Fisher Scientific, 5200A (prepared by diluting standard polystyrene particle groups with ion-exchanged water)). Circularity is calculated by dividing the circumference of a true circle having the same projected area as the image of the hollow resin particles by the circumference of the image of the hollow resin particles. Within the particle circularity measurement range of 0.97 to 1.0, the equivalent circle diameter (particle size) was measured for 100,000 particles, and the number of hollow resin particles with a particle size of 10.0 μm or larger and the number of hollow resin particles with a particle size of 8 μm or larger but less than 10 μm were calculated separately. Here, the number of hollow resin particles with a particle size of 8 μm or larger but less than 10 μm is calculated by dividing the number of hollow resin particles with a particle size of 8.0 μm or larger but less than 10.0 μm by the number of hollow resin particles with a particle size of 10.0 μm. This process was performed 10 times (i.e., measuring a total of 1,000,000 particles), and the sum of the number of hollow resin particles with a volume average particle size of 10.0 μm or more and the number of hollow resin particles with a particle size of 8 μm or more but less than 10 μm was obtained. These sums were used as the "number of coarse particles with a particle size of 10 μm or more" and the "number of coarse particles with a particle size of 8 μm or more but less than 10 μm", respectively.

[0022] When using a PARSHE ANALYZER (manufactured by HOSOKAWA MICRON) as a flow-through particle imaging analyzer, the hollow resin particle aqueous dispersion prepared as described above is introduced into the flow-through particle imaging analyzer (HOSOKAWA MICRON, PARSHE ANALYZER; equipped with a standard objective lens (10x)), and the measurement is performed under the following conditions. PAS sheath fluid (manufactured by HOSOKAWA MICRON) is used as the sheath fluid. Other operating procedures are the same as those described for the FPIA-3000S. Particle size measurement range (sphere-to-volume standard): 0.5 μm to 200.0 μm; sphericity measurement range: 0.97 to 1.00.

[0023] The hollow resin particles of the embodiments of the present invention, obtained by the Coulter Counter method (pore size 50 μm), have a particle size of 10 μm or larger, and the proportion of these particles relative to the total number of particles with a particle size of 1 μm to 30 μm is 1.0 vol% or less. In this specification, the aforementioned proportion of particles with a particle size of 10 μm or larger, obtained by the Coulter Counter method (pore size 50 μm), relative to the total number of particles with a particle size of 1 μm to 30 μm is described as the "presence proportion of particles with a particle size of 10 μm or larger". The presence proportion of particles with a particle size of 10 μm or larger in the hollow resin particles of the embodiments of the present invention is preferably 0.70 vol% or less, more preferably 0.50 vol% or less, more preferably 0.30 vol% or less, even more preferably 0.20 vol% or less, particularly preferably 0.10 vol% or less, and most preferably 0.01 vol% or less. In the embodiments of the present invention, the proportion of hollow resin particles with a particle size of 10 μm or more may be 0.00 by volume.

[0024] The hollow resin particles of the embodiments of the present invention preferably have a porosity of 10% to 80%, more preferably 15% to 75%, even more preferably 15% to 70%, even more preferably 20% to 65%, particularly preferably 20% to 60%, and most preferably 23% to 55%. If the porosity of the hollow resin particles is within the above range, the hollow resin particles can have superior particle strength.

[0025] The volume average particle size (volume average primary particle size) of the hollow resin particles in the embodiments of the present invention is not particularly limited and can be appropriately set according to the purpose or use. The volume average particle size of the hollow resin particles in the embodiments of the present invention is, for example, 0.1 μm to 10.0 μm, preferably 0.1 μm to 5.0 μm, more preferably 0.2 μm to 5.0 μm or less, even more preferably 0.3 μm to 5.0 μm, particularly preferably 0.5 μm to 5.0 μm, and most preferably 1.0 μm to 5.0 μm. When the average particle size of the hollow resin particles is less than 0.1 μm, the shell thickness becomes relatively thin, which may prevent the formation of hollow resin particles with sufficient strength. When the average particle size of the hollow resin particles is greater than 10.0 μm, the polymer produced by the polymerization of monomer components in suspension polymerization may not easily separate from the solvent, thereby making it difficult to form a shell. Volume average particle size can be determined using, for example, a laser diffraction / scattering particle size distribution measuring device manufactured by BECKMAN COULTER.

[0026] The coefficient of variation of the volume average particle size of the hollow resin particles in the embodiments of the present invention is not particularly limited, but can be appropriately set according to the purpose or use. For example, the coefficient of variation of the volume average particle size of the hollow resin particles in the embodiments of the present invention is 40.0% or less, preferably 30.0% or less, more preferably 25.0% or less, and even more preferably 23.0% or less. For example, the coefficient of variation of the volume average particle size of the hollow resin particles in the embodiments of the present invention can be 1.0% or more, 5.0% or more, or 10.0% or more.

[0027] In the embodiments of the present invention, the amount of metal residue in the hollow resin particles is preferably 100 ppm or less, and more preferably 50 ppm or less. If the amount of metal residue in the hollow resin particles exceeds 100 ppm, there is a risk that the excellent low dielectric properties may not be exhibited, or that the low dielectric properties may not be uniform, or that the insulation of the component used may be impaired. Furthermore, if the amount of metal residue in the hollow resin particles exceeds 100 ppm, it may also become a cause of component corrosion. For example, the combined K and Na content in the hollow resin particles is preferably 50 ppm or less, more preferably 30 ppm or less, even more preferably 20 ppm or less, and most preferably 15 ppm or less.

[0028] ≪1-2. Shell Portion≫ The shell portion preferably comprises a polymer (P1), which is obtained by polymerizing the free radical polymerizable monomer component (M) through a reaction of a composition comprising a free radical polymerizable monomer component (M). That is, the polymer (P1) can be obtained by the polymerization reaction of the free radical polymerizable monomer component (M). The free radical polymerizable monomer component (M) is typically composed of vinyl monomers. Hereinafter, the free radical polymerizable monomer component (M) will be referred to as "monomer component (M)".

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

[0030] In view of the point that the effects of the present invention can be further demonstrated, the polymer (P1) in the shell 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.

[0031] The monomer component (M) preferably includes a crosslinking monomer (a). Also, the monomer component (M) preferably includes a monofunctional monomer (b). The monomer component (M) preferably includes both the crosslinking monomer (a) and the monofunctional monomer (b). Therefore, the polymer (P1) is preferably obtained, for example, by polymerizing the monomer component (M) containing the crosslinking monomer (a) and the monofunctional monomer (b), and has structural units derived from the crosslinking monomer (a) and structural units derived from the monofunctional monomer (b).

[0032] Accordingly, polymer (P1) can be defined as that which is obtained by the reaction of monomer component (M). This is because polymer (P1) becomes polymer by the reaction of monomer component (M), so polymer (P1) cannot be directly defined based on its structure. Furthermore, there are generally impractical situations ("impossible / impractical situations"), so polymer (P1) is properly defined as a "matter" based on the definition of "obtained by the reaction of monomer component (M)".

[0033] The crosslinking monomer (a) can be any suitable crosslinking monomer that has crosslinking properties (having two or more free radical polymerizable double bonds in the backbone) without impairing the effects of the present invention, with crosslinking vinyl monomers being preferred. Examples of such crosslinking monomers (a) include: divinylbenzene, divinylnaphthalene, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, decaethylene glycol di(meth)acrylate, pentadecylethylene glycol di(meth)acrylate, pentacontahecta ethylene glycol di(meth)acrylate, 1,3-endobutyl di(meth)acrylate, allyl (meth)acrylate, trimethylolpropane tri(meth)acrylate, neopentyl terephthalate tetraacrylate, neopentyl glycol di(meth)acrylate, etc. The crosslinking monomer (a) preferably includes aromatic crosslinking monomers such as divinylbenzene and divinylnaphthalene, which have aromatic functional groups and two or more free radical polymerizable double bonds in the backbone. The crosslinking monomer (a) can be used alone or in combination with two or more.

[0034] In terms of further demonstrating the effects of the present invention, the crosslinking monomer (a) in the monomer component (M) is preferably 20% to 99% by weight, more preferably 20% to 97% by weight, more preferably 20% to 96% by weight, more preferably 25% to 96% by weight, even more preferably 30% to 95% by weight, particularly preferably 35% to 90% by weight, and most preferably 35% to 85% by weight. The effects of the present invention are further demonstrated by the shell comprising a polymer (P1) having such a structure.

[0035] The monofunctional monomer (b) can be any suitable monofunctional monomer as long as it has a molecular structure with a single free radical polymerizable double bond in its backbone, without impairing the effects of the present invention. Monofunctional vinyl monomers are preferred. Examples of such monofunctional monomers (b) include: styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, tert-butylstyrene, vinylnaphthalene, styrene sulfonic acid, styrene sulfonates (sodium styrene sulfonate, ammonium styrene sulfonate, etc.), vinyl benzoic acid (o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid), vinylphenol (o-vinylphenol, m-vinylphenol, p-vinylphenol), etc., aromatic monofunctional monomers; methyl methacrylate (methyl methacrylate, methyl acrylate), ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate. Isobutyl methacrylate, dibutyl methacrylate, tributyl methacrylate, pentyl methacrylate, isoamyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, isooctyl methacrylate, nonyl methacrylate, isononyl methacrylate, decyl methacrylate, isodecanyl methacrylate, undecyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, tetradecyl methacrylate, pentadecyl methacrylate, hexadecyl methacrylate Heptadecanyl methacrylate, octadecyl methacrylate, isostearyl methacrylate, nonadecanyl methacrylate, eicosyl methacrylate, and other alkyl methacrylates with 1 to 20 carbon atoms in the alkyl group bonded to the ester; cyclohexyl methacrylate, isothiocyanate methacrylate, dicyclopentyl methacrylate, and other alkyl methacrylates with an alicyclic structure in the ester portion; hydroxyalkyl methacrylate monomers such as hydroxyethyl methacrylate; methacrylic acid; 2-methacryloxyethyl succinic acid, 2-methacryloxyethyl phthalic acid, 2-methacryloxyethyl hexahydrophthalic acid, 2-methyl... Hydrophilic monomers containing carboxyl groups, such as 2-acryloyloxyethyl maleic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl succinic acid, and 2-acryloyloxyethyl phthalic acid; polyethylene glycol propylene glycol monomethacrylate; glycidyl acrylate, allyl glycidyl ether, 4-hydroxybutyl (meth)acrylate glycidyl ether, etc., monomers containing glycidyl groups; 1,2-epoxy-4-vinylcyclohexane, (3,4-epoxycyclohexyl)methyl acrylate, etc., monomers containing epoxy groups; acrylamide derivative monomers such as 4-vinylphenyl glycidyl ether (meth)acrylamide; (meth)acrylonitrile monomers; etc.The monofunctional monomer (b) system is preferably composed of aromatic monofunctional monomers, with styrene, α-methylstyrene, tributylstyrene, or vinylnaphthalene being more preferred. The monofunctional monomer (b) system can be used alone or in combination with two or more monomers.

[0036] Insofar as the effects of the present invention are further manifested, the content of the monofunctional monomer (b) in the monomer component (M) is preferably 1% to 80% by weight, more preferably 3% to 80% by weight, more preferably 4% to 80% by weight, more preferably 4% to 75% by weight, even more preferably 5% to 70% by weight, particularly preferably 10% to 65% by weight, and most preferably 15% to 65% by weight. The effects of the present invention are further manifested by the shell comprising a polymer (P1) having such a structure.

[0037] In view of the point that the effects of the present invention can be further demonstrated, the total content of the crosslinking monomer (a) and the monofunctional monomer (b) 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.

[0038] The monomer component (M) may include any suitable other monomers that are different from either the crosslinking monomer (a) or the monofunctional monomer (b) described above, without impairing the effects of the present invention. There may be only one other monomer or two or more other monomers.

[0039] Other monomers may include, for example: ethylene-halogenated monomers such as vinyl chloride; ethylene-carboxylic acid ester monomers such as vinyl acetate; olefin monomers such as ethylene; unsaturated amide monomers; vinyl alcohol; silane coupling agents containing vinyl groups; phosphate ester monomers (trade name "KAYAMER (registered trademark) PM-21"), etc. The monomer component (M) may also not contain other monomers.

[0040] In order to further demonstrate the effects of the present invention, the monomer component (M) in the composition is preferably 85% to 100% by weight, more preferably 90% to 100% by weight. If the content of the monomer component (M) in the composition exceeds the above range and is too low, there is a risk that the effects of the present invention will not be manifested. Here, the monomer component (M) does not contain polymerization initiators and surfactants used in the polymerization reaction.

[0041] Preferably, the composition includes a polymer component (P2) in addition to the monomer component (M). The polymer component (P2) is a polymer different from the polymer (P1). The polymer component (P2) may or may not contain polymerizable functional groups. The polymer component (P2) may or may not react with the monomer component (M).

[0042] The number average molecular weight of the polymer component (P2) is preferably between 500 and 200,000. By including such a polymer component (P2), phase separation of polymeric oil droplets during suspension polymerization can be promoted, and uniform particles can be easily formed. As a result, hollow resin particles with fewer coarse particles and excellent particle strength can be obtained. In addition, when using a polymer component (P2) with a number average molecular weight of less than 500, phase separation may not be easily achieved, and it may be difficult to form a shell. When using a polymer component (P2) with a number average molecular weight greater than 200,000, the average particle size may increase due to the increased viscosity of the oil droplets, or the particles may become irregularly shaped, or it may be difficult to form a shell. Examples of such polymer components (P2) include: polystyrene, polyethylene, polypropylene, aliphatic olefin polymers with 4 or more carbon atoms (which may be linear or have branched side chains), polyphenylene ether, modified polyphenylene ether, polymethyl methacrylate, block copolymers of styrene and butadiene (e.g., styrene-butadiene-styrene block copolymer (SBS), etc.), block copolymers of styrene and isoprene (e.g., styrene-isoprene-styrene block copolymer (SIS), etc.), poly(meth)acrylate (which may be aliphatic chains with 1 or more carbon atoms, linear, or branched), paraffin wax, etc. Furthermore, at least one of the unsaturated bonds in the above-mentioned polymer component (P2) can undergo a hydrogenation reaction. The polymer component (P2) may be only one type or may consist of two or more types.

[0043] When the polymer component (P2) can react with the monomer component (M), the polymer (P1) may, for example, contain structural units derived from the crosslinking monomer (a), structural units derived from the monofunctional monomer (b), and structural units derived from the polymer component (P2). When the polymer component (P2) does not react with the monomer component (M), or when the reactivity of the polymer component (P2) is low, the shell contains both the polymer (P1) and the polymer component (P2).

[0044] The polymer component (P2) may contain a hydrocarbon resin. The hydrocarbon resin may be any suitable compound without impairing 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 selected from at least one of the group consisting of aliphatic / aromatic hydrocarbon resins, aromatic hydrocarbon resins, and aliphatic hydrocarbon resins; more preferably, it is selected from at least one of the group consisting of aliphatic / aromatic hydrocarbon resins and aromatic hydrocarbon resins; and even more preferably, it is an aliphatic / aromatic hydrocarbon resin. Based on the above, the reduction of coarse hollow resin particles can be achieved. These hydrocarbon resins may be used alone or in combination of two or more.

[0045] Aliphatic / aromatic hydrocarbon resins refer to hydrocarbon resins synthesized by copolymerization of aliphatic and aromatic hydrocarbons. Aliphatic / aromatic hydrocarbon resins are, for example, resins polymerized using styrene, vinyltoluene, indene, isoprene, etc. as main raw materials.

[0046] Aromatic hydrocarbon resins are resins polymerized from styrene, vinyltoluene, indene, etc. as main raw materials.

[0047] Alicyclic hydrocarbon resins are resins obtained by hydrogenating aliphatic / aromatic hydrocarbon resins or aromatic hydrocarbon resins, for example.

[0048] Aliphatic hydrocarbon resin is a hydrocarbon resin formed by polymerizing one or more aliphatic hydrocarbons with polymerizable unsaturated bonds.

[0049] In view of the point that the effects of the present invention can be further demonstrated, when the total amount of monomer components (M) is 100 parts by weight, the content of polymer components (P2) in the composition is preferably 0.1 parts by weight to 30 parts by weight, more preferably 0.1% by weight to 20% by weight, even more preferably 0.5% by weight to 18% by weight, particularly preferably 1% by weight to 15% by weight, and most preferably 2% by weight to 10% by weight.

[0050] ≪1-3. Uses of Hollow Resin Particles≫ The hollow resin particles of the embodiments of the present invention can be used in various applications. In terms of further utilizing the effects of the present invention, the hollow resin particles of the embodiments of the present invention are suitable as additives for semiconductor components, additives for optical materials such as light diffusers or anti-glare / low-reflection materials, additives for coatings, and additives for printing inks, etc., and representatively, they are suitable for use in resin compositions for semiconductor components. As an example of the use of the hollow resin particles of the embodiments of the present invention, the following description pertains to resin compositions for semiconductor components.

[0051] The resin composition system for semiconductor components of the present invention comprises hollow resin particles of the present invention.

[0052] The term "semiconductor component" refers to a component that constitutes a semiconductor, such as a semiconductor package or a semiconductor module. In this specification, the term "resin composition for semiconductor components" refers to a resin composition used in semiconductor components.

[0053] A semiconductor packaging system is a component consisting of an IC chip as an essential component and is constructed using at least one of the following components: molding resin, underfill material, molding underfill material, die bond material, prepreg for semiconductor package substrate, metal foil laminate for semiconductor package substrate, and additive material for printed circuit board for semiconductor package.

[0054] A semiconductor module is a device that uses a semiconductor package as an essential component and is constructed using at least one of the following components: a prepreg for printed circuit boards, a metal foil laminate for printed circuit boards, a laminate material for printed circuit boards, a solder resist material, a cover film, an electromagnetic wave shielding film, and a bonding pad for printed circuit boards.

[0055] ≪≪2. Method for manufacturing hollow resin particles≫≫ The hollow resin particles of the embodiments of the present invention can be manufactured by any suitable method without impairing the effects of the present invention.

[0056] The method for manufacturing hollow resin particles in this invention (polymerization method) is not particularly limited as long as it is a known polymerization method. For example, methods such as emulsification polymerization, suspension polymerization, seed (emulsification) polymerization, dispersion polymerization, mini-emulsion polymerization, and microemulsion polymerization can be listed.

[0057] In the method for manufacturing hollow resin particles (polymerization method) of the present invention, polymerization initiators, surfactants (emulsifiers), dispersants, etc. may be used as needed.

[0058] Emulsion polymerization is a polymerization method in which an aqueous medium, a monomer that is difficult to dissolve in the medium, and a surfactant (emulsifier) ​​are mixed, and a polymerization initiator that is soluble in the aqueous medium is added thereto, and polymerization is carried out. Emulsion polymerization is characterized by having less uniformity in the particle size of the resulting resin particles.

[0059] Suspension polymerization is a polymerization method in which monomers are mechanically stirred in an aqueous medium, thereby suspending the monomers in the aqueous medium and polymerizing them. When compared with the particles produced by emulsion polymerization, the particles generated by suspension polymerization are characterized by larger particle size and a wider particle size distribution. Furthermore, by using a homogenizer, ultrasonic processor, nanomizer (registered trademark), microfluidiczer (registered trademark), nanovater (registered trademark), or a coarse particle treatment device (NVR) (registered trademark), particles with a relatively steep particle size distribution can also be obtained.

[0060] Seed polymerization uses polymer microparticles obtained by polymerizing monomers as seed particles. The monomers are absorbed into the seed particles in a medium, and the seed particles swell with the monomers before the monomers polymerize within the seed particles. By growing the seed particles, seed polymerization can obtain resin particles with a larger particle size than the original seed particles. Seed emulsion polymerization uses a water-soluble polymerization initiator to grow seed particles while polymerization is underway.

[0061] Dispersion polymerization is a method in which monomers are dispersed in a polymerization solvent that may contain a dispersing stabilizer, and a polymerization initiator is added to polymerize the monomers. To prevent particles from sticking together during polymerization, it is preferably carried out under stirring with ultrasonic irradiation and / or with a mechanical stirring device such as a magnetic stir bar. Dispersion polymerization is characterized by easy control of particle size and easy acquisition of resin particles.

[0062] In terms of obtaining hollow resin particles with particularly uniform particle size and a small number of coarse particles, the manufacturing method of the embodiment of the present invention is preferably suspension polymerization, seed polymerization, or emulsion polymerization, and suspension polymerization using a micro emulsifier is even more preferred.

[0063] A representative embodiment of the method for manufacturing hollow resin particles of the present invention includes a polymerization step, wherein the polymerization step involves dispersing an oil phase containing a free radical polymerizable monomer component (M), a polymerization initiator, and an organic solvent in an aqueous phase containing an aqueous medium, and performing suspension polymerization. The monomer component (M) preferably includes a crosslinking monomer (a) and a monofunctional monomer (b). The oil phase preferably includes a polymer component (P2) in addition to the monomer component (M), the polymerization initiator, and the organic solvent.

[0064] The hollow resin particles of the embodiment of the present invention can be easily manufactured according to the above manufacturing method.

[0065] The descriptions of the monomer component (M) and the polymer component (P2) can be referred to in the aforementioned section on the shell. When the total amount of the monomer component (M) is taken as 100 parts by weight, the content of the polymer component (P2) is preferably 0.1 parts by weight to 30 parts by weight, more preferably 0.1% by weight to 20% by weight, even more preferably 0.5% by weight to 18% by weight, particularly preferably 1% by weight to 15% by weight, and most preferably 2% by weight to 10% by weight.

[0066] The organic solvent may be one or more. As for the organic solvent, any suitable organic solvent may be used without impairing the effects of the present invention. Preferably, such organic solvents are those with a boiling point below 100°C. By using an organic solvent with a boiling point below 100°C, it is easier to remove solvent from the hollow portions of the obtained hollow resin particles, and manufacturing costs can be reduced.

[0067] Examples of organic solvents with a boiling point of less than 100°C include: heptane, hexane, cyclohexane, methyl acetate, ethyl acetate, methyl ethyl ketone, chloroform, and carbon tetrachloride.

[0068] The amount of organic solvent used is within the range that does not impair the effects of the present invention, and any suitable amount may be used. For example, the amount used is 10 to 250 parts by weight relative to 100 parts by weight of monomer component (M).

[0069] The oil phase preferably contains a polymerization initiator. The polymerization initiator may be one type or two or more. Any suitable polymerization initiator may be used without impairing the effects of the invention.

[0070] The polymerization initiator is preferably a free radical polymerization initiator, especially a thermal polymerization initiator. 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.

[0071] Polymerization initiator systems include, for example: 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropanediamine]n hydrate (trade name "VA-057"), 4,4'-azobis(4-cyanograzine) (trade name "V-501"), 2,2'-azobis[2-(2-imidazolin-2-yl)propane] (trade name "VA-061" and its dihydrochloride, trade name "VA-044"), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propane] (trade name "VA-086"), 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl] Water-soluble azo compounds including: 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionic acid} (trade name "VA-080"), 2,2'-azobis{2-methyl-N-[2-(1-hydroxybutyl)]propionic acid} (trade name "VA-085") (all manufactured by Fuji Film and Koko Pure Chemical Industries Co., Ltd.); cumene hydroperoxide, di-tert-butyl peroxide, diisopropylphenyl peroxide, benzoyl peroxide, lauryl peroxide, dimethylbis(tert-butylperoxy)hexane, and dimethylbis(tert-butylperoxy)... Hexyne-3, bis(tert-butylperoxyisopropyl)benzene, bis(tert-butylperoxy)trimethylcyclohexane, butyl-bis(tert-butylperoxy)valerate, tert-butyl 2-ethylhexaneperoxyate, dibenzoyl peroxide, p-menthane hydroperoxide, tert-butyl-2-ethylperoxyhexanoate, tert-butyl-2-ethylperoxyacetate, and tert-butylperoxybenzoate, etc.; 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 Oil-soluble nitrile-azo compounds such as 2'-azobis(2-methylhexanonitrile), 2,2'-azobis(2,3,3-trimethylbutyronitrile), 2,2'-azobis(2,4,4-trimethylvaleronitrile), 2,2'-azobis(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-carboxynitrile), 2-(aminomethoxyazo)isobutyronitrile, and 4,4'-azobis(4-cyanovaleric acid); etc.

[0072] Furthermore, a redox initiator can be used as a polymerization initiator, which is a combination of the above-mentioned polymerization initiators of persulfate and organic peroxide, and reducing agents such as sodium formaldehyde sulfoxylate, sodium bisulfite, ammonium bisulfite, sodium thiosulfate, ammonium thiosulfate, hydrogen peroxide, sodium hydroxymethanesulfinate, L-ascorbic acid and its salts, cuprous salts, and ferrous salts.

[0073] Among these, the polymerization initiator is preferably selected from 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropanediamine]n hydrate (trade name "VA-057"), 4,4'-azobis(4-cyanograzine) (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)propane] (trade name "VA-086"), 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propane} (trade name "VA-080"), 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propane} (trade name "VA-080"), 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propane} ( The product is at least one of the following: trade name "VA-082"; 2,2'-azobis{2-methyl-N-[2-(1-hydroxybutyl)]-propionamide} (trade name "VA-085"); (both manufactured by Fuji Film and Koko Pure Chemical Industries, Ltd.); 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile); 2,2'-azobis(2,4-dimethylpentanonitrile); 2,2'-azobisisobutyronitrile; 2,2'-azobis(2-methylbutyronitrile); 1,1'-azobis(cyclohexane-1-carboxynitrile); 4,4'-azobis(4-cyanovaleric acid); cumene hydroperoxide; di-tert-butylperoxide; diisopropylphenylperoxide; benzoylperoxide; tert-butyl-2-ethylperoxyhexanoate; and laurylperoxide.

[0074] To the extent that the effects of the present invention are not impaired, the amount of polymerization initiator used can be any suitable amount. Such an amount relative to 100 parts by weight of monomer component (M) is, for example, preferably 0.05 to 5.0 parts by weight, more preferably 0.08 to 3.0 parts by weight, even more preferably 0.1 to 2.0 parts by weight, particularly preferably 0.1 parts by weight or more but less than 2.0 parts by weight, and most preferably 0.1 to 1.9 parts by weight.

[0075] In addition to the above-mentioned components, the oil phase may contain any other suitable components without impairing the effects of the present invention. Such other components may be only one or more.

[0076] Examples of aqueous media include water, and mixtures of water and lower alcohols (ethanol, isopropanol, etc., with 5 or fewer carbon atoms). Water is preferably selected from at least one of the groups consisting of ion-exchanged water and distilled water.

[0077] The amount of aqueous medium used is within the range that does not impair the effects of the present invention, and any suitable amount can be used. Preferably, the amount used is 100 to 2000 parts by weight relative to 100 parts by weight of the oil phase, and more preferably 200 to 1000 parts by weight. By adjusting the amount of aqueous medium used to the above range, the dispersion stability of the monomers during polymerization is improved, and the formation of resin particle agglomerates can be suppressed during polymerization.

[0078] The aqueous phase system preferably contains a dispersing stabilizer. Any suitable dispersing stabilizer may be used without impairing the effects of the invention. The dispersing stabilizer may be only one type or may be two or more types.

[0079] Examples of dispersing stabilizers include water-soluble polymers such as polyvinyl alcohol, polycarboxylic acid, cellulose compounds (hydroxyethyl cellulose, carboxymethyl cellulose, etc.), and polyvinylpyrrolidone. Examples of dispersing stabilizers also 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 metasilate, calcium sulfate, barium sulfate, and colloidal silica. Among these, magnesium pyrophosphate is preferred because it is easier to remove from hollow resin particles and less likely to remain on the surface of the hollow resin particles.

[0080] To the extent that the effects of the present invention are not impaired, any suitable amount of dispersant stabilizer may be used. It is preferred that the dispersant stabilizer be used at 0.5 to 10 parts by weight relative to 100 parts by weight of an aqueous medium.

[0081] The aqueous phase system preferably contains a surfactant. Any suitable surfactant may be used without impairing the effects of the invention. The surfactant may be one type or two or more types. Examples of such surfactants include: anionic surfactants, cationic surfactants, nonionic surfactants, and zwitterionic surfactants.

[0082] Anionic surfactants include, for example: sodium oleate; fatty acid soaps such as potassium castor oil soap; polysulfonates; polycarboxylates; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; alkyl aryl sulfonates; alkyl naphthalene sulfonates; alkyl sulfonates; dialkyl sulfonates; dialkyl sulfosuccinates; alkyl phosphates; alkyl phosphate esters; sodium salt of β-naphthalene sulfonate formalin condensate and other naphthalene sulfonate formalin condensates or their salts; polyoxyethylene ethyl nonyl phenyl ether sulfate and other polyoxyethylene ethyl alkyl phenyl ether sulfates; polyoxyethylene ethyl styryl phenyl ether phosphate; polyoxyethylene ethyl alkyl ether phosphate; polyoxyethylene ethyl lauryl ether sulfate sodium, polyoxyethylene ethyl lauryl ether sulfate and other polyoxyethylene ethyl alkyl ether sulfates; polyoxyethylene ethyl alkyl sulfates; polyoxyethylene ethyl alkyl phosphate sulfonates; glyceryl borate fatty acid esters; polyoxyethylene ethyl glyceryl fatty acid esters. Anionic surfactants can be one type or two or more. Furthermore, ammonium salts are preferred as the relative ionic cation of the anionic group. Using such surfactants can reduce the amount of metal residue.

[0083] 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 type of cationic surfactant, or there may be two or more types.

[0084] Nonionic surfactants include, for example: (meth)acrylate sulfate surfactants (commercially available products, such as RMA-564, RMA-568, RMA-1114, etc. manufactured by Nippon Emulsifier Co., Ltd.); polyoxyethylene alkyl-branched decyl ethers; polyoxyethylene ethyl tridecyl ether, polyoxyethylene ethyl isodecanyl ether, polyoxyethylene ethyl lauryl ether, polyoxyethylene ethyl cetyl ether, etc.; polyoxyethylene ethyl naphthyl ether, polyoxyethylene ethyl phenyl ether, etc.; polyoxyethylene alkyl alkyl aryl ethers; polyoxyethylene alkyl aryl ethers; polyether polyols; polyoxyethylene ethyl styrene phenyl ether; polyoxyethylene ethyl polyoxypropylene glycol; polyoxyethylene ethyl glycerol isostearate; polyoxyethylene fatty acid esters; sorbitol fatty acid esters; polyoxysorbitol fatty acid esters; polyoxyethylene alkylamines; glycerol fatty acid esters; ethylene-propylene block polymers. The nonionic surfactant system may consist of only one type or two or more types.

[0085] Examples of zwitterionic surfactants include: lauryl dimethylamine oxide, alkyl diaminoethyl glycine hydrochloride, sodium lauryl aminopropionate, alkyl betaine, etc. There may be only one type of zwitterionic surfactant, or there may be two or more types.

[0086] A vinyl-containing reactive surfactant can be used as the surfactant. There may be only one vinyl-containing reactive surfactant or two or more. When a vinyl-containing reactive surfactant is used, it is incorporated into the polymer (P1), allowing the surfactant to effectively adhere to the surface of particles in the suspension polymerization, thereby improving the interfacial activity. Therefore, excellent interfacial activity can be obtained, suppressing particle aggregation or agglomeration during manufacturing, reducing the formation of out-of-specification particles, and reducing coarse particles.

[0087] Examples of reactive surfactants containing vinyl groups include: anionic surfactants containing vinyl groups and nonionic surfactants containing vinyl groups.

[0088] Examples of anionic surfactants containing vinyl groups include: ammonium polyoxyethylene-1-(allyloxymethyl)alkyl ether sulfate, ammonium polyoxyethylene-styrene-propylene-phenyl ether sulfate, ammonium polyoxyethylene-alkylalkenyl ether sulfate, α-sulfon-ω-(1-alkoxymethyl-2-(2-propenyloxy)ethoxy)-poly(oxy-1,2-ethanediyl)ammonium, polyoxypropylene-allyl ether phosphate, and bis(polyoxyethylene-phenyl ether)methacrylate sulfate. Furthermore, ammonium salts are preferred as the anti-cation of the anionic group. By using such surfactants, the average particle size of hollow resin particles can be further reduced, and coarse particles can be decreased. Additionally, the amount of metal residue can be reduced.

[0089] Commercially available products of polyoxyethylene-1-(allyloxymethyl)alkyl ether ammonium sulfate include, for example, the trade name "AQUARON KH-10" and the trade name "AQUARON KH-1025" (25% by weight aqueous solution of "AQUARON KH-10") manufactured by First Industrial Pharmaceutical Co., Ltd.

[0090] Commercially available products of polyoxyethylene styrene-propylene phenyl ether sulfate ammonium can be listed as follows: "AQUARON AR-10", "AQUARON AR-20", "AQUARON AR-3025" (25% aqueous solution of "AQUARON AR-30") and "AQUARON AR-1025" (25% aqueous solution of "AQUARON AR-10") manufactured by First Industrial Pharmaceutical Co., Ltd.

[0091] Commercially available products of polyoxyalkylene ether ammonium sulfate include, for example, the product "LATEMUL PD-104" manufactured by Kao Corporation.

[0092] Commercially available products of α-sulfon-ω-(1-alkoxymethyl-2-(2-propenyloxy)ethoxy)-poly(oxy-1,2-ethanediyl)ammonium can be listed as follows: "ADEKA REASOAP SR-10" and "ADEKA REASOAP SR-20" manufactured by ADEKA Co., Ltd.

[0093] Commercially available products of polyoxypropylene allyl ether phosphate include, for example, "ADEKA REASOAP PP-70" manufactured by ADEKA Co., Ltd.

[0094] Commercially available products of bis(polyoxyethylene ethyl phenyl ether) methacrylate sulfate include, for example, "ANTOX MS-60" manufactured by Japan Emulsifier Co., Ltd.

[0095] Examples of nonionic surfactants containing vinyl groups include: polyoxyethylene styrene-propylene phenyl ether, polyoxyethylene-1-(allyloxymethyl)alkyl ether, and polyoxyethylene alkylalkenyl ether.

[0096] Commercially available products of polyoxyethylene styrene-based propylene phenyl ethers include, for example, the products manufactured by First Industrial Pharmaceutical Co., Ltd. under the trade names "AQUARON AN-10", "AQUARON AN-20", "AQUARON AN-30", and "AQUARON AN-5065".

[0097] Commercially available polyoxyethylene-1-(allyloxymethyl)alkyl ethers can be listed as follows: "AQUARON KN-10", "AQUARON KN-20", "AQUARON KN-30", "AQUARON KN-5065" manufactured by Daiichi Industrial Pharmaceutical Co., Ltd., and "ADEKA REASOAP ER-10", "ADEKA REASOAP ER-20", "ADEKA REASOAP ER-30", "ADEKA REASOAP ER-40" manufactured by ADEKA Co., Ltd.

[0098] Commercially available polyoxyalkylene ethers can be listed as, for example, the products manufactured by Kao Corporation under the brand names "LATEMUL PD-420", "LATEMUL PD-430", and "LATEMUL PD-450".

[0099] To the extent that the effects of the present invention are not impaired, the amount of surfactant used can be any suitable amount. Preferably, such an amount is 0.001 to 5 parts by weight relative to 100 parts by weight of the aqueous phase; more preferably, 0.005 to 3 parts by weight; and even more preferably, 0.01 to 1 part by weight.

[0100] To the extent that the effects of the present invention are not impaired, the aqueous system may contain any other suitable components in addition to the components described above.

[0101] Any suitable method may be used to mix the oil phase and the aqueous phase as long as suspension polymerization can be carried out without compromising the effects of the present invention.

[0102] The suspension is prepared by mixing an oil phase and an aqueous phase and stirring. Typically, this is done by dispersing the oil phase in the aqueous phase. The oil phase can be dispersed in the aqueous phase in droplet form, and any suitable dispersion method can be used without compromising the effects of the invention. A representative example of such a dispersion method is the use of a homogenizer, such as an ultrasonic homogenizer or a high-pressure homogenizer.

[0103] For example, the preferred manufacturing method of an embodiment of the present invention includes: in the polymerization step, the aqueous phase contains a dispersing stabilizer, and after the oil phase is dispersed in the aqueous phase, emulsification is performed using a high-pressure emulsifier at a pressure of 1 MPa to 200 MPa.

[0104] Any suitable polymerization temperature may be used as long as it is suitable for suspension polymerization and does not impair the effects of the present invention. Such polymerization temperatures are, for example, 30°C to 95°C.

[0105] The polymerization time can be any suitable time as long as it is appropriate for suspension polymerization and does not impair the effects of the present invention. Such polymerization time is preferably 1 hour to 20 hours.

[0106] It is preferable to perform a post-polymerization heating process to obtain hollow resin particles with high finish.

[0107] The temperature at which the subsequent heating is performed after polymerization is preferably within the range that does not impair the effects of the present invention, and any suitable temperature may be used. Thus, the temperature at which the subsequent heating is performed is preferably 50°C to 120°C.

[0108] The subsequent heating time after polymerization is preferably within the range that does not impair the effects of the present invention, and any suitable time can be used. Thus, the subsequent heating time is preferably 1 hour to 10 hours.

[0109] For a slurry containing particles obtained by the polymerization step, particles may be obtained as needed by distillation, solvent removal, filtration, washing, drying, and classification.

[0110] Preferably, the particles obtained in the polymerization step, as determined by a flow-through particle image analyzer under the following measurement conditions A, have a particle size of 10 μm or larger per 1,000,000 particles (number of coarse particles with a particle size of 10 μm or larger) of 80 or less. (Measurement Condition A) Particle size measurement range (sphere-to-volume standard): 0.5 μm to 200.0 μm Circularity measurement range: 0.97 to 1.00

[0111] The number of coarse particles with a diameter of 10 μm or larger obtained by the polymerization step under measurement conditions A using a flow particle image analyzer is preferably 60 or less, even more preferably 50 or less, and particularly preferably 45 or less.

[0112] Furthermore, relative to the total number of particles with a diameter of 1 μm to 30 μm, the proportion of particles with a diameter of 10 μm or larger obtained in the polymerization step is preferably 1.0% by volume or less, as determined by the Coulter counter method (pore size 50 μm).

[0113] The proportion of particles with a particle size of 10 μm or larger obtained in the polymerization step is preferably 0.70% by volume or less, more preferably 0.60% by volume or less, and particularly preferably 0.50% by volume or less.

[0114] To obtain hollow resin particles with fewer coarse particles, it is preferable to include a classification step for classifying the particles obtained in the polymerization step. The classification step may include at least one selected from the group consisting of dry classification and wet classification. The classification method is not particularly limited; for example, known means such as sieving, meshing, non-woven filters, centrifugation, and air classification can be used for classification. In the classification step, the slurry containing the particles obtained in the polymerization step may be subjected to steps such as solvent removal, washing, or drying as needed, and then the particles may be classified by air classification. Alternatively, the slurry may be wet-classified through a filter with a desired absolute filtration accuracy (e.g., absolute filtration accuracy of 10 μm or less), and then subjected to steps such as solvent removal, washing, or drying as needed. Based on the above configuration, hollow resin particles with fewer coarse particles can be obtained.

[0115] The number of coarse particles with a diameter of 10 μm or larger obtained in the grading step under the above-mentioned measurement conditions A by using a flow-through particle image analyzer is preferably 45 or less, more preferably 40 or less, more preferably 30 or less, more preferably 20 or less, more preferably 10 or less, even more preferably 5 or less, particularly preferably 3 or less, best preferably 1 or less, and can be 0. Based on the above configuration, hollow resin particles with a very low number of coarse particles and excellent particle strength can be obtained.

[0116] The number of coarse particles with a particle size of 8 μm or larger but less than 10 μm, obtained from the particle size distribution in the grading step using a flow-through particle imaging analyzer under the aforementioned measurement conditions A, is preferably 55 or less, more preferably 50 or less, more preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, particularly preferably 15 or less, and most preferably 10 or less. Based on the above configuration, hollow resin particles with superior particle strength can be obtained. [Example]

[0117] Hereinafter, specific examples are given to illustrate the present invention, but the present invention is not limited to these examples.

[0118] <Determination of Volume Average Particle Size> The volume average particle size was measured using a COULTER Multisizer TM4e (a measuring device manufactured by BECKMAN COULTER Corporation). The measurement was performed using a calibrated aperture according to the Multisizer TM4e user manual issued by BECKMAN COULTER Corporation. The aperture used for measurement was appropriately selected based on the size of the particles being measured. The current and gain were appropriately set according to the size of the selected aperture. For example, when selecting an aperture with a size of 50 μm, the current was set to -800 and the gain was set to 4. For the test sample, 0.1 g of particles were dispersed in 10 ml of 0.1 wt% polyoxyethylene sorbitol monolaurate "Tween 20" aqueous solution using a Touch Mixer (YAMATO Scientific Corporation, "TOUCH MIXER MT-31") and an ultrasonic cleaner (VELVO-CLEAR Corporation, "ULTRASONIC CLEANER VS-150"). During the test, the mixture was slowly stirred in a beaker until no more air bubbles were introduced, and the test was stopped at the point when 100,000 particles were measured. The volume average particle size was determined from the volumetric particle size distribution obtained from the test results.

[0119] <Coefficient of Variation of Volume Average Particle Size> The coefficient of variation (CV value) of the volume average particle size is calculated by the following formula (1). Coefficient of variation [%] = (Standard deviation of particle size distribution based on particle volume ÷ Volume average particle size) × 100 ・・・(1)

[0120] <Determination of the number of coarse particles> [Number of particles with a diameter of 10 μm or larger / Number of particles with a diameter of 8 μm or larger but less than 10 μm] The number of coarse particles with a diameter of 10 μm or larger and the number of coarse particles with a diameter of 8 μm or larger but less than 10 μm were determined using a flow-through particle image analyzer. The flow-through particle image analyzer used was an FPIA-3000S (manufactured by SYSMEX). Alternatively, either a PARSHE ANALYZER (manufactured by HOSOKAWA MICRON) can be used. An aqueous solution of surfactant (dodecylbenzene sulfonate) was prepared by adding 0.01 parts to 4.94 parts of ion-exchanged water. 0.06 parts of hollow resin particles were added to an aqueous surfactant solution. The particles were dispersed in the surfactant solution using a disperser (ultrasonic scrubber (VELVO-CLEAR, VS-150)) and ultrasound was applied for 10 minutes to obtain an aqueous dispersion of hollow resin particles for testing. The obtained aqueous dispersion of hollow resin particles was introduced into a flow-through particle imaging analyzer (SYSMEX, FPIA-3000S; equipped with a standard objective lens (10x)) and measured under the following conditions. The sheath fluid used was a Particle Sheath (SYSMEX, PSE-900A). Measurement Mode: HPF mode. Particle size measurement range (sphere-to-volume standard): 0.5 μm to 200.0 μm. Circularity measurement range: 0.97 to 1.00. Before measurement, a suspension of standard polymer particle groups (e.g., Thermo Fisher Scientific, 5200A (standard polystyrene particle groups diluted with deionized water)) is used, and the automatic focus adjustment of the aforementioned flow-through particle imaging analyzer is performed. Circularity is calculated from the diameter of a true circle having the same projected area as the image of the hollow resin particles, divided by the circumference of the image of the hollow resin particles. Within the particle circularity measurement range of 0.97 to 1.0, the diameter (particle size) of the equivalent circle is measured for 100,000 particles, and the number of hollow resin particles with a diameter of 10.0 μm or larger and the number of hollow resin particles with a diameter of 8 μm or larger but less than 10 μm are calculated. Here, the number of hollow resin particles with a particle size of 8 μm or larger but less than 10 μm is calculated by dividing the number of hollow resin particles with a particle size of 8.0 μm or larger but less than 10.0 μm by the number of hollow resin particles with a particle size of 10.0 μm. This operation is performed 10 times (i.e., a total of 1,000,000 particles are measured), and the sum of the number of hollow resin particles with a volume average particle size of 10.0 μm or larger and the number of hollow resin particles with a particle size of 8 μm or larger but less than 10 μm is obtained.These sums are respectively defined as "the number of coarse particles with a diameter of 10 μm or more" and "the number of coarse particles with a diameter of 8 μm or more but less than 10 μm".

[0121] <Proportion of Particles with a Diameter of 10 μm or Larger> The proportion of particles with a diameter of 10 μm or larger relative to the total proportion of particles with a diameter of 1 μm to 30 μm was determined using a Coulter Multisizer TM4e (BECKMAN COULTER Co., Ltd.) with a 50 μm diameter aperture for measuring 100,000 particles, similar to the determination of the volume average particle size. The proportion of particles with a diameter of 10 μm or larger relative to particles with a diameter of 1 μm to 30 μm was confirmed from the volume-based particle size distribution obtained from the measurement results.

[0122] <Internal Structure of Hollow Resin Particles> The internal structure of the hollow resin particles was determined by cross-sectional SEM images of the particles. Hollow resin particles were mixed with photocurable resin "D-800" (manufactured by NEC Corporation), and a cured material was obtained by irradiation with ultraviolet light. The cured material was then cut with pliers, and the cross-section was smoothly machined using a cutting tool. A sample was then applied using a sputtering apparatus (manufactured by NEC Corporation, "Auto Fine Coater JFC-1300"). Next, the cross-section of the sample was imaged using a scanning electron microscope (manufactured by Hitachi HIGH TECHNOLOGIES Co., Ltd., "SU1510") with a secondary electron detector. The magnification was set to 3000x. The observed internal structure of the particles was characterized by a single hollow structure where the voids consist of only a single air layer, and the resin layer acts as a shell surrounding the voids; and by an internally porous structure where the voids consist of multiple air layers, and the resin layer acts as a shell surrounding multiple voids.

[0123] <Porosity> The porosity of the hollow resin particles is obtained from the apparent density and true density of the hollow resin particles. The apparent density of the hollow resin particles is measured using a vibratory densitometer (ANTON PAAR, trade name "DMA1001"). Specifically, hollow resin particles and a dispersant (Tōa Synthetic Co., Ltd., trade name "ARUFON UP-1020", density 1.027 g / cm 3 (25°C)) are mixed using a degassing mixer (THINKY Co., Ltd., trade name "AWATORI ARE-100") to prepare an evaluation mixture, with the hollow resin particles accounting for 2% by weight. The evaluation mixture is filled into the measuring unit of the vibratory densitometer, and the vibration number of the mixture in the measuring unit is measured. The density of the mixture is calculated from the following formula (2). The apparent density of the air-filled hollow resin particles is calculated from the density of the mixture and the dispersant and the weight ratio of each component in the mixture using the following formula (3). The true density of the hollow resin particles is determined and calculated using a vibratory densitometer (ANTON PAAR, trade name "DMA1001") in the same manner as the apparent density. Here, pre-crushed hollow resin particle flakes are used instead of hollow resin particles to calculate the density of the resin portion after removing the voids, which is the true density. In formula (2), f represents the vibration number [Hz], M represents the weight of the measuring unit [g], V represents the volume of the measuring unit [cm 3], ρ represents the density of the sample filling the measuring unit [g / cm 3], and c represents the spring constant [N / mm]. In equation (3), ρp represents the apparent density (or true density) [g / cm³] of the hollow resin particles, ρd represents the density [g / cm³] of the dispersant, xp represents the weight proportion of hollow resin particles (or pre-crushed hollow resin particle flakes) in the sample, and xd represents the weight proportion of the dispersant in the sample. The porosity of the hollow resin particles is calculated from the apparent density and true density using the following equation (4): Porosity (%) = 100 - (apparent density / true density) × 100 ・・・(4)

[0124] <Particle Fragmentation Assessment> The particles were pulverized using a jet mill (Current Jet, Nissin Engineering Co., Ltd.). A sputtering apparatus (Autofine Coater JFC-1300, Nippon Electronics Co., Ltd.) was used to coat the surface of the pulverized particles, creating a sample. The sample's appearance was then photographed using a secondary electron detector on a scanning electron microscope (Hitachi High Technology Co., Ltd., SU1510). At 1000x magnification, five random points were photographed, and the particle fragility was assessed based on the number of particles showing fractures or gaps. The assessment criteria are as follows: ◎: 0 particles showing fractures or gaps. 〇: 1 to 3 particles showing fractures or gaps. △: 4 to 5 particles showing fractures or gaps. ×: 5 or more particles showing fractures or gaps.

[0125] <Assessment of Total K and Na Content> The content of K and Na elements was determined for the metal residue in the hollow resin particles. Specifically, approximately 1.0 g of the precisely weighed hollow resin particle sample was ashed by heating at 500°C for 1 hour. The resulting ash was mixed with 1 mL of concentrated hydrochloric acid (Ultrapur-100 ultra-high purity reagent manufactured by Kanto Chemical Co., Ltd.). After filtering the insoluble components of the mixture through ADVANTEC No.7 filter paper, the filtrate was filled to 25 mL with distilled water to obtain the test solution. ICP-N PLC analysis was performed on the test solution under the following conditions. The concentration of each element was determined from a pre-prepared calibration line. The amount of each element was calculated using the following formula: Amount [ppm] = Concentration of element [μg / mL] × 25 [mL] ÷ Sample amount [g] The total content of K and Na was calculated from the amount of each element. Here, when calculating the total content of K and Na, elements whose measurement results are below the lower limit of quantitation are not considered. That is, the total amount of K and Na components above the lower limit of quantitation is taken as the total value of K and Na content. The lower limit of quantitation for K is 0.5 ppm, and the lower limit of quantitation for Na is 0.3 ppm. (ICP Measurement Conditions) Measurement Apparatus: Shimadzu Corporation "ICPE-9000" Multi-type ICP luminescence spectrophotometer. Elements measured: K, Na. Observation direction: Axial direction. High-frequency output: 1.20 kW. Carrier flow rate: 0.7 L / min. Plasma flow rate: 10.0 L / min. Auxiliary flow rate: 0.6 L / min. Exposure time: 30 seconds. Calibration standard solutions: SPEX Corporation "XSTC-13" general-purpose mixed standard solution (31 elements mixed, substrate 5% HNO3), approximately 10 mg / L each; "XSTC-8" general-purpose mixed standard solution (13 elements mixed, substrate H₂O / trace HF), approximately 10 mg / L each. (Ashing Conditions) Measurement Apparatus: Microwave high-temperature furnace (Phoenix large-capacity type, CEM Corporation). Ashing conditions: 500℃ × 1 hour (sample amount = approximately 1.0 g).

[0126] (Example 1) In a beaker, 320 parts by weight of a 2.0% by weight aqueous dispersion of magnesium pyrophosphate and 0.15 parts by weight of sodium lauryl sulfate were stirred and mixed to prepare an aqueous phase. Then, in a beaker different from the aqueous phase, 12 parts by weight of styrene, 7.1 parts by weight of ethyl vinylbenzene, 30 parts by weight of divinylbenzene, 23 parts by weight of heptane, 5 parts by weight of a high-branched hydrocarbon wax (Nucera Solutions "VYBAR TM260", Mn: 2,600 to 4,000), and 0.75 parts by weight of a polymerization initiator were stirred and mixed to prepare an oil phase. The obtained oil phase was added to the beaker containing the aqueous phase and stirred at 8000 rpm for 10 minutes using a TK homogenizer (Primix) to obtain a pre-emulsion. The pre-emulsion was further treated using a coarse-particle processing system (manufactured by Yoshida Machinery Co., Ltd., model "NVR-EM055-P20-0600-Exp") under high pressure emulsification conditions of 18 MPa processing pressure and 1 MPa outlet pressure to obtain a finely refined emulsion. The emulsion was added to a pressure-resistant polymerizer equipped with a stirring device, thermometer, and cooling mechanism. Nitrogen gas was purged for 3 minutes to create an inert gas environment, and then the temperature was raised to 75°C and polymerization was carried out for 4 hours. Afterward, the temperature was further raised to 90°C and the polymerization reaction was carried out for 10 hours. After the polymerization step was terminated, hydrochloric acid was added to decompose magnesium pyrophosphate. The resulting product was dehydrated using a centrifuge and washed with deionized water to obtain a cake containing hollow resin particles. This cake was dried in a vacuum oven at 90°C under reduced pressure for 48 hours to obtain particles (A1). The obtained particles (A1) contained 35 coarse particles with a diameter of 8 μm or larger but less than 10 μm, and 20 coarse particles with a diameter of 10 μm or larger. The proportion of particles with a diameter of 10 μm or larger in particle (A1) to particles with a diameter of 1 μm to 30 μm was 0.32% by volume. SEM observation of the cross-section of particle (A1) confirmed that the internal structure had a single hollow section. Particle (A1) was subjected to a 10 μm top cut using an air classifier (manufactured by Nissin Engineering Co., Ltd., "Turbo Classifier (registered trademark) TC-15NS") to obtain hollow resin particles (B1). The obtained hollow resin particles (B1) contained 7 coarse particles with a diameter of 8 μm or larger but less than 10 μm. The combined K and Na content of the hollow resin particles (B1) was 13 ppm. Other physical properties and evaluation results of hollow resin particles (B1) are described in Table 3.

[0127] (Example 2) Except for the change of polymerization initiator as shown in Table 1, particles (A2) were obtained by the same process as particles (A1) in Example 1. The obtained particles (A2) contained 36 coarse particles with a diameter of 8 μm or larger but less than 10 μm, and 15 coarse particles with a diameter of 10 μm or larger. The proportion of particles with a diameter of 10 μm or larger in particles (A2) to particles with a diameter of 1 μm to 30 μm was 0.24% by volume. SEM observation of the cross-section of particles (A2) confirmed that the internal structure had a single hollow section. Particles (A2) were subjected to a 10 μm top cut using an air classifier (manufactured by Nissin Engineering Co., Ltd., "Turbo Classifier (registered trademark) TC-15NS") to obtain hollow resin particles (B2). Nine coarse particles with a diameter greater than 8 μm but less than 10 μm were found in the obtained hollow resin particles (B2). The combined K and Na content of the hollow resin particles (B2) was 9 ppm. Other physical properties and evaluation results of the hollow resin particles (B2) are recorded in Table 3.

[0128] (Example 3) Except as shown in Table 1, polyphenylene ether (SABIC Corporation's "Noryl (registered trademark) SA90 resin", Mn: 1,900) was used to replace the highly branched hydrocarbon wax, the polymerization initiator was changed, and the initial polymerization temperature was changed from 75°C to 60°C, the other processes were the same as those used for particles (A1) in Example 1 to obtain particles (A3). The number of coarse particles with a diameter of 8 μm or larger but less than 10 μm in the obtained particles (A3) was 38, and the number of coarse particles with a diameter of 10 μm or larger was 22. The proportion of particles with a diameter of 10 μm or larger in particles (A3) to particles with a diameter of 1 μm to 30 μm was 0.34% by volume. SEM observation of the cross-section of particles (A3) confirmed that the internal structure had a single hollow section. Hollow resin particles (B3) were obtained by 10 μm top-cutting of particles (A3) using an air classifier (manufactured by Nissin Engineering Co., Ltd., "Turbo Classifier (registered trademark) TC-15NS"). Nine coarse particles with a diameter of 8 μm or larger but less than 10 μm were found in the obtained hollow resin particles (B3). The combined K and Na content of the hollow resin particles (B3) was 10 ppm. Other physical properties and evaluation results of the hollow resin particles (B3) are described in Table 3.

[0129] (Example 4) Except for replacing the highly branched hydrocarbon wax with polystyrene (Mn: 70,000 to 90,000) and changing the polymerization initiator as shown in Table 1, the particles (A4) were obtained by processing in the same manner as the particles (A1) in Example 1. The number of coarse particles with a particle size of 8 μm or larger but less than 10 μm in the obtained particles (A4) was 28, and the number of coarse particles with a particle size of 10 μm or larger was 21. The proportion of particles with a particle size of 10 μm or larger in particles (A4) to particles with a particle size of 1 μm to 30 μm was 0.32% by volume. By observing the cross-section of the particles (A4) by SEM, it was confirmed that the internal structure had a single hollow part. The particles (A4) were subjected to 10 μm top cutting using an air classifier (manufactured by Nisshin Engineering Co., Ltd., "Turbo Classifier (registered trademark) TC-15NS") to obtain hollow resin particles (B4). The obtained hollow resin particles (B4) contained 7 coarse particles with a diameter greater than 8 μm but less than 10 μm. The combined K and Na content of the hollow resin particles (B4) was 11 ppm. Other physical properties and evaluation results of the hollow resin particles (B4) are recorded in Table 3.

[0130] (Example 5) Except for the change in the composition of the oil phase as shown in Table 1, particles (A5) were obtained by processing the same method as particles (A1) in Example 1. The obtained particles (A5) contained 38 coarse particles with a diameter of 8 μm or larger but less than 10 μm, and 23 coarse particles with a diameter of 10 μm or larger. The proportion of particles with a diameter of 10 μm or larger in particles (A5) to particles with a diameter of 1 μm to 30 μm was 0.32% by volume. SEM observation of the cross-section of particles (A5) confirmed that the internal structure had a single hollow section. Particles (A5) were subjected to a 10 μm top cut using an air classifier (manufactured by Nissin Engineering Co., Ltd., "Turbo Classifier (registered trademark) TC-15NS") to obtain hollow resin particles (B5). The number of coarse particles with a diameter of 8 μm or larger but less than 10 μm in the obtained hollow resin particles (B5) was 8. The combined K and Na content of the hollow resin particles (B5) was 12 ppm. Other physical properties and evaluation results of the hollow resin particles (B5) are recorded in Table 3.

[0131] (Example 6) Except for the change in the composition of the oil phase as shown in Table 1, particles (A6) were obtained by the same process as particles (A1) in Example 1. The obtained particles (A6) contained 41 coarse particles with a diameter of 8 μm or larger but less than 10 μm, and 23 coarse particles with a diameter of 10 μm or larger. The proportion of particles with a diameter of 10 μm or larger in particles (A6) to particles with a diameter of 1 μm to 30 μm was 0.32% by volume. SEM observation of the cross-section of particles (A6) confirmed that the internal structure had a single hollow section. Hollow resin particles (B6) were obtained by 10 μm top-cutting using an air classifier (manufactured by Nissin Engineering Co., Ltd., "Turbo Classifier (registered trademark) TC-15NS"). Nine coarse particles with a diameter greater than 8 μm but less than 10 μm were found in the obtained hollow resin particles (B6). The combined K and Na content of the hollow resin particles (B6) was 10 ppm. Other physical properties and evaluation results of the hollow resin particles (B6) are recorded in Table 3.

[0132] (Example 7) Except for the change in the composition of the oil phase as shown in Table 1, particles (A7) were obtained by processing the same method as particles (A1) in Example 1. The obtained particles (A7) contained 38 coarse particles with a diameter of 8 μm or larger but less than 10 μm, and 26 coarse particles with a diameter of 10 μm or larger. The proportion of particles with a diameter of 10 μm or larger in particles (A7) to particles with a diameter of 1 μm to 30 μm was 0.38% by volume. SEM observation of the cross-section of particles (A7) confirmed that the internal structure had a single hollow section. Particles (A7) were subjected to a 10 μm top cut using an air classifier (manufactured by Nissin Engineering Co., Ltd., "Turbo Classifier (registered trademark) TC-15NS") to obtain hollow resin particles (B7). The obtained hollow resin particles (B7) contained 7 coarse particles with a diameter greater than 8 μm but less than 10 μm. The combined K and Na content of the hollow resin particles (B7) was 9 ppm. Other physical properties and evaluation results of the hollow resin particles (B7) are recorded in Table 3.

[0133] (Example 8) Except for the change in the composition of the oil phase as shown in Table 1, particles (A8) were obtained by processing the same method as particles (A1) in Example 1. The number of coarse particles (A8) with a diameter of 8 μm or larger but less than 10 μm was 51, and the number of coarse particles with a diameter of 10 μm or larger was 39. The proportion of particles with a diameter of 10 μm or larger in particles (A8) to particles with a diameter of 1 μm to 30 μm was 0.48% by volume. SEM observation of the cross-section of particles (A8) confirmed that the internal structure had a single hollow section. Hollow resin particles (B8) were obtained by 10 μm top-cutting using an air classifier (manufactured by Nissin Engineering Co., Ltd., "Turbo Classifier (registered trademark) TC-15NS"). The obtained hollow resin particles (B8) contained 14 coarse particles with a diameter greater than 8 μm but less than 10 μm. The combined K and Na content of the hollow resin particles (B8) was 13 ppm. Other physical properties and evaluation results of the hollow resin particles (B8) are recorded in Table 3.

[0134] (Example 9) Except for the change in the composition of the oil phase as shown in Table 1, particles (A9) were obtained by the same process as particles (A1) in Example 1. The number of coarse particles (A9) with a diameter of 8 μm or larger but less than 10 μm was 39, and the number of coarse particles with a diameter of 10 μm or larger was 24. The proportion of particles with a diameter of 10 μm or larger in particles (A9) to particles with a diameter of 1 μm to 30 μm was 0.30% by volume. SEM observation of the cross-section of particles (A9) confirmed that the internal structure had a single hollow section. Hollow resin particles (B9) were obtained by 10 μm top-cutting using an air classifier (manufactured by Nissin Engineering Co., Ltd., "Turbo Classifier (registered trademark) TC-15NS"). The number of coarse particles (8 μm or larger but less than 10 μm) in the obtained hollow resin particles (B9) was 8. The combined K and Na content of the hollow resin particles (B9) was 12 ppm. Other physical properties and evaluation results of the hollow resin particles (B9) are recorded in Table 3.

[0135] (Example 10) Except for the change in the composition of the oil phase as shown in Table 1, the particles (A10) were obtained by the same procedure as those in Example 1. The obtained particles (A10) contained 25 coarse particles with a diameter of 8 μm or larger but less than 10 μm, and 12 coarse particles with a diameter of 10 μm or larger. The proportion of particles with a diameter of 10 μm or larger in particles (A10) to particles with a diameter of 1 μm to 30 μm was 0.38% by volume. SEM observation of the cross-section of the particles (A10) confirmed that the internal structure had a single hollow section. The particles (A10) were subjected to a 10 μm top cut using an air classifier (manufactured by Nissin Engineering Co., Ltd., "Turbo Classifier (registered trademark) TC-15NS") to obtain hollow resin particles (B10). Five coarse particles with a diameter greater than 8 μm but less than 10 μm were found in the obtained hollow resin particles (B10). The combined K and Na content of the hollow resin particles (B10) was 12 ppm. Other physical properties and evaluation results of the hollow resin particles (B10) are recorded in Table 3.

[0136] (Example 11) Except for the change in the composition of the oil phase as shown in Table 2, the particles (A11) were obtained by the same procedure as those in Example 1. The obtained particles (A11) contained 24 coarse particles with a diameter of 8 μm or larger but less than 10 μm, and 25 coarse particles with a diameter of 10 μm or larger. The proportion of particles with a diameter of 10 μm or larger in particles (A11) to particles with a diameter of 1 μm to 30 μm was 0.32% by volume. SEM observation of the cross-section of the particles (A11) confirmed that the internal structure had a single hollow section. The particles (A11) were subjected to a 10 μm top cut using an air classifier (manufactured by Nisshin Engineering Co., Ltd., "Turbo Classifier (registered trademark) TC-15NS") to obtain hollow resin particles (B11). The number of coarse particles with a diameter of 8 μm or larger but less than 10 μm in the obtained hollow resin particles (B11) was 10. The combined K and Na content of the hollow resin particles (B11) was 14 ppm. Other physical properties and evaluation results of the hollow resin particles (B11) are recorded in Table 3.

[0137] (Example 12) Except for the change in the composition of the oil phase as shown in Table 2, the particles (A12) were obtained by the same procedure as those in Example 1. The obtained particles (A12) contained 51 coarse particles with a diameter of 8 μm or larger but less than 10 μm, and 37 coarse particles with a diameter of 10 μm or larger. The proportion of particles with a diameter of 10 μm or larger in particles (A12) to particles with a diameter of 1 μm to 30 μm was 0.44% by volume. SEM observation of the cross-section of the particles (A12) confirmed that the internal structure had a single hollow section. The particles (A12) were subjected to a 10 μm top cut using an air classifier (manufactured by Nisshin Engineering Co., Ltd., "Turbo Classifier (registered trademark) TC-15NS") to obtain hollow resin particles (B12). The obtained hollow resin particles (B12) contained 13 coarse particles with a diameter greater than 8 μm but less than 10 μm. The combined K and Na content of the hollow resin particles (B12) was 12 ppm. Other physical properties and evaluation results of the hollow resin particles (B12) are recorded in Table 3.

[0138] (Example 13) Except for the change in the composition of the oil phase as shown in Table 2, the particles (A13) were obtained by the same procedure as those in Example 1 (A1). The obtained particles (A13) contained 51 coarse particles with a diameter of 8 μm or larger but less than 10 μm, and 38 coarse particles with a diameter of 10 μm or larger. The proportion of particles with a diameter of 10 μm or larger in particles (A13) to particles with a diameter of 1 μm to 30 μm was 0.49% by volume. SEM observation of the cross-section of the particles (A13) confirmed that the internal structure had a single hollow section. The particles (A13) were subjected to a 10 μm top cut using an air classifier (manufactured by Nissin Engineering Co., Ltd., "Turbo Classifier (registered trademark) TC-15NS") to obtain hollow resin particles (B13). The number of coarse particles (8 μm or larger but less than 10 μm) in the obtained hollow resin particles (B13) was 15. The combined K and Na content of the hollow resin particles (B13) was 10 ppm. Other physical properties and evaluation results of the hollow resin particles (B13) are recorded in Table 3.

[0139] (Example 14) Except for the change in the composition of the oil phase as shown in Table 2, the particles (A14) were obtained by the same procedure as those in Example 1. The obtained particles (A14) contained 27 coarse particles with a diameter of 8 μm or larger but less than 10 μm, and 18 coarse particles with a diameter of 10 μm or larger. The proportion of particles with a diameter of 10 μm or larger in particles (A14) to particles with a diameter of 1 μm to 30 μm was 0.28% by volume. SEM observation of the cross-section of the particles (A14) confirmed that the internal structure had a single hollow section. The particles (A14) were subjected to a 10 μm top cut using an air classifier (manufactured by Nissin Engineering Co., Ltd., "Turbo Classifier (registered trademark) TC-15NS") to obtain hollow resin particles (B14). The obtained hollow resin particles (B14) contained 6 coarse particles with a diameter greater than 8 μm but less than 10 μm. The combined K and Na content of the hollow resin particles (B14) was 11 ppm. Other physical properties and evaluation results of the hollow resin particles (B14) are recorded in Table 3.

[0140] (Example 15) Except for the change in the composition of the oil phase as shown in Table 2, the particles (A15) were obtained by the same procedure as those in Example 1. The obtained particles (A15) contained 37 coarse particles with a diameter of 8 μm or larger but less than 10 μm, and 19 coarse particles with a diameter of 10 μm or larger. The proportion of particles with a diameter of 10 μm or larger in particles (A15) to particles with a diameter of 1 μm to 30 μm was 0.48% by volume. SEM observation of the cross-section of the particles (A15) confirmed that the internal structure had a single hollow section. The particles (A15) were subjected to a 10 μm top cut using an air classifier (manufactured by Nissin Engineering Co., Ltd., "Turbo Classifier (registered trademark) TC-15NS") to obtain hollow resin particles (B15). Nine coarse particles with a diameter greater than 8 μm but less than 10 μm were found in the obtained hollow resin particles (B15). The combined K and Na content of the hollow resin particles (B15) was 9 ppm. Other physical properties and evaluation results of the hollow resin particles (B15) are recorded in Table 3.

[0141] (Example 16) Except for the change in the composition of the oil phase as shown in Table 2, the particles (A16) were obtained by the same procedure as those in Example 1 (A1). The number of coarse particles (A16) with a diameter of 8 μm or larger but less than 10 μm was 42, and the number of coarse particles with a diameter of 10 μm or larger was 41. The proportion of particles with a diameter of 10 μm or larger in particles (A16) to particles with a diameter of 1 μm to 30 μm was 0.49% by volume. SEM observation of the cross-section of the particles (A16) confirmed that the internal structure had a single hollow section. The particles (A16) were subjected to a 10 μm top cut using an air classifier (manufactured by Nisshin Engineering Co., Ltd., "Turbo Classifier (registered trademark) TC-15NS") to obtain hollow resin particles (B16). The obtained hollow resin particles (B16) contained 14 coarse particles with a diameter greater than 8 μm but less than 10 μm. The combined K and Na content of the hollow resin particles (B16) was 14 ppm. Other physical properties and evaluation results of the hollow resin particles (B16) are recorded in Table 3.

[0142] (Example 17) Except for the change in the composition of the oil phase as shown in Table 2, the particles (A17) were obtained by the same procedure as those for particles (A1) in Example 1. The obtained particles (A17) contained 36 coarse particles with a diameter of 8 μm or larger but less than 10 μm, and 15 coarse particles with a diameter of 10 μm or larger. The proportion of particles with a diameter of 10 μm or larger in particles (A17) to particles with a diameter of 1 μm to 30 μm was 0.24% by volume. SEM observation of the cross-section of the particles (A17) confirmed that the internal structure had a single hollow portion. After the polymerization step in the particle (A17) manufacturing process was completed, the slurry containing the particles (A17) was passed through a filter with an absolute filtration accuracy of 10 μm (manufactured by JNC Filter Co., Ltd., BM-10) for wet classification. The magnesium pyrophosphate was decomposed by adding hydrochloric acid to the slurry, followed by dehydration using a centrifuge and washing with deion-exchanged water to obtain a cake containing hollow resin particles. This cake was then dried in a vacuum oven at 90°C under reduced pressure for 48 hours to obtain hollow resin particles (B17). The obtained hollow resin particles (B17) contained 3 coarse particles with a diameter greater than 8 μm but less than 10 μm. The combined K and Na content of the hollow resin particles (B17) was 13 ppm. Other physical properties and evaluation results of the hollow resin particles (B17) are recorded in Table 3.

[0143] (Comparative Example 1) In a beaker, 320 parts by weight of a 2.0% by weight aqueous dispersion of magnesium pyrophosphate and 0.15 parts by weight of sodium lauryl sulfate were stirred and mixed to prepare an aqueous phase. Next, in a beaker different from the aqueous phase, 3 parts by weight of styrene, 3.6 parts by weight of ethyl vinylbenzene, 15.4 parts by weight of divinylbenzene, 50 parts by weight of heptane, 1 part by weight of a highly branched hydrocarbon wax (Mn: 2,600), and 0.50 parts by weight of a polymerization initiator were stirred and mixed to prepare an oil phase. The obtained oil phase was added to the beaker containing the aqueous phase and stirred at 8000 rpm for 10 minutes using a TK homogenizer (manufactured by Primix) to obtain a pre-emulsion. The pre-emulsion was further treated using a coarse-particle processing system (manufactured by Yoshida Machinery Co., Ltd., model "NVR-EM055-P20-0600-Exp") under high pressure emulsification conditions of 18 MPa processing pressure and 1 MPa outlet pressure to obtain a finely refined emulsion. The emulsion was added to a pressure-resistant polymerizer equipped with a stirring device, thermometer, and cooling mechanism. Nitrogen gas was purged for 3 minutes to create an inert gas environment, and then the temperature was raised to 75°C for polymerization for 4 hours. Afterward, the temperature was raised to 90°C for polymerization for 10 hours. After the polymerization step was completed, hydrochloric acid was added to decompose magnesium pyrophosphate. The resulting product was dehydrated using a centrifuge and washed with deionized water to obtain a cake containing hollow resin particles. This cake was dried in a vacuum oven at 90°C under reduced pressure for 48 hours to obtain particles. The obtained particles were then screened using a 45 μm mesh metal mesh. Hollow resin particles (C1) that passed through a metal mesh and fell below were used as Comparative Example 1. The cross-section of the obtained hollow resin particles (C1) was observed using SEM, confirming that the internal structure had a single hollow portion. The number of coarse particles (C1) with a diameter of 8 μm or larger but less than 10 μm was 101. Other physical properties and evaluation results of the hollow resin particles (C1) are described in Table 3. Furthermore, although airflow classification was attempted for the hollow resin particles (C1) under the same conditions as for the particles (A1) in Example 1, cracks or gaps were observed on the surface of the classified particles.

[0144] (Comparative Example 2) Except for the change in the composition of the oil phase as shown in Table 2, the particles (C2) were obtained by the same procedure as the hollow resin particles (C1) in Comparative Example 1. The obtained particles (C2) were confirmed to be irregularly shaped and not hollow. There were 98 coarse particles with a diameter of 8 μm or larger but less than 10 μm in the obtained particles (C2). Other physical properties and evaluation results of particles (C2) are recorded in Table 3. However, since particles (C2) were confirmed to be irregularly shaped, particle breakage evaluation was not performed.

[0145] (Comparative Example 3) Except for the change in the composition of the oil phase as shown in Table 2, hollow resin particles (C3) were obtained by the same procedure as those in Comparative Example 1 (C1). When the cross-section of the obtained hollow resin particles (C3) was observed using SEM, it was confirmed that the hollow structure surrounded by the shell was composed of a porous material. The number of coarse particles (C3) with a diameter of 8 μm or larger but less than 10 μm was 116. Other physical properties and evaluation results of the hollow resin particles (C3) are recorded in Table 3.

[0146] [Table 1]

[0147] [Table 2]

[0148] The abbreviations in Tables 1 and 2 are as follows: LPO: Laurethyl peroxide (manufactured by Nippon Oil Co., Ltd., trade name "PEROYL L") BPO: Benzoyl peroxide (manufactured by Nippon Oil Co., Ltd., trade name "NYPER BW") t-BuPEHx: Tertiary butyl-2-ethylperoxyhexanoate (manufactured by Nippon Oil Co., Ltd., trade name "PERBUTYL O") ADVN: 2,2'-Azobis(2,4-dimethylvaleronitrile) (manufactured by Fuji FILM and Wako Pure Chemical Industries Co., Ltd., trade name "V-65") DAMP: Dimethyl 2,2'-Azobis(2-methylpropionic acid) (manufactured by Fuji FILM and Wako Pure Chemical Industries Co., Ltd., trade name "V-601")

[0149] [Table 3][Industrial Availability]

[0150] The hollow resin particles of the embodiments of the present invention, and the hollow resin particles obtained by the manufacturing method of the embodiments of the present invention, are suitable for use in semiconductor components, etc.

Claims

1. A hollow resin particle having a shell and a hollow portion surrounded by the shell, wherein, The porosity is 5% to 90%, and the number of particles with a diameter of 10 μm or larger per 1,000,000 particles, as determined by a flow particle imaging analyzer under the following measurement conditions A, is 10 or less; the aforementioned shell contains a polymer (P1), which is obtained by polymerizing the aforementioned free radical polymerizable monomer component (M) through a reaction of a composition containing a free radical polymerizable monomer component (M); the aforementioned composition contains a polymer component (P2), and the number-average molecular weight of the aforementioned polymer component (P2) is 500 to 200,000 (measurement conditions A); the particle size measurement range (sphere-converted volume basis) is 0.5 μm to 200.0 μm; the roundness measurement range is 0.97 to 1.

00.

2. Hollow resin particles as described in claim 1, wherein, The aforementioned free radical polymerizable monomer component (M) includes a crosslinking monomer (a).

3. Hollow resin particles as described in claim 2, wherein, The aforementioned free radical polymerizable monomer component (M) contains the aforementioned crosslinking monomer (a) in a proportion of 20% to 96% by weight.

4. Hollow resin particles as described in claim 2, wherein, The aforementioned free radical polymerizable monomer component (M) includes a monofunctional monomer (b).

5. Hollow resin particles as described in claim 4, wherein, The aforementioned free radical polymerizable monomer component (M) contains the aforementioned monofunctional monomer (b) in a proportion of 4% to 80% by weight.

6. Hollow resin particles as described in claim 1, wherein, When the total amount of the aforementioned free radical polymerizable monomer component (M) is taken as 100 parts by weight, the aforementioned polymer component (P2) is 0.1 to 20 parts by weight.

7. Hollow resin particles as described in claim 1, wherein, The volume average particle size ranges from 0.1 μm to 5.0 μm.

8. Hollow resin particles as described in claim 1, wherein, The coefficient of variation of the volume average particle size is less than 25%.

9. The hollow resin particles as described in claim 1 are used as an additive for semiconductor components.

10. A resin composition for semiconductor components comprising the hollow resin particles described in claim 9.

11. The hollow resin particles as described in claim 1 are used as additives for optical materials.