Resin microparticles, methods for producing the same, and applications thereof.

Abstract

To provide resin fine particles reduced in metal components and elution ion components, and having an excellent dielectric characteristic, and to provide a method for producing the resin fine particles.SOLUTION: Resin fine particles have the total content of components A measured by an inductive coupling type plasma emission spectrometry of 100 ppm or less, the total amount of elution ion components B measured by an ion chromatograph of 100 ppm or less, and a dielectric loss tangent at a frequency of 10 GHz of 0.0050 or less. The components A are Al, Ba, Ca, Cr, Cu, Fe, K, Mg, Mn, Na, P, S, Si, Sr and Zn. The ion components B are fluoride ion, chloride ion, nitrite ion, bromide ion, nitric ion, phosphate ion, and sulphate ion.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to resin microparticles, a method for producing the same, and applications thereof. [Background technology]

[0002] Resin microparticles are used in a wide range of applications, including as antiblocking agents for light diffusing plates and various film films, various film modifiers, spacers between minute parts of various electronic devices, pore-forming agents for various battery components, and core particles of conductive microparticles that are responsible for electrical connections.

[0003] In recent years, the semiconductor materials market has seen various studies aimed at miniaturizing and improving the performance of electronic circuits. For example, it has been reported that by adding fillers to various semiconductor materials such as encapsulants, interlayer insulating films, and copper-clad laminates, semiconductor materials with improved physical properties such as elasticity can be obtained while maintaining good dielectric properties (Patent Document 1). However, when resin nanoparticles are applied to such applications, the resin nanoparticles are required to be small enough to miniaturize the semiconductor materials, to have a low dielectric loss tangent to the particles themselves, and to have their metallic or ionic components reduced in advance to prevent ion migration.

[0004] Emulsion polymerization and seed polymerization are manufacturing methods that can produce resin nanoparticles with an average particle size of 1 μm or less. However, these polymerization methods use a large amount of surfactant when emulsifying oil droplets, which leads to a problem of a large amount of residual ionic components in the resulting resin nanoparticles. As a technique to reduce residual ionic components, a washing process to wash the particles has been reported (Patent Document 2), but a large amount of washing water is required for more precise washing, which presents problems in terms of production and cost.

[0005] Low-ionic resin microparticles manufactured without the use of surfactants and emulsifiers have been reported (Patent Document 3). However, the low-ionic resin microparticles described in Patent Document 3 have a problem in that the particles themselves have a high dielectric loss tangent because they have polar groups such as amino groups on their surface.

[0006] Hollow particles that can reduce the dielectric constant of semiconductor materials have been reported (Patent Document 4). However, because they are hollow particles, they have problems with strength. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2023-165254 [Patent Document 2] International Publication No. 2015 / 045448 [Patent Document 3] Japanese Patent Publication No. 2005-082695 [Patent Document 4] Japanese Patent Publication No. 2022-117594 [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] This invention was made to solve the above-mentioned conventional problems, and its main objective is to provide resin nanoparticles that have reduced metal and eluted ion components and excellent dielectric properties. Furthermore, it aims to provide a method for producing such resin nanoparticles. Finally, it aims to provide applications for such resin nanoparticles. [Means for solving the problem]

[0009] [1] The resin fine particles according to the embodiment of the present invention are The total content of component A, as measured by inductively coupled plasma emission spectrometry, is 100 ppm or less. The total amount of eluted ion component B measured by ion chromatography is 100 ppm or less. The dielectric loss tangent at a frequency of 10 GHz is 0.0050 or less. Component A: Al, Ba, Ca, Cr, Cu, Fe, K, Mg, Mn, Na, P, S, Si, Sr, and Zn Ionic component B: Fluoride ions, chloride ions, nitrite ions, bromide ions, nitrate ions, phosphate ions, and sulfate ions [2] The resin fine particles described in [1] above may have a dielectric loss tangent of 0.0030 or less. [3] The resin fine particles described in [1] or [2] above include a polymer (P) obtained by reaction of a composition containing a radical polymerizable monomer component (M), The above monomer component (M) may include a crosslinkable monomer (a) and an aromatic monofunctional monomer (b). [4] In the resin fine particles described in [3] above, the crosslinkable monomer (a) may include an aromatic crosslinkable monomer. [5] In the resin fine particles described in [3] or [4] above, the composition may contain a reactive surfactant (A). [6] The resin fine particles described in any one of [1] to [5] above may have a volume average particle diameter of 0.05 μm or more and 2 μm or less. [7] The resin fine particles described in any one of [1] to [6] above may have a particle size of 10 μm or larger, with the proportion of particles being 0.01 volume% or less. [8] The resin fine particles described in any one of [1] to [7] above may be in the form of a dry powder. [9] The resin fine particles described in any one of [1] to [8] above may have a coefficient of variation of volume average particle size of 25% or less.

[10] The resin fine particles described in any one of [1] to [9] above may be used as an additive for electronic materials.

[11] The resin fine particles described in any one of [1] to [9] above may be used as an additive for optical materials.

[12] Any resin fine particles described in any one of [1] to [9] above may be used as an additive for paints.

[13] Any resin fine particles described in any one of [1] to [9] above may be used as an additive for ink.

[14] The method for producing resin fine particles according to embodiments of the present invention is The method for producing resin fine particles according to any one of [1] to

[13] above, Two-stage polymerization consisting of a first polymerization step and a second polymerization step is carried out, In the first polymerization step, a radically polymerizable monomer component (M1) containing a monofunctional monomer (b1) is subjected to emulsion polymerization, In the second polymerization step, a radically polymerizable monomer component (M2) containing a monofunctional monomer (b2) and a crosslinkable monomer (a) is subjected to emulsion polymerization.

[15] In the method for producing resin fine particles according to

[14] above, the first polymerization step and the second polymerization step may be carried out in a single reactor.

[16] In the method for producing resin fine particles according to

[14] or

[15] above, a reactive surfactant may be used in at least one selected from the first polymerization step and the second polymerization step.

[17] In the method for producing resin fine particles according to any one of

[14] to

[16] above, a water-soluble azo compound may be used as a polymerization initiator in at least one selected from the first polymerization step and the second polymerization step.

[18] In the method for producing resin fine particles according to any one of

[14] to

[17] above, a non-reactive surfactant may not be used in the first polymerization step and the second polymerization step.

[19] In the method for producing resin fine particles according to any one of

[14] to

[18] above, the monofunctional monomer (b2) in the second polymerization step may contain an aromatic monofunctional monomer, and the crosslinkable monomer (a) may contain an aromatic crosslinkable monomer. [Effect of the Invention]

[0010] According to an embodiment of the present invention, resin fine particles with reduced metal components and eluted ion components and excellent dielectric properties can be provided. Further, a method for producing such resin fine particles can be provided. Furthermore, uses of such resin fine particles can be provided. [Embodiments for Carrying Out the Invention]

[0011] The following describes embodiments of the present invention, but the present invention is not limited to these embodiments.

[0012] In this specification, the expression "(meth)acrylic" means "acrylic and / or methacrylic," the expression "(meth)acrylate" means "acrylate and / or methacrylate," and the expression "(meth)acrylonitrile" means "acrylonitrile and / or methacrylonitrile."

[0013] ≪≪Resin fine particles≫≫ The resin fine particles according to the embodiment of the present invention have a total content of component A below 100 ppm or less, and a total amount of eluted ion component B below 100 ppm or less. Component A: Al, Ba, Ca, Cr, Cu, Fe, K, Mg, Mn, Na, P, S, Si, Sr, and Zn Ionic component B: Fluoride ion (F - ), chloride ions (Cl - ), nitrite ion (NO2 - ), bromide ions (Br - ), nitrate ion (NO3 - ), phosphate ion (PO4 3- ), and sulfate ions (SO4 2- )

[0014] The total content of component A in the resin microparticles is measured by inductively coupled plasma (ICP) emission spectroscopy. The total amount of eluted ion component B in the resin microparticles is measured by ion chromatography. In this specification, the total content of component A in the resin microparticles means the mass of component A per unit mass of the resin microparticles, and the total amount of eluted ion component B in the resin microparticles means the mass of eluted ion component B per unit mass of the resin microparticles. Therefore, 1 ppm = 1 mg / kg for both the total content of component A and the total amount of eluted ion component B.

[0015] Thus, resin microparticles with a low total content of component A and a low total amount of eluted ion component B do not affect the performance of the component even when used in fine components, and are particularly suitable for use in miniaturized semiconductor components. If the total content of component A in the resin microparticles exceeds 100 ppm, the performance of the component obtained by mixing the resin microparticles with resin, etc., may be reduced by component A eluted from the resin microparticles. Similarly, if the total amount of eluted ion component B in the resin microparticles exceeds 100 ppm, the performance of the component obtained by mixing the resin microparticles with resin, etc., may be reduced by the ion components eluted from the resin microparticles. For example, when using resin microparticles with a high total content of component A or a high total amount of eluted ion component B in a semiconductor component, there is a risk that component A or ion component B eluted from the resin microparticles may cause ion migration.

[0016] The total content of component A in the resin fine particles according to the embodiments of the present invention is preferably 70 ppm or less, more preferably 50 ppm or less, even more preferably 30 ppm or less, even more preferably 20 ppm or less, particularly preferably 15 ppm or less, and most preferably 12 ppm or less. The lower limit of the total content of component A in the resin fine particles according to the embodiments of the present invention may be, for example, 0 ppm or more, or 0.1 ppm or more.

[0017] The total amount of eluted ion component B in the resin fine particles according to the embodiments of the present invention is preferably 100 ppm or less, more preferably 70 ppm or less, even more preferably 50 ppm or less, even more preferably 30 ppm or less, particularly preferably 15 ppm or less, and most preferably 12 ppm or less. The lower limit of the total amount of eluted ion component B in the resin fine particles according to the embodiments of the present invention may be, for example, 0 ppm or more, and may also be 0.1 ppm or more.

[0018] The resin nanoparticles according to the embodiment of the present invention have a dielectric loss tangent of 0.0050 or less at a frequency of 10 GHz. Resin nanoparticles with such low dielectric loss tangents can exhibit excellent dielectric properties in resins mixed with these resin nanoparticles. Examples of excellent dielectric properties include low dielectric constant and low dielectric loss tangent.

[0019] The resin fine particles according to the embodiments of the present invention have a dielectric loss tangent at a frequency of 10 GHz, preferably 0.0040 or less, more preferably 0.0030 or less, even more preferably 0.0020 or less, particularly preferably 0.0015 or less, and most preferably 0.0010 or less. The lower limit of the above dielectric loss tangent may preferably be 0 or more.

[0020] The resin fine particles according to the embodiments of the present invention have a relative permittivity at a frequency of 10 GHz, preferably 1.0 to 2.5, more preferably 1.0 to 2.4, even more preferably 1.0 to 2.3, and particularly preferably 1.0 to 2.2.

[0021] The volume-average particle diameter (volume-average primary particle diameter) of the resin fine particles according to the embodiments of the present invention is not particularly limited and can be set appropriately depending on the purpose and application. The volume-average particle diameter of the resin fine particles according to the embodiments of the present invention is, for example, 3 μm or less, preferably 0.2 μm or less, more preferably 1.5 μm or less, and even more preferably 1.0 μm or less. The volume-average particle diameter of the resin fine particles according to the embodiments of the present invention is, for example, 0.05 μm or more, preferably 0.07 μm or more, and even more preferably 0.1 μm or more. The volume-average particle diameter of the resin fine particles according to the embodiments of the present invention is preferably 0.05 μm or more and 2 μm or less, more preferably 0.08 μm or more and 2 μm or less, and even more preferably 0.1 μm or more and 1 μm or less. The volume-average particle size can be measured using, for example, a laser diffraction / scattering particle size distribution analyzer manufactured by Beckman Coulter.

[0022] The coefficient of variation of the volume-average particle diameter of the resin fine particles according to the embodiments of the present invention is not particularly limited and can be set appropriately depending on the purpose and application. The coefficient of variation of the volume-average particle diameter of the resin fine particles according to the embodiments of the present invention is, for example, 40% or less, preferably 30% or less, more preferably 25% or less, and even more preferably 20% or less. The coefficient of variation of the volume-average particle diameter of the resin fine particles according to the embodiments of the present invention may be, for example, 1% or more, 5% or more, and even 10% or more. The coefficient of variation of the volume-average particle size of resin microparticles is a value calculated by the following formula (1), and represents the distribution range of the data. Coefficient of variation [%] = (Standard deviation of the volume-based particle size distribution of resin microparticles ÷ Volume-average particle diameter of resin microparticles) × 100 (1)

[0023] The resin fine particles according to the embodiments of the present invention have a particle size of 10 μm or larger, and the proportion of particles with a particle size of 10 μm or more is, for example, 0.01% by volume or less, preferably 0% by volume. The above proportion can be measured using a number-based ratio, for example, the method described in the examples below.

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

[0025] <Polymer P> The resin fine particles according to embodiments of the present invention typically include a polymer (P) obtained by the reaction of a composition containing a radical polymerizable monomer component (M). The monomer component (M) preferably includes a vinyl monomer, and more preferably includes a crosslinkable monomer (a) and an aromatic monofunctional monomer (b). Therefore, a preferred embodiment of the polymer (P) has structural units derived from the crosslinkable monomer (a) and structural units derived from the aromatic monofunctional monomer (b).

[0026] The polymer (P) may be of one type or two or more types.

[0027] The polymer (P) content in the resin fine particles according to the embodiments of the present invention is preferably 60% to 100% by mass, more preferably 70% to 100% by mass, even more preferably 80% to 100% by mass, even more preferably 90% to 100% by mass, particularly preferably 95% to 100% by mass, and most preferably 98% to 100% by mass, in order to better express the effects of the present invention.

[0028] The crosslinkable monomer (a) has two or more double bonds in its molecule. Any suitable crosslinkable monomer can be used as the crosslinkable monomer (a), as long as it does not impair the effects of the present invention, as long as it is a crosslinkable monomer that has two or more double bonds in its molecule. Examples of crosslinkable 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, pentadecaethylene glycol di(meth)acrylate, pentacontahectaethylene glycol di(meth)acrylate, 1,3-butylenedi(meth)acrylate, allyl(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetraacrylate, neopentyl glycol di(meth)acrylate, and the like. In order to better express the effects of the present invention, the crosslinkable monomer (a) is preferably an aromatic crosslinkable monomer having two or more aromatic functional groups and radically polymerizable double bonds in its skeleton, such as divinylbenzene and divinylnaphthalene, and divinylbenzene is more preferred. The crosslinkable monomer (a) may be used alone or two or more may be used.

[0029] As the aromatic monofunctional monomer (b), any suitable aromatic monofunctional monomer can be used as long as it has a molecular structure in which an aromatic functional group and one radically polymerizable double bond are present in the skeleton, provided that the effects of the present invention are not impaired. Examples of aromatic monofunctional monomers (b) include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, t-butylstyrene, ethyl vinylbenzene, vinylnaphthalene, styrene sulfonic acid, styrene sulfonate, vinyl benzoic acid, vinyl phenol, etc. Examples of styrene sulfonates include sodium styrene sulfonate and ammonium styrene sulfonate. Examples of vinyl benzoic acid include o-vinyl benzoic acid, m-vinyl benzoic acid, and p-vinyl benzoic acid. Examples of vinyl phenol include o-vinyl phenol, m-vinyl phenol, and p-vinyl phenol. To further enhance the effects of the present invention, the aromatic monofunctional monomer (b) is preferably at least one selected from the group consisting of styrene, α-methylstyrene, t-butylstyrene, and ethylvinylbenzene, and more preferably at least one selected from the group consisting of styrene and ethylvinylbenzene. These aromatic monofunctional monomers (b) may be used individually or in combination of two or more.

[0030] The total content of the crosslinkable monomer (a) and the aromatic monofunctional monomer (b) in the monomer component (M) is preferably 50% to 100% by mass, more preferably 80% to 100% by mass, even more preferably 90% to 100% by mass, and particularly preferably 95% to 100% by mass, in order to better express the effects of the present invention.

[0031] The content of the crosslinkable monomer (a) in the monomer component (M) is preferably 1% to 50% by mass, more preferably 2% to 40% by mass, even more preferably 3% to 30% by mass, even more preferably 5% to 25% by mass, particularly preferably 8% to 20% by mass, and most preferably 9% to 18% by mass, in order to better express the effects of the present invention.

[0032] The content of aromatic monofunctional monomer (b) in monomer component (M) is preferably 50% to 99% by mass, more preferably 60% to 98% by mass, even more preferably 70% to 97% by mass, particularly preferably 75% to 96% by mass, and most preferably 80% to 95% by mass, in order to better express the effects of the present invention.

[0033] The monomer component (M) may include any other suitable radical polymerizable monomer (m) that is different from either the crosslinkable monomer (a) or monofunctional monomer (b) described above, as long as it does not impair the effects of the present invention. Accordingly, the polymer (P) may have structural units derived from the crosslinkable monomer (a), structural units derived from the aromatic monofunctional monomer (b), and structural units derived from the other radical polymerizable monomer (m).

[0034] Other radical polymerizable monomers (m) include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and (meth)acrylic acid. Isooctyl methacrylate, nonyl methacrylate, isononyl methacrylate, decyl methacrylate, isodecyl methacrylate, undecyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, tetradecyl methacrylate, pentadecyl methacrylate, hexadecyl methacrylate, heptadecyl methacrylate, octadecyl methacrylate, isostearyl methacrylate, nonadecyl methacrylate, eicosyl methacrylate, etc. Alkyl (meth)acrylate esters with 1 to 20 carbon atoms in the alkyl group bonded to the phosphate group; (meth)acrylate esters having an alicyclic structure in the ester portion, such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; hydroxyalkyl (meth)acrylate monomers such as hydroxyethyl (meth)acrylate; (meth)acrylic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydro Carboxy group-containing monomers such as phthalic acid, 2-methacryloyloxyethyl maleic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl succinic acid, and 2-acryloyloxyethyl phthalic acid; glycidyl group-containing monomers such as glycidyl (meth)acrylate, allyl glycidyl ether, and 4-hydroxybutyl (meth)acrylate glycidyl ether; and epoxy group-containing monomers such as 1,2-epoxy-4-vinylcyclohexane and (meth)acrylate (3,4-epoxycyclohexyl)methyl;Examples include acrylamide derivative monomers such as 4-vinylphenylglycidyl ether (meth)acrylamide; (meth)acrylonitrile monomers, halogenated vinyl monomers such as vinyl chloride; vinyl carboxylate monomers such as vinyl acetate; olefin monomers such as ethylene; unsaturated imide monomers: vinyl alcohol; silane coupling agents having a vinyl group; and the like. Such other radical polymerizable monomers (m) may be one type or two or more types. The monomer component (M) does not necessarily contain other radical polymerizable monomers (m).

[0035] The content ratio of other radical polymerizable monomers (m) in monomer component (M) is preferably 0% to 50% by mass, more preferably 0% to 20% by mass, even more preferably 0% to 10% by mass, particularly preferably 0% to 5% by mass, and most preferably 0% to 2% by mass, in order to better exhibit the effects of the present invention.

[0036] The content of monomer component (M) in the composition is preferably 85% to 100% by mass, more preferably 90% to less than 100% by mass, even more preferably 95% to less than 100% by mass, particularly preferably 97% to less than 100% by mass, and most preferably 98% to 99% by mass, in order to better exhibit the effects of the present invention. If the content of monomer component (M) in the composition is too low and outside the above range, the effects of the present invention may not be exhibited, for example, excellent dielectric properties may not be exhibited. Here, monomer component (M) does not include polymerization initiators and surfactants used in the polymerization reaction.

[0037] The composition preferably contains a reactive surfactant (A) in addition to the monomer component (M). Therefore, the polymer (P) preferably has structural units derived from an aromatic monofunctional monomer (b), structural units derived from a crosslinkable monomer (a), and structural units derived from a reactive surfactant (A), and may also have structural units derived from a crosslinkable monomer (a), structural units derived from an aromatic monofunctional monomer (b), structural units derived from another radical polymerizable monomer (m), and structural units derived from a reactive surfactant (A).

[0038] Reactive surfactants (A) typically have one or more double bonds in their molecule. Examples of reactive surfactants (A) include anionic reactive surfactants and nonionic reactive surfactants.

[0039] Examples of anionic reactive surfactants include JS-20 or RS-3000 of Eleminor (registered trademark) manufactured by Sanyo Chemical Industries, Ltd., KH-10, KH-1025, KH-05, HS-10, HS-1025, BC-0515, BC-10, BC-1025, BC-20, BC-2020, AR-1025, or AR-2025 of Aqualon (registered trademark) manufactured by Daiichi Kogyo Seiyaku Co., Ltd., MS-60 of Antox (registered trademark) manufactured by Nippon Emulsifier Co., Ltd., S-120, S-180A, S-180, or PD-104 of Latemul (registered trademark) manufactured by Kao Corporation, and SR-1025 or SE-10N of Adekarya Soap (registered trademark) manufactured by ADEKA Corporation. From the viewpoint of improving the dispersibility of resin fine particles, anionic reactive surfactants having oxyalkylene chains in their molecular chains are preferred.

[0040] Examples of nonionic reactive surfactants include alkyl ethers (commercial products such as Adekarya Soap ER-10, ER-20, ER-30, ER-40 from ADEKA Corporation, and Latemul PD-420, PD-430, PD-450 from Kao Corporation); alkylphenyl ethers or alkylphenyl esters (commercial products such as Aqualon RN-10, RN-20, RN-30, RN-50, AN-10, AN-20, AN-30, AN-5065 from Daiichi Kogyo Seiyaku Co., Ltd.; Adekarya Soap NE-10, NE-20, NE-30, NE-40 from ADEKA Corporation); and (meth)acrylate sulfate esters (commercial products such as RMA-564, RMA-568, RMA-1114 from Nippon Emulsifier Co., Ltd.). From the viewpoint of dispersion stability of resin fine particles, nonionic reactive surfactants that have oxyalkylene chains in their molecular chains are preferred.

[0041] In the composition, the content of the reactive surfactant (A) is preferably 0 to 10 parts by mass, more preferably more than 0 parts by mass and 8 parts by mass or less, even more preferably more than 0 parts by mass and 5 parts by mass or less, particularly preferably more than 0 parts by mass and 3 parts by mass or less, and most preferably 0.1 to 2 parts by mass, in order to better exhibit the effects of the present invention when the monomer component (M) (total of crosslinkable monomer (a), aromatic monofunctional monomer (b), and other radical polymerizable monomer (m)) is 100 parts by mass. If the content is too high outside the above range, the effects of the present invention may not be exhibited, for example, excellent dielectric properties may not be exhibited. If the content is too low outside the above range, the effects of the present invention may not be exhibited, for example, the dispersion stability of the particles may be poor and resin fine particles may not be obtained.

[0042] <<<Applications of Resin Microparticles>>> The resin fine particles according to the embodiments of the present invention can be used in a variety of applications. In terms of making better use of the effects of the present invention, the resin fine particles according to the embodiments of the present invention are suitable for use as additives for electronic materials such as semiconductor components, optical components such as light diffusers and anti-glare / low-reflection materials, paint additives, and ink additives. In particular, since the resin fine particles according to the embodiments of the present invention have a small particle size, reduced metal components and eluted ion components, and excellent dielectric properties, it is possible to produce small or thin semiconductor components by adding a sufficient amount of resin fine particles, thereby improving dielectric properties while preventing ion migration.

[0043] ≪≪Method for Manufacturing Resin Microparticles≫≫ Resin fine particles according to embodiments of the present invention can be produced, for example, by emulsion polymerization of the above-mentioned monomers.

[0044] A method for producing resin fine particles according to embodiments of the present invention typically includes a two-step polymerization process consisting of a first polymerization step and a second polymerization step. In the first polymerization step, a radical polymerizable monomer component (M1) containing a monofunctional monomer (b1) is subjected to emulsion polymerization. In the second polymerization step, a radical polymerizable monomer component (M2) containing a monofunctional monomer (b2) and a crosslinkable monomer (a) is subjected to emulsion polymerization.

[0045] Emulsion polymerization is a polymerization method in which a liquid medium, a monomer component that is poorly soluble in the medium, and a surfactant are mixed, and a polymerization initiator that is soluble in the medium is added to carry out polymerization. Emulsion polymerization can reduce the variation in particle size of resin microparticles.

[0046] According to the manufacturing method of the embodiment of the present invention, resin fine particles can be produced in which metal components and eluted ion components are reduced and which have excellent dielectric properties.

[0047] The first polymerization step and the second polymerization step are preferably carried out in a single reactor, and more preferably carried out sequentially in a single reactor. By carrying out the first polymerization step and the second polymerization step in a single reactor, the proportion of coarse particles in the resin fine particles can be reduced.

[0048] <First polymerization step> In the first polymerization step, a monomer component (M1) containing a monofunctional monomer (b1) is typically emulsion polymerized to produce a crude product containing a polymer. This polymer is typically used as seed particles in the second polymerization step.

[0049] (Monofunctional monomer) Examples of monofunctional monomers (b1) include the monofunctional monomers listed as other radical polymerizable monomers (m) in the polymer P of the resin nanoparticles described above, and the monofunctional monomers listed as aromatic monofunctional monomers (b) in the polymer P of the resin nanoparticles described above. Methyl (meth)acrylate is preferred as monofunctional monomer (b1). In some cases, styrene is preferred as monofunctional monomer (b1). Alternatively, monofunctional monomer (b1) may be the same material as monofunctional monomer (b2) in the second polymerization step described later. Monofunctional monomer (b1) may be one type or two or more types.

[0050] The content ratio of monofunctional monomer (b1) in monomer component (M1) is preferably 50% to 100% by mass, more preferably 80% to 100% by mass, even more preferably 90% to 100% by mass, particularly preferably 95% to 100% by mass, and most preferably 98% to 100% by mass, in order to better express the effects of the present invention.

[0051] In the first polymerization step, as described above, emulsion polymerization is carried out using a composition containing a monomer component (M1), a liquid medium, a surfactant, and a polymerization initiator to obtain a crude product containing seed particles, which are polymers of the monomer component (M1), and a liquid medium.

[0052] (Liquid medium) The liquid medium used in the first polymerization step is not particularly limited. Examples of liquid media include water, organic solvents, and mixtures thereof. In the production method according to embodiments of the present invention, an aqueous medium is preferred as the liquid medium, and examples of such media include water, methyl alcohol, lower alcohols such as ethyl alcohol, and mixtures of water and lower alcohols.

[0053] (Surfactants) The surfactant used in the first polymerization step can be any suitable surfactant as long as it does not impair the effects of the present invention. There may be only one type of surfactant or two or more types. It is preferable that the surfactant includes a reactive surfactant in order to better express the effects of the present invention. Examples of reactive surfactants include anionic reactive surfactants and nonionic reactive surfactants. As an anionic reactive surfactant, for example, the anionic reactive surfactant listed as reactive surfactant (A) in the polymer P of the resin nanoparticles described above can be used. As a nonionic reactive surfactant, for example, the nonionic reactive surfactant listed as reactive surfactant (A) in the polymer P of the resin nanoparticles described above can be used. It is preferable that the surfactant does not include a non-reactive surfactant.

[0054] Furthermore, it is preferable not to use any emulsifying agents other than reactive surfactants in the first polymerization step.

[0055] The amount of surfactant used in the first polymerization step is preferably 0.01 to 20 parts by mass, more preferably 0.05 to 18 parts by mass, and even more preferably 0.1 to 16 parts by mass, per 100 parts by mass of monomer component (M1) in the first polymerization step.

[0056] (Polymerization initiator) The polymerization initiator used in the first polymerization step can be any suitable polymerization initiator as long as it does not impair the effects of the present invention. Radical polymerization initiators, particularly thermal polymerization initiators, are preferred as polymerization initiators. Examples of polymerization initiators include water-soluble azo compounds, persulfates (e.g., ammonium persulfate, potassium persulfate, sodium persulfate, etc.), hydrogen peroxide, organic peroxides, and oil-soluble nitrile-azo compounds.

[0057] Polymerization initiators include, for example, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]n-hydrate (trade name "VA-057"), 4,4'-azobis(4-cyanovaleric acid) (trade name "V-501"), 2,2'-azobis[2-(2-imidazolin-2-yl)propane] and its dihydrochloride salts (trade names "VA-061", "VA-044"), and 2,2'-azobis[2-methyl-N- (2-hydroxyethyl)propionamide] (product name "VA-086"), 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide} (product name "VA-080"), 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide} (product name "VA-082"), 2,2'-azobis{2-methyl- Water-soluble azo compounds such as N-[2-(1-hydroxybutyl)]-propionamide} (trade name "VA-085") (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.); organic peroxides such as cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide, dimethylbis(tert-butylperoxy)hexane, dimethylbis(tert-butylperoxy)hexine-3, bis(tert-butylperoxyisopropyl)benzene, bis(tert-butylperoxy)trimethylcyclohexane, butyl-bis(tert-butylperoxy)valerate, tert-butyl 2-ethylhexaneperoxyate, dibenzoyl peroxide, paramentane hydroperoxide, and tert-butylperoxybenzoate;2,2'-Azobisisobutyronitrile, 2,2'-Azobis(2-methylbutyronitrile), 2,2'-Azobis(2-isopropylbutyronitrile), 2,2'-Azobis(2,3-dimethylbutyronitrile), 2,2'-Azobis(2,4-dimethylbutyronitrile), 2,2'-Azobis(2-methylcapronitrile), 2,2'-Azobis(2,3,3-trimethylbutyronitrile), 2,2'-Azobis(2,4,4-trimethylvaleronitrile), 2,2'-Azobis( Examples include oil-soluble nitrile-azo compounds such as 2,4-dimethylvaleronitrile, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(4-ethoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(4-n-butoxy-2,4-dimethylvaleronitrile), 1,1'-azobis(cyclohexane-1-carbonitride), 2-(carbamoylazo)isobutyronitrile, and 4,4'-azobis(4-cyanopentanoic acid); etc. Furthermore, a redox-type initiator may be used as a polymerization initiator, which is a combination of the above-mentioned persulfate and organic peroxide polymerization initiators and a reducing agent such as sodium sulfoxylate formaldehyde, sodium bisulfite, ammonium bisulfite, sodium thiosulfate, ammonium thiosulfate, hydrogen peroxide, sodium hydroxymethanesulfinate, L-ascorbic acid or its salts, cuprous salts, or ferrous salts. Among these, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]n-hydrate (product name "VA-057"), 4,4'-azobis(4-cyanovaleric acid) (product name "V-501"), 2,2'-azobis[2-(2-imidazolin-2-yl)propane] (product name "VA-061"), and 2,2'-azobis[2-methyl-N-(2-hydroxyethyl )propionamide] (product name "VA-086"), 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide} (product name "VA-080"), 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide} (product name "VA-082"), 2,2'-azobis{2-methyl-N It is preferable to use one or more water-soluble azo compounds such as {2-(1-hydroxybutyl)]-propionamide} (trade name "VA-085") (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonnitrile), 4,4'-azobis(4-cyanopentanoic acid), cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and lauroyl peroxide, and it is more preferable to use a water-soluble azo compound. This makes it possible to reduce the total content of component A and the total amount of eluted ion component B in the resin fine particles. These polymerization initiators may be used individually or in combination of two or more.

[0058] The amount of polymerization initiator used in the first polymerization step is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and even more preferably 0.1 to 1 part by mass, per 100 parts by mass of monomer component (M1) in the first polymerization step.

[0059] The polymerization temperature in the first polymerization step can be any suitable polymerization temperature, as long as it is suitable for emulsion polymerization and does not impair the effects of the present invention. Such polymerization temperatures are preferably 30°C to 120°C, and more preferably 50°C to 90°C.

[0060] The polymerization time in the first polymerization step can be any appropriate polymerization time, as long as it is suitable for emulsion polymerization and does not impair the effects of the present invention. Such polymerization time is preferably 1 to 48 hours, and more preferably 1 to 24 hours, at the initial polymerization temperature.

[0061] <Second polymerization step> In the second polymerization step, emulsion polymerization is carried out using a composition containing a radical polymerizable monomer component (M2). Typically, this composition comprises a liquid medium, a monomer component (M2), a surfactant, and may further contain a polymerization initiator.

[0062] In the second polymerization step, typically, the monomer component (M2) is emulsion polymerized in the presence of the polymer obtained in the first polymerization step. That is, the emulsion polymerization in the second polymerization step is seed emulsion polymerization, using the polymer obtained in the first polymerization step as seed particles. In the second polymerization step, it is preferable to add a composition containing the monomer component (M2) to the polymer (seed particles) obtained in the first polymerization step and carry out polymerization.

[0063] Seed emulsion polymerization is a method in which polymers are used as seed particles, and the seed particles are grown while monomers are polymerized using a water-soluble polymerization initiator. In other words, seed emulsion polymerization is an emulsion polymerization method in which, in the presence of seed particles made of polymers, a liquid medium, a monomer component that is poorly soluble in the medium, and a surfactant are mixed, and polymerization is carried out by adding a polymerization initiator that is soluble in the medium.

[0064] The seed particles may be in the form of a dispersion. In the second polymerization step, it is preferable to add a composition containing monomer components (M2) to the crude product obtained in the first polymerization step and carry out polymerization.

[0065] As described above, it is preferable that the first polymerization step and the second polymerization step be carried out in a single reactor. Therefore, it is preferable that the second polymerization step be carried out in the same reactor as the first polymerization step, and more preferably that it be carried out immediately after the first polymerization step in the reactor in which the first polymerization step was carried out. Accordingly, it is preferable that the second polymerization step be carried out by adding a composition containing monomer components (M2) to the reactor used in the first polymerization step, which contains the crude product of the first polymerization step, and carrying out seed emulsion polymerization. Here, carrying out the first polymerization step and the second polymerization step consecutively means, for example, that after emulsion polymerization in the first polymerization step, the second polymerization step is carried out without removing the polymer (seed particles) from the reactor and / or without intentionally lowering the temperature of the reactor (i.e., without cooling the crude product of the first polymerization step).

[0066] (Cross-linkable monomer) The crosslinkable monomer (a) is the same as the crosslinkable monomer (a) listed in <polymer P> of the <<resin fine particles>> described above. One type of crosslinkable monomer (a) may be used alone, or two or more types may be used.

[0067] (Monofunctional monomer) The monofunctional monomer (b2) is preferably an aromatic monofunctional monomer. Examples of aromatic monofunctional monomers include those listed as aromatic monofunctional monomer (b) in the polymer P of the resin fine particles described above. The monofunctional monomer (b2) is preferably at least one selected from the group consisting of styrene, α-methylstyrene, t-butylstyrene, and ethylvinylbenzene, and more preferably at least one selected from the group consisting of styrene and ethylvinylbenzene. These aromatic monofunctional monomers (b2) may be used individually or in combination of two or more.

[0068] The total content of the crosslinkable monomer (a) and monofunctional monomer (b2) in the monomer component (M2) is preferably 50% to 100% by mass, more preferably 80% to 100% by mass, even more preferably 90% to 100% by mass, particularly preferably 95% to 100% by mass, and most preferably 98% to 100% by mass, in order to better express the effects of the present invention.

[0069] (Liquid medium) The liquid medium used in the second polymerization step is not particularly limited, and the medium described in the first polymerization step can be used, and the preferred range is the same as described in the first polymerization step. In the manufacturing method according to the embodiment of the invention, the liquid medium is preferably an aqueous medium, and for example, water, methyl alcohol, lower alcohols such as ethyl alcohol, a mixture of water and a lower alcohol can be used.

[0070] The amount of liquid medium used can be any appropriate amount, as long as it does not impair the effects of the present invention. The amount of medium at the start of the second polymerization step (for example, the total amount of medium used in the first polymerization step and the second polymerization step) is preferably 10 to 5000 parts by mass, more preferably 50 to 3000 parts by mass, even more preferably 100 to 2000 parts by mass, and particularly preferably 120 to 1000 parts by mass, based on 100 parts by mass of the total amount of monomer component (M1) and monomer component (M2).

[0071] (Surfactants) The surfactant used in the second polymerization step can be any suitable surfactant, as long as it does not impair the effects of the present invention. In the second polymerization step, the surfactants described in the first polymerization step can be used. There may be only one surfactant or two or more surfactants. It is preferable that the surfactants include a reactive surfactant in order to better exhibit the effects of the present invention.

[0072] When a surfactant is used in the second polymerization step, the amount of surfactant used (the amount added during the second polymerization step) is preferably 0.05 to 7 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.15 to 3 parts by mass, based on 100 parts by mass of the total amount of monomer component (M1) and monomer component (M2).

[0073] The total amount of surfactant used in the production method according to the embodiment of the present invention is preferably 0.05 to 7 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.15 to 4 parts by mass, based on 100 parts by mass of the total amount of monomer component (M1) and monomer component (M2).

[0074] In at least one of the first polymerization step and the second polymerization step, it is preferable to use a reactive surfactant. That is, it is preferable that at least one of the compositions selected from the monomer component (M1) in the first polymerization step and the monomer component (M2) in the second polymerization step contains a reactive surfactant.

[0075] In the first and second polymerization steps, non-reactive surfactants can be used to the extent that they do not impair the effects of the present invention, but it is preferable that non-reactive surfactants are not used. That is, it is preferable that the above composition containing monomer component (M1) in the first polymerization step and the above composition containing monomer component (M2) in the second polymerization step contain a reactive surfactant. Examples of non-reactive surfactants include anionic non-reactive surfactants such as sodium oleate; fatty acid soaps such as potassium castor oil soap; alkyl sulfate esters such as sodium lauryl sulfate and ammonium lauryl sulfate; alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate; alkylnaphthalene sulfonates; alkanesulfonates; dialkyl sulfosuccinates; alkyl phosphate esters; naphthalene sulfonic acid formalin condensate; polyoxyethylene alkylphenyl ether sulfate; polyoxyethylene sulfonated phenyl ether phosphate; polyoxyethylene alkyl ether phosphate; polyoxyethylene alkyl sulfate ester; and polyoxyalkylene branched decyl ether, polyoxyethylene tridecyl ether, polyoxyalkylene alkyl ether, polyoxyalkyl Examples of nonionic reactive surfactants include sialcyl tridecyl ether, polyoxyethylene isodecyl ether, polyoxyalkylene lauryl ether, polyether polyol, polyoxyethylene styrene phenyl ether, polyoxyethylene naphthyl ether, polyoxyethylene phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene lauryl ether, polyoxyethylene oleyl cetyl ether, polyoxyethylene glyceryl isostearate, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxysorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, and oxyethylene-oxypropylene block polymer.

[0076] (Polymerization initiator) The polymerization initiator used in the second polymerization step can be any suitable radical polymerization initiator, provided that it does not impair the effects of the present invention. In the second polymerization step, the polymerization initiators listed in the first polymerization step can be used, and the preferred range is the same as described in the first polymerization step. The polymerization initiator used in the first polymerization step and the polymerization initiator used in the second polymerization step may be the same.

[0077] In at least one of the first polymerization step and the second polymerization step, it is preferable to use a water-soluble azo compound as a polymerization initiator.

[0078] The amount of polymerization initiator used in the second polymerization step (the amount added during the second polymerization step) is preferably 0.05 to 5.0 parts by mass, more preferably 0.08 to 3.0 parts by mass, and even more preferably 0.1 to 2.0 parts by mass, based on 100 parts by mass of the total amount of monomer component (M1) and monomer component (M2).

[0079] The total amount of polymerization initiator used in the production method according to the embodiment of the present invention is preferably 0.05 to 5.0 parts by mass, more preferably 0.08 to 3.0 parts by mass, and even more preferably 0.1 to 2.0 parts by mass, based on 100 parts by mass of the total amount of monomer component (M1) and monomer component (M2).

[0080] The polymerization temperature in the second polymerization step can be any suitable polymerization temperature, as long as it is suitable for emulsion polymerization and does not impair the effects of the present invention. Such polymerization temperatures are preferably 30°C to 120°C, more preferably 50°C to 100°C. For example, the polymerization temperature in the second polymerization step may be 30°C to 90°C as the initial polymerization temperature, and then increased to 70°C to 120°C as the later polymerization temperature.

[0081] The polymerization time in the second polymerization step can be any appropriate polymerization time, as long as it is suitable for emulsion polymerization and does not impair the effects of the present invention. Such polymerization time is preferably 1 to 48 hours, and more preferably 1 to 24 hours, at the initial polymerization temperature.

[0082] <Other processes> After the second polymerization step described above, the particles may be washed, classified, dried, or otherwise processed as needed. [Examples]

[0083] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0084] <Volume-average particle size> The volume-average particle size of the resin microparticles was measured using a laser diffraction / scattering particle size distribution analyzer (Beckman Coulter, "LS 13 320"). By subjecting a dispersion of the resin microparticles to measurement, the volume-based particle size distribution and its standard deviation were obtained. The arithmetic mean diameter in the obtained volume-based particle size distribution was defined as the volume-average particle size of the resin microparticles. The measurement conditions for the laser diffraction / scattering particle size distribution analyzer are as follows. Sample Dispersion Module: Universal Liquid Module Medium: Ion-exchanged water Refractive index of the medium: 1.333 Refractive index of the sample: Refractive index of resin microparticles The refractive index of the above resin fine particles was calculated using the weighted average of the refractive indices of each monomer homopolymer used in the manufacturing process, weighted by the amount of each monomer used.

[0085] <Coefficient of variation of volume-averaged particle diameter> The coefficient of variation (CV value) of the volume-average particle size of the resin microparticles was calculated using the following formula. Coefficient of variation [%] = (Standard deviation of the volume-based particle size distribution of resin microparticles ÷ Volume-average particle diameter of resin microparticles) × 100

[0086] <Percentage of particles with a particle size of 10 μm or more> The percentage of particles with a particle size of 10 μm or more is measured using a Coulter Multisizer TM 4e (measurement device manufactured by Beckman Coulter, Inc.). The measurement is carried out using an aperture calibrated according to the Multisizer TM 4e Users Manual. It is assumed that the measurement is performed using an aperture calibrated according to the Multisizer Note that the aperture used for the measurement is appropriately selected according to the size of the resin fine particles to be measured. Current (aperture current) and Gain (gain) are appropriately set according to the size of the selected aperture. For example, when an aperture with a size of 50 μm is selected, Current (aperture current) is set to -800 and Gain (gain) is set to 4. As the measurement sample, 0.1 g of resin fine particles are dispersed in 10 ml of an aqueous solution of 0.1 wt% polyoxyethylene sorbitan monolaurate "Tween 20" using a touch mixer (manufactured by Yamato Scientific Co., Ltd., "TOUCHMIXER MT-31") and an ultrasonic cleaner (manufactured by Vervo Clea Co., Ltd., "ULTRASONIC CLEANER VS-150") to obtain a dispersion, which is used as the measurement sample. During the measurement, the inside of the beaker is gently stirred so that no bubbles enter, and the measurement is terminated when 100,000 resin fine particles are measured. In the volume-based particle size distribution obtained from the measurement results, the percentage of particles with a particle size of 10 μm or more is confirmed.

[0087] <Total content of component A> (Measurement sample) A dispersion containing resin fine particles is dried using a spray dryer (manufactured by Sakamoto Giken Co., Ltd., machine name: Spray Dryer, type: Atomizer Take-up type, model number: TRS-3WK) under the following device conditions, and the dried product is used as the measurement sample. (Spray dryer device conditions) Dispersion supply rate of resin fine particles: 25 mL / min Atomizer rotation speed: 12000 rpm Air volume: 2 m 3 / min Inlet temperature (temperature at the inlet of the spray dryer through which a dispersion liquid containing resin microparticles is sprayed): 150℃ Outlet temperature (the outlet temperature of the nozzle on the spray dryer from which the dried particles are discharged): 70℃ (Measurement method) The total content of component A was measured as follows: Approximately 1.0 g of the accurately weighed sample was heated at 500°C for 1 hour to produce a ash. The resulting ash was mixed with 1 mL of concentrated hydrochloric acid (Ultrapur-100 ultra-high purity reagent, manufactured by Kanto Chemical Co., Ltd.). The insoluble matter in the mixture was filtered through ADVANTEC No. 7 filter paper, and the filtrate was diluted to 25 mL with distilled water to prepare the test solution. ICP emission spectroscopy was performed on the test solution under the following conditions. The concentration of each element was determined from a pre-prepared calibration curve. The amount of each element was calculated using the following formula. Component amount [ppm] = Measured element concentration [μg / mL] x 25 [mL] ÷ Sample amount [g] The total content of component A was calculated from the amount of each element measured. In calculating the total content of component A, elements whose measurement results were below the detection limit were not considered. That is, the sum of the amounts of elements above the detection limit was used as the total content of component A. The detection limits for elements P and K were 0.5 ppm, and for the other elements, they were 0.3 ppm. (ICP measurement conditions) Measurement device: Shimadzu Corporation "ICPE-9000" multi-type ICP emission spectrometer Measured elements: Al, Ba, Ca, Cr, Cu, Fe, K, Mg, Mn, Na, P, S, Si, Sr, Zn Observation direction: Axis High-frequency output: 1.20kW Carrier flow rate: 0.7 L / min Plasma flow rate: 10.0 L / min Auxiliary flow rate: 0.6L / min Exposure time: 30 seconds Calibration standard solutions: SPEX Corporation "XSTC-13" general-purpose mixed standard solution, 31-element mixture (base 5% HNO3), approximately 10 mg / L each; "XSTC-8" general-purpose mixed standard solution, 13-element mixture (base H2O / trace HF), approximately 10 mg / L each. (ashing conditions) Measurement equipment: Microwave muffle furnace Phoenix high-capacity type (manufactured by CEM) Ashing conditions: 500°C × 1 hr (sample amount = approximately 1.0 g)

[0088] <Total amount of eluted ion component B> (Measurement sample) The obtained resin fine particles were dried using a spray dryer under the same conditions as described above for the total content of component A, and this was used as the measurement sample. (Measurement method) The eluted ion component B was measured as follows. A 50 mL container was prepared, and approximately 50 mL of deionized water was added and washed three times. Approximately 0.2 g of the sample was accurately weighed into the washed 50 mL container. 1 mL of washing ethanol (Clinsolve P) was added and mixed well, and then another 50 mL of deionized water was added and mixed well. The resulting mixture was subjected to ultrasonic cleaning and extraction for approximately 10 minutes, and then filtered through an aqueous 0.20 μm chromatographic disk. This was used as the test solution for ion chromatography measurement. A calibration curve was created by measuring the standard solution under the following measurement conditions. Next, the test solution was measured under the same conditions. The concentration of each measured ion in the sample was determined from the calibration curve using the peak area values ​​of each ion obtained from the chromatogram. The standard solution used for the calibration curve was "Anion Mixed Standard Solution 1" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. The amount of eluted ion component for each measured ion in the sample was calculated using the following formula. Amount of eluted ions [ppm] = Measured ion concentration [μg / mL] × 51 [mL] ÷ Sample volume [g] The total amount of eluted ion component B was calculated from the amount of eluted ion component for each measured ion. In calculating the total amount of eluted ion component B, ions whose measurement results were below the limit of quantification were not considered. That is, the sum of the eluted ion component amounts of ions above the limit of quantification was taken as the total amount of eluted ion component B. The limit of quantification was 2 ppm. (Ion chromatography measurement conditions) Measuring device: "IC-2001" manufactured by Tosoh Corporation Measured ion: F - Cl - NO2 - , Br - NO3 - , PO4 3- SO4 2- Column: TOSOH Corporation "TSKGEL superIC-AZ" Mobile phase: 3.2mM Na2CO3+1.9mM NaHCO3 Flow rate: 0.8mL / min Column temperature: 40℃ Injection volume: 30μL

[0089] <Dielectric properties of resin microparticles> (Measurement sample) The obtained resin fine particles were dried using a spray dryer under the same conditions as described above for the total content of component A, and this was used as the measurement sample. (Measurement method) The dielectric properties of the sample were measured using a dielectric constant measuring device (ADMS01Nc series) manufactured by AET. The measurements were performed at a frequency of 10 GHz, in a measurement environment of 23°C, and with a relative humidity of 51 ± 1%. The relative permittivity and dielectric loss tangent of the resin nanoparticles were calculated based on perturbation theory using a resonator.

[0090] [Example 1] In a pressure-resistant polymerization reactor equipped with a stirring device, thermometer, and cooling mechanism, 240 parts by mass of deionized water and 0.03 parts by mass of Aqualon AR-1025 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., 25% purity) as a reactive surfactant were mixed to prepare the first aqueous phase. Next, 4 parts by mass of methyl methacrylate were added to the reactor, nitrogen gas was blown in for 3 minutes, then the reactor was sealed and the temperature was raised to 60°C. In a separate container, 0.04 parts by mass of 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]n hydrate was dissolved in 2 parts by mass of deionized water as a polymerization initiator to prepare a polymerization initiator solution. The polymerization initiator solution was added to the reactor, which had reached 60°C, and the polymerization reaction was carried out for 2 hours (first polymerization step).

[0091] In a separate container, 76 parts by mass of deionized water, 0.9 parts by mass of Aqualon AR-1025 as a reactive surfactant, and 0.36 parts by mass of 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]n hydrate as a polymerization initiator were mixed to prepare a second aqueous phase. Next, 67 parts by mass of styrene and 9 parts by mass of divinylbenzene (NS Styrene Monomer Co., Ltd., DVB-810) were mixed and added to the second aqueous phase. The mixture was then stirred at 8000 rpm for 10 minutes using a TK homomixer (Primix Co., Ltd.) to obtain a monomer mixture. The monomer mixture was added to the reactor, which had completed the first polymerization step, over a period of 3 hours. After the addition was complete, polymerization was carried out at 60°C for 2 hours, and then the temperature was raised to 85°C for another 2 hours (second polymerization step).

[0092] After the polymerization reaction was completed, the resulting dispersion was cooled and then classified by passing it through a 500-mesh (24 μm mesh opening) screen to obtain a dispersion containing the resin fine particles of Example 1. The volume-average particle size of the resin microparticles in Example 1 was 0.36 μm, and the coefficient of variation (CV value) of the volume-average particle size was 14%. In Example 1, the proportion of particles with a particle size of 10 μm or larger was 0% by volume. Table 1 shows the measurement results of the total content of component A and the total amount of eluted ion component B in the resin microparticles of Example 1.

[0093] [Example 2] Except for changing the amount of Aqualon AR-1025 used in the first polymerization step from 0.03 parts by mass to 2.5 parts by mass, the procedure was carried out in the same manner as in Example 1 to obtain the resin fine particles of Example 2. The volume-average particle size of the resin microparticles in Example 2 was 0.13 μm, and the coefficient of variation (CV value) of the volume-average particle size was 19%. In Example 2, the proportion of particles with a particle size of 10 μm or larger was 0% by volume. Table 1 shows the measurement results of the total content of component A and the total amount of eluted ion component B in the resin microparticles of Example 2.

[0094] [Example 3] In a pressure-resistant polymerization reactor equipped with a stirring device, thermometer, and cooling mechanism, 240 parts by mass of deionized water and 0.01 parts by mass of Aqualon AR-1025 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., 25% purity) as a reactive surfactant were mixed to prepare the first aqueous phase. Next, 4 parts by mass of methyl methacrylate were added to the reactor, nitrogen gas was blown in for 3 minutes, then the reactor was sealed and the temperature was raised to 75°C. In a separate container, 0.04 parts by mass of 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] was dissolved in 2 parts by mass of deionized water as a polymerization initiator to prepare a polymerization initiator solution. The polymerization initiator solution was added to the reactor, which had reached 75°C, and the polymerization reaction was carried out for 2 hours (first polymerization step).

[0095] In a separate container, 76 parts by mass of deionized water, 0.8 parts by mass of Aqualon AR-1025 as a reactive surfactant, and 0.36 parts by mass of 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] as a polymerization initiator were mixed to prepare a second aqueous phase. Next, 54 parts by mass of styrene and 22 parts by mass of divinylbenzene (NS Styrene Monomer Co., Ltd., DVB-810) were mixed and added to the second aqueous phase. The mixture was then stirred at 8000 rpm for 10 minutes using a TK homomixer (Primix Co., Ltd.) to obtain a monomer mixture. The monomer mixture was added to the reactor, which had completed the first polymerization step, over a period of 5 hours. After the addition was complete, the temperature was raised to 85°C and polymerization was carried out for 3 hours, and then the temperature was further raised to 100°C and polymerization was carried out for 5 hours (second polymerization step).

[0096] After the polymerization reaction was completed, the resulting dispersion was cooled and then classified by passing it through a 500-mesh (24 μm mesh opening) screen to obtain the dispersion containing the resin fine particles of Example 3. The volume-average particle size of the resin microparticles in Example 3 was 0.58 μm, and the coefficient of variation (CV value) of the volume-average particle size was 13%. In Example 3, the proportion of particles with a particle size of 10 μm or larger was 0% by volume. Table 1 shows the measurement results of the total content of component A and the total amount of eluted ion component B in the resin microparticles of Example 3.

[0097] [Example 4] Except for changing the reactive surfactant in the first polymerization step from Aqualon AR-1025: 0.03 parts by mass to Eleminol JS-20 (manufactured by Sanyo Chemical Industries, Ltd., 40% purity): 0.02 parts by mass, and changing the reactive surfactant in the second polymerization step from Aqualon AR-1025: 0.9 parts by mass to Eleminol JS-20 (manufactured by Sanyo Chemical Industries, Ltd., 40% purity): 0.8 parts by mass, the procedure was carried out in the same manner as in Example 1 to obtain the resin fine particles of Example 4. The volume-average particle size of the resin microparticles in Example 4 was 0.34 μm, and the coefficient of variation (CV value) of the volume-average particle size was 13%. In the resin microparticles of Example 4, the proportion of particles with a particle size of 10 μm or larger was 0% by volume. Table 1 shows the measurement results of the total content of component A and the total amount of eluted ion component B in the resin microparticles of Example 4.

[0098] [Example 5] Except for changing 9 parts by mass of divinylbenzene (NS Styrene Monomer Co., Ltd., DVB-810) in the second polymerization step to 9 parts by mass of neopentyl glycol dimethacrylate, the procedure was carried out in the same manner as in Example 1 to obtain the resin fine particles of Example 5. The volume-average particle size of the resin microparticles in Example 5 was 0.37 μm, and the coefficient of variation (CV value) of the volume-average particle size was 14%. In Example 5, the proportion of particles with a particle size of 10 μm or larger was 0% by volume. Table 1 shows the measurement results of the total content of component A and the total amount of eluted ion component B in the resin microparticles of Example 5.

[0099] <Manufacturing Example 1> In a reactor equipped with a stirrer, thermometer, and cooling mechanism, an aqueous phase was prepared by mixing 270 parts by mass of deionized water and 0.07 parts by mass of sodium styrenesulfonate as an emulsifying agent. Next, a mixture of 120 parts by mass of methyl methacrylate and 2.4 parts by mass of 1-octanthiol as a chain transfer agent was added to the aqueous phase in the reactor. After purging the reactor with nitrogen for 5 minutes, the temperature was raised to 80°C. At 80°C, a polymerization initiator solution, in which 0.05 parts by mass of potassium persulfate was dissolved in 10 parts by mass of deionized water, was added. After that, the reactor was purged with nitrogen again for 5 minutes, and the emulsion polymerization reaction was carried out by stirring at 80°C for 5 hours. After this, the temperature was further raised to 100°C and held for 3 hours before cooling to prepare a slurry containing resin particles. This was used as seed particles.

[0100] [Comparative Example 1] An aqueous phase was prepared by mixing 70 parts by mass of deionized water and 0.35 parts by mass of eleminol JS-20 as a reactive surfactant in a container. An oil phase was prepared by thoroughly mixing 61 parts by mass of styrene and 9 parts by mass of divinylbenzene (NS Styrene Monomer Co., Ltd., DVB-810) in a separate container. The oil phase was added to the aqueous phase and stirred at 8000 rpm for 10 minutes using a TK homomixer (Primix Co., Ltd.) to obtain a monomer mixture. In a reactor equipped with a stirring device, thermometer, and cooling mechanism, 220 parts by mass of deionized water and 33 parts by mass of seed particles prepared in Production Example 1 were added. After purging with nitrogen for 5 minutes, the temperature was raised to 70°C. In a separate container, a polymerization initiator solution was prepared by dissolving 0.2 parts by mass of 4,4'-azobis(4-cyanovaleric acid) as a polymerization initiator in a mixture of 5 parts by mass of ethanol and 5 parts by mass of deionized water. The polymerization initiator solution was added when the temperature in the reactor reached 70°C. Subsequently, the monomer mixture was added to the reactor over 4 hours to carry out the polymerization reaction. After the reaction, the temperature was further raised to 95°C and the reaction was carried out for 3 hours. After the polymerization reaction, the resulting dispersion was cooled and classified by passing it through a 400-mesh mesh to obtain a dispersion containing the resin fine particles of Comparative Example 1. The volume-average particle size of the resin fine particles in Comparative Example 1 was 0.38 μm, and the coefficient of variation of the volume-average particle size was 15%.

[0101] [Comparative Example 2] The procedure was carried out in the same manner as in Comparative Example 1, except that 0.35 parts by mass of eleminol JS-20 was replaced with 0.21 parts by mass of phosphanol RS-610 (manufactured by Toho Chemical Industry Co., Ltd.), a non-reactive surfactant, to obtain a dispersion containing resin fine particles of Comparative Example 2. The volume-average particle size of the resin fine particles in Comparative Example 2 was 0.37 μm, and the coefficient of variation of the volume-average particle size was 15%.

[0102] [Table 1]

[0103] The results in Table 1 show that the resin fine particles obtained in Examples 1 to 5 had reduced total content of component A and total amount of eluted ion component B, and also possessed excellent dielectric properties.

[0104] Resin fine particles according to embodiments of the present invention can be used in semiconductor components and the like.

Claims

1. Resin fine particles are dry powders consisting of a polymer (P) obtained by the reaction of a composition containing a radical polymerizable monomer component (M), The volume-average particle size of the resin fine particles is 0.05 μm or more and 2 μm or less. The total content of component A, as measured by inductively coupled plasma emission spectrometry, is 100 ppm or less. The total amount of eluted ion component B measured by ion chromatography is 100 ppm or less. The dielectric loss tangent at a frequency of 10 GHz is 0.0050 or less. The radical polymerizable monomer component (M) includes a crosslinkable monomer (a), an aromatic monofunctional monomer (b), and another radical polymerizable monomer (m) different from the crosslinkable monomer (a) and the aromatic monofunctional monomer (b). The content ratio of the crosslinkable monomer (a) in the radical polymerizable monomer component (M) is 8% by mass to 25% by mass. The content ratio of the other radical polymerizable monomer (m) in the radical polymerizable monomer component (M) is 5% by mass to 10% by mass. The crosslinkable monomer (a) is at least one selected from the group consisting of divinylbenzene and divinylnaphthalene. The aromatic monofunctional monomer (b) is at least one selected from the group consisting of styrene, α-methylstyrene, t-butylstyrene, and ethylvinylbenzene. The composition comprises a reactive surfactant (A), Resin fine particles. Component A: Al, Ba, Ca, Cr, Cu, Fe, K, Mg, Mn, Na, P, S, Si, Sr, and Zn Ionic component B: Fluoride ions, chloride ions, nitrite ions, bromide ions, nitrate ions, phosphate ions, and sulfate ions

2. The resin fine particles according to claim 1, wherein the dielectric loss tangent is 0.0030 or less.

3. The resin fine particles according to claim 1, wherein the proportion of particles with a particle diameter of 10 μm or more is 0.01% by volume or less.

4. The resin fine particles according to claim 1, wherein the coefficient of variation of the volume-average particle diameter is 25% or less.

5. Resin fine particles according to any one of claims 1 to 4, used as an additive for electronic materials.

6. Resin fine particles according to any one of claims 1 to 4, used as an additive for optical materials.

7. Resin fine particles according to any one of claims 1 to 4, used as an additive for paints.

8. Resin fine particles according to any one of claims 1 to 4, used as an additive for ink.

9. A method for producing resin fine particles according to any one of claims 1 to 4, A two-stage polymerization process consisting of a first polymerization step and a second polymerization step, Drying of the particles, Perform In the first polymerization step, a radical polymerizable monomer component (M1) containing a monofunctional monomer (b1) is subjected to emulsion polymerization. In the second polymerization step, a radical polymerizable monomer component (M2) containing a monofunctional monomer (b2) and a crosslinkable monomer (a) is subjected to emulsion polymerization. In the first polymerization step and the second polymerization step, a reactive surfactant is used, and a non-reactive surfactant is not used. The reactive surfactant is at least one selected from the group consisting of anionic reactive surfactants and nonionic reactive surfactants. The reactive surfactant has an oxyalkylene chain in its molecular chain, The monofunctional monomer (b1) comprises at least one selected from the group consisting of an aromatic monofunctional monomer and another radical polymerizable monomer (m) different from the crosslinkable monomer (a) and the aromatic monofunctional monomer. The content ratio of the crosslinkable monomer (a) in the total of the radical polymerizable monomer component (M1) and the radical polymerizable monomer component (M2) is 8% by mass to 25% by mass. The content ratio of the other radical polymerizable monomer (m) in the total of the radical polymerizable monomer component (M1) and the radical polymerizable monomer component (M2) is 5% by mass to 10% by mass. The crosslinkable monomer (a) is at least one selected from the group consisting of divinylbenzene and divinylnaphthalene. The monofunctional monomer (b2) and the aromatic monofunctional monomer are each independently at least one selected from the group consisting of styrene, α-methylstyrene, t-butylstyrene, and ethylvinylbenzene. A method for producing resin microparticles.

10. The method for producing resin fine particles according to claim 9, wherein the first polymerization step and the second polymerization step are carried out in a single reactor.

11. A method for producing resin fine particles according to claim 9, wherein a water-soluble azo compound is used as a polymerization initiator in at least one selected from the first polymerization step and the second polymerization step.

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