Resin fine particle, and production method and use of the same

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] The present invention relates to resin microparticles, a method for producing the same, and uses thereof. [Background technology]

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

[0003] In recent years, the semiconductor materials market has seen a variety of studies being conducted to miniaturize and improve the performance of electronic circuits. For example, it has been reported that adding fillers to various semiconductor materials, such as sealants, interlayer insulating films, and copper-clad laminates, can result in semiconductor materials with improved physical properties, such as elasticity, while maintaining good dielectric properties (Patent Document 1). However, when using resin microparticles for such applications, the resin microparticles must be made smaller to miniaturize the semiconductor materials, have a low dielectric loss tangent of the particles themselves, and have their metal or ionic components reduced in advance to prevent ion migration.

[0004] Emulsion polymerization and seed polymerization are methods for producing resin microparticles with an average particle size of 1 μm or less. However, these polymerizations use a large amount of surfactant when emulsifying oil droplets, which poses a problem of residual ionic components in the resulting resin microparticles. A washing process for washing particles has been reported as a technique for reducing residual ionic components (Patent Document 2), but more precise washing requires a large amount of washing water, which poses problems in terms of production and cost.

[0005] Low ionic resin particles produced without using surfactants or emulsifiers have been reported (Patent Document 3). However, the low ionic resin particles 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 the particle surface.

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

[0007] [Patent Document 1] Japanese Patent Application Publication No. 2023-165254 [Patent Document 2] International Publication No. 2015 / 045448 [Patent Document 3] Japanese Patent Application Laid-Open No. 2005-082695 [Patent Document 4] Japanese Patent Publication No. 2022-117594 Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention has been made to solve the above-mentioned problems of the prior art, and its main object is to provide resin microparticles that have reduced metal components and eluted ion components and have excellent dielectric properties, a method for producing such resin microparticles, and uses of such resin microparticles. [Means for solving the problem]

[0009] [1] The resin microparticles according to an embodiment of the present invention are The total content of component A 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 Ion component B: fluoride ions, chloride ions, nitrite ions, bromide ions, nitrate ions, phosphate ions, and sulfate ions [2] The resin particles described in [1] above may have a dielectric loss tangent of 0.0030 or less. [3] The resin microparticles according to the above [1] or [2] contain a polymer (P) obtained by the reaction of a composition containing a radical polymerizable monomer component (M), The monomer component (M) may contain a crosslinkable monomer (a) and an aromatic monofunctional monomer (b). [4] In the resin particles described in [3] above, the crosslinkable monomer (a) may contain an aromatic crosslinkable monomer. [5] In the resin fine particles described in the above [3] or [4], the composition may contain a reactive surfactant (A). [6] The resin particles according to 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 content of particles having a particle diameter of 10 μm or more of 0.01% by 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 according to any one of [1] to [8] above may have a coefficient of variation of the volume average particle diameter of 25% or less.

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

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

[12] The resin fine particles according to any one of the above [1] to [9] may be used as a paint additive.

[13] The resin fine particles according to any one of [1] to [9] above may be used as an ink additive.

[14] A method for producing resin microparticles according to an embodiment of the present invention includes: The method for producing resin microparticles according to any one of [1] to

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

[15] In the method for producing resin microparticles according to the above item

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

[16] In the method for producing resin microparticles according to the above

[14] or

[15] , 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 microparticles described in any one of

[14] to

[16] above, a water-soluble azo-based 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 microparticles 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 microparticles 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. [Effects of the Invention]

[0010] According to an embodiment of the present invention, it is possible to provide resin microparticles that have reduced metal components and eluted ion components and have excellent dielectric properties. It is also possible to provide a method for producing such resin microparticles. It is also possible to provide uses of such resin microparticles. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, embodiments of the present invention will be described, 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 particles according to the embodiment of the present invention have a total content of the following component A of 100 ppm or less, and a total amount of the following eluted ionic component B of 100 ppm or less. Component A: Al, Ba, Ca, Cr, Cu, Fe, K, Mg, Mn, Na, P, S, Si, Sr, and Zn Ion component B: fluoride ion (F - ), chloride ions (Cl - ), nitrite ion (NO2 - ), bromide ion (Br - ), nitrate ions (NO3 - ), phosphate ions (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) atomic emission spectrometry. The total amount of eluted ionic 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 mass of the resin microparticles, and the total amount of eluted ionic component B in the resin microparticles means the mass of eluted ionic component B per mass of the resin microparticles. Therefore, 1 ppm = 1 mg / kg in terms of the total content of component A and the total amount of eluted ionic component B.

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

[0016] The total content of component A in the resin microparticles according to the embodiment 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 microparticles according to the embodiment of the present invention is, for example, 0 ppm or more, and may be 0.1 ppm or more.

[0017] The total amount of eluted ionic components B of the resin microparticles according to the embodiment 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 ionic components B of the resin microparticles according to the embodiment of the present invention is, for example, 0 ppm or more, and may be 0.1 ppm or more.

[0018] The resin particles according to the present invention have a dielectric loss tangent of 0.0050 or less at a frequency of 10 GHz. Such resin particles with a low dielectric loss tangent themselves can exhibit the excellent dielectric properties of the resin in which they are mixed. Examples of excellent dielectric properties include a low dielectric constant and a low dielectric loss tangent.

[0019] The resin particles according to the embodiment of the present invention have a dielectric loss tangent at a frequency of 10 GHz of 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 dielectric loss tangent may preferably be 0 or more.

[0020] The resin particles according to the embodiment of the present invention preferably have a relative dielectric constant at a frequency of 10 GHz of 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 microparticles according to an embodiment of the present invention is not particularly limited and can be appropriately set depending on the purpose and application. The volume average particle diameter of the resin microparticles according to an embodiment 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 microparticles according to an embodiment 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 microparticles according to an embodiment 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 microparticles according to the embodiment of the present invention is not particularly limited and can be appropriately set depending on the purpose and use. The coefficient of variation of the volume average particle diameter of the resin microparticles according to the embodiment 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 microparticles according to the embodiment of the present invention may be, for example, 1% or more, 5% or more, or even 10% or more. The coefficient of variation of the volume average particle diameter of the resin fine particles is a value calculated by the following formula (1), and represents the distribution width of the data. Coefficient of variation [%] = (standard deviation of volume-based particle size distribution of resin microparticles ÷ volume-average particle diameter of resin microparticles) × 100 (1)

[0023] In the resin microparticles according to an embodiment of the present invention, the proportion of particles having a particle diameter of 10 μm or more is, for example, 0.01% by volume or less, and preferably 0% by volume. The proportion is measured by the proportion based on the number, and for example, the method described in the Examples below can be used.

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

[0025] <Polymer P> The resin microparticles according to the present invention typically contain a polymer (P) obtained by the reaction of a composition containing a radically polymerizable monomer component (M). The monomer component (M) preferably contains a vinyl monomer, more preferably 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 only, or of two or more types.

[0027] The content of polymer (P) in the resin microparticles according to an embodiment of the present invention is preferably 60% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, even more preferably 80% by mass to 100% by mass, still more preferably 90% by mass to 100% by mass, particularly preferably 95% by mass to 100% by mass, and most preferably 98% by mass to 100% by mass, in order to further enhance the effects of the present invention.

[0028] The crosslinkable monomer (a) has two or more double bonds in the molecule. Any appropriate crosslinkable monomer can be used as the crosslinkable monomer (a) as long as it has crosslinkability (has two or more double bonds in the molecule) and does not impair the effects of the present invention. Examples of the crosslinkable monomer (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, pentacontahexaethylene glycol di(meth)acrylate, 1,3-butylene di(meth)acrylate, allyl (meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetraacrylate, and neopentyl glycol di(meth)acrylate. In order to more effectively exhibit the effects of the present invention, the crosslinkable monomer (a) is preferably an aromatic crosslinkable monomer having an aromatic functional group and two or more radically polymerizable double bonds in the skeleton, such as divinylbenzene, divinylnaphthalene, etc., and more preferably divinylbenzene. The crosslinkable monomer (a) may be used alone or in combination of two or more.

[0029] As the aromatic monofunctional monomer (b), any appropriate aromatic monofunctional monomer can be used as long as it has a molecular structure having an aromatic functional group and one radically polymerizable double bond in the skeleton, as long as the effects of the present invention are not impaired. Examples of the aromatic monofunctional monomer (b) include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, t-butylstyrene, ethylvinylbenzene, vinylnaphthalene, styrene sulfonic acid, styrene sulfonate, vinylbenzoic acid, and vinylphenol. Examples of styrene sulfonate include sodium styrene sulfonate and ammonium styrene sulfonate. Examples of vinylbenzoic acid include o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid. Examples of vinylphenol include o-vinylphenol, m-vinylphenol, and p-vinylphenol. In order 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 alone 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% by mass to 100% by mass, more preferably 80% by mass to 100% by mass, even more preferably 90% by mass to 100% by mass, and particularly preferably 95% by mass to 100% by mass, in order to further exhibit the effects of the present invention.

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

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

[0033] The monomer component (M) may contain any other appropriate radical polymerizable monomer (m) different from the above-mentioned crosslinkable monomer (a) and monofunctional monomer (b) within the scope that does not impair the effects of the present invention. Therefore, 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 other radical polymerizable monomers (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, methyl ... isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, isostearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, and the like. (Meth)acrylic acid alkyl esters having 1 to 20 carbon atoms in the alkyl group bonded to the ester; (meth)acrylic acid esters having an alicyclic structure in the ester moiety 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 succinate, 2-methacryloyloxyethyl phthalate, and 2-methacryloyloxyethyl hexahydro Carboxy group-containing monomers such as phthalic acid, 2-methacryloyloxyethyl maleate, 2-acryloyloxyethylhexahydrophthalic 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; epoxy group-containing monomers such as 1,2-epoxy-4-vinylcyclohexane and (3,4-epoxycyclohexyl)methyl (meth)acrylate;Examples of the other radical polymerizable monomers (m) include acrylamide derivative monomers such as 4-vinylphenylglycidyl ether (meth)acrylamide; (meth)acrylonitrile-based monomers, halogenated vinyl-based monomers such as vinyl chloride; vinyl carboxylate-based monomers such as vinyl acetate; olefin-based monomers such as ethylene; unsaturated imide-based monomers; vinyl alcohol; and silane coupling agents having a vinyl group. The other radical polymerizable monomers (m) may be of one type or two or more types. The monomer component (M) may not contain other radical polymerizable monomers (m).

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

[0036] The content of the 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, so as to more effectively exhibit the effects of the present invention. If the content of the monomer component (M) in the composition is too low and outside the above range, the effects of the present invention may not be exhibited, and for example, excellent dielectric properties may not be exhibited. Here, the monomer component (M) does not include the polymerization initiator and surfactant 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 the aromatic monofunctional monomer (b), structural units derived from the crosslinkable monomer (a), and structural units derived from the reactive surfactant (A), and may have structural units derived from the crosslinkable monomer (a), structural units derived from the aromatic monofunctional monomer (b), structural units derived from other radical polymerizable monomers (m), and structural units derived from the reactive surfactant (A).

[0038] The reactive surfactant (A) typically has one or more double bonds in the molecule. Examples of the reactive surfactant (A) include anionic reactive surfactants and nonionic reactive surfactants.

[0039] Examples of anionic reactive surfactants include JS-20 or RS-3000 from Sanyo Chemical Industries, Ltd.'s Eleminol (registered trademark), 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 from Daiichi Kogyo Seiyaku Co., Ltd.'s Aqualon (registered trademark), Antox (registered trademark) MS-60 from Nippon Nyukazai Co., Ltd., S-120, S-180A, S-180, or PD-104 from Kao Corporation's Latemul (registered trademark), and SR-1025 or SE-10N from ADEKA Corporation's Adeka Reasoap (registered trademark). From the viewpoint of improving the dispersibility of resin microparticles, anionic reactive surfactants having an oxyalkylene chain in the molecular chain are preferred.

[0040] Examples of nonionic reactive surfactants include alkyl ether surfactants (commercially available products include Adeka Reasoap ER-10, ER-20, ER-30, and ER-40 manufactured by ADEKA Corporation, and Latemul PD-420, PD-430, and PD-450 manufactured by Kao Corporation); alkyl phenyl ether surfactants or alkyl phenyl ester surfactants (commercially available products include Aqualon RN-10, RN-20, RN-30, RN-50, AN-10, AN-20, AN-30, and AN-5065 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.; and Adeka Reasoap NE-10, NE-20, NE-30, and NE-40 manufactured by ADEKA Corporation); and (meth)acrylate sulfate ester surfactants (commercially available products include RMA-564, RMA-568, and RMA-1114 manufactured by Nippon Nyukazai Co., Ltd.). From the viewpoint of dispersion stability of the resin particles, the nonionic reactive surfactant preferably has an oxyalkylene chain in the molecular chain.

[0041] The content of the reactive surfactant (A) in the composition is preferably 0 to 10 parts by mass, more preferably more than 0 to 8 parts by mass, even more preferably more than 0 to 5 parts by mass, particularly preferably more than 0 to 3 parts by mass, and most preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the monomer component (M) (the total of the crosslinkable monomer (a), the aromatic monofunctional monomer (b), and the other radically polymerizable monomer (m)), in order to better exhibit the effects of the present invention. 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 deteriorated, making it impossible to obtain resin microparticles.

[0042] <<Uses of resin microparticles>> Resin microparticles according to embodiments of the present invention can be used in a variety of applications. Because they can further utilize the effects of the present invention, resin microparticles according to 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 components, paint additives, and ink additives. In particular, resin microparticles according to embodiments of the present invention have a small particle size, reduced metal components and eluted ionic components, and excellent dielectric properties. Therefore, it is possible to fabricate small or thin semiconductor components containing a sufficient amount of resin microparticles, thereby preventing ion migration and achieving improved dielectric properties.

[0043] <<Method for producing resin microparticles>> The resin microparticles according to the embodiment of the present invention can be produced, for example, by emulsion polymerization of the above-mentioned monomers.

[0044] The method for producing resin microparticles according to an embodiment of the present invention typically includes two-stage polymerization steps: a first polymerization step and a second polymerization step. In the first polymerization step, a radically polymerizable monomer component (M1) containing a monofunctional monomer (b1) is emulsion-polymerized. In the second polymerization step, a radically polymerizable monomer component (M2) containing a monofunctional monomer (b2) and a crosslinkable monomer (a) is emulsion-polymerized.

[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 then a polymerization initiator that is soluble in the medium is added to the mixture 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, it is possible to manufacture resin microparticles that have reduced metal components and eluted ion components and have excellent dielectric properties.

[0047] The first polymerization step and the second polymerization step are preferably carried out in a single reactor, more preferably continuously 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, typically, a monomer component (M1) containing a monofunctional monomer (b1) is emulsion polymerized to produce a crude product containing a polymer, which is typically used as seed particles in the second polymerization step.

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

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

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

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

[0053] (surfactant) The surfactant used in the first polymerization step may be any appropriate surfactant as long as it does not impair the effects of the present invention. The surfactant may be one type or two or more types. To further enhance the effects of the present invention, the surfactant preferably contains a reactive surfactant. Examples of the reactive surfactant include anionic reactive surfactants and nonionic reactive surfactants. Examples of the anionic reactive surfactant include the anionic reactive surfactants listed as the reactive surfactant (A) in the <Polymer P> section of the above-mentioned <<Resin Particles>>. Examples of the nonionic reactive surfactant include the nonionic reactive surfactants listed as the reactive surfactant (A) in the <Polymer P> section of the above-mentioned <<Resin Particles>>. It is preferable that the surfactant does not contain a non-reactive surfactant.

[0054] In the first polymerization step, it is preferable not to use any other emulsifying aids other than the reactive surfactant.

[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, relative to 100 parts by mass of the monomer component (M1) in the first polymerization step.

[0056] (Polymerization initiator) The polymerization initiator used in the first polymerization step may be any appropriate 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 the polymerization initiator. 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] Examples of the polymerization initiator include 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 (trade names "VA-061" and "VA-044"), 2,2'-azobis[2-methyl-N- (2-hydroxyethyl)propionamide] (trade name "VA-086"), 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide} (trade name "VA-080"), 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide} (trade name "VA-082"), 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide} (trade name "VA-084"), 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide} (trade name "VA-085"), 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide} (trade name "VA-086 ... water-soluble azo compounds such as N-[2-(1-hydroxybutyl)]-propionamide} (trade name "VA-085") (both 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)hexyne-3, bis(tert-butylperoxyisopropyl)benzene, bis(tert-butylperoxy)trimethylcyclohexane, butyl-bis(tert-butylperoxy)valerate, tert-butyl 2-ethylhexaneperoxyate, dibenzoyl peroxide, paramenthane hydroperoxide, and tert-butyl peroxybenzoate;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( 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-carbonitrile), 2-(carbamoylazo)isobutyronitrile, and 4,4'-azobis(4-cyanopentanoic acid); Alternatively, a redox initiator may be used as the polymerization initiator, which is a combination of the above-mentioned persulfate and organic peroxide polymerization initiator with a reducing agent such as sodium sulfoxylate formaldehyde, sodium hydrogen sulfite, ammonium hydrogen sulfite, sodium thiosulfate, ammonium thiosulfate, hydrogen peroxide, sodium hydroxymethanesulfinate, L-ascorbic acid or a salt thereof, a cuprous salt, or a ferrous salt. Among these, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]n hydrate (trade name "VA-057"), 4,4'-azobis(4-cyanovaleric acid) (trade name "V-501"), 2,2'-azobis[2-(2-imidazolin-2-yl)propane] (trade name "VA-061"), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl) )propionamide] (trade name "VA-086"), 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide} (trade name "VA-080"), 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide} (trade name "VA-082"), 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide} (trade name "VA-084"), 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide} (trade name "VA-085"), 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide} (trade name "VA-086 ... It is preferable to use one or more compounds selected from the group consisting of water-soluble azo compounds such as {-[2-(1-hydroxybutyl)]-propionamide} (trade name "VA-085") (both 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-carbonitrile), 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 reduces the total content of component A and the total amount of eluted ionic component B in the resin microparticles. These polymerization initiators may be used alone or in combination of two or more.

[0058] The amount of the 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, relative to 100 parts by mass of the monomer component (M1) in the first polymerization step.

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

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

[0061] <Second polymerization step> In the second polymerization step, emulsion polymerization is carried out using a composition containing the radically polymerizable monomer component (M2). The composition typically contains a liquid medium, the 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 carry out polymerization by adding a composition containing the monomer component (M2) to the polymer (seed particles) obtained in the first polymerization step.

[0063] Seeded emulsion polymerization is a method in which a polymer is used as seed particles and a water-soluble polymerization initiator is used to grow the seed particles while polymerizing a monomer. That is, seeded emulsion polymerization is an emulsion polymerization in which a liquid medium, a monomer component that is poorly soluble in the medium, and a surfactant are mixed in the presence of seed particles made of a polymer, and a polymerization initiator that is soluble in the medium is added to carry out polymerization.

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

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

[0066] (Crosslinking monomer) The crosslinkable monomer (a) is the same as the crosslinkable monomer (a) exemplified in <Polymer P> in the above-mentioned <<Resin Fine Particles>>. The crosslinkable monomer (a) may be used alone or in combination of two or more.

[0067] (monofunctional monomer) The monofunctional monomer (b2) is preferably an aromatic monofunctional monomer. Examples of the aromatic monofunctional monomer include the monofunctional monomers listed as the aromatic monofunctional monomer (b) in the section <<Polymer P>> of the above-mentioned <<Resin Fine Particles>>. 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 alone or in combination of two or more.

[0068] The total content of the crosslinkable monomer (a) and the monofunctional monomer (b2) in the monomer component (M2) is preferably 50% by mass to 100% by mass, more preferably 80% by mass to 100% by mass, even more preferably 90% by mass to 100% by mass, particularly preferably 95% by mass to 100% by mass, and most preferably 98% by mass to 100% by mass, in order to further exhibit 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 also the same as that described in the first polymerization step. In the production method according to an embodiment of the invention, the liquid medium is preferably an aqueous medium, and for example, water, a lower alcohol such as methyl alcohol or ethyl alcohol, a mixture of water and a lower alcohol, etc. can be used.

[0070] The amount of the liquid medium used may be any appropriate amount as long as it does not impair the effects of the present invention. The amount of the medium at the start of the second polymerization step (for example, the total amount of the medium used in the first and second polymerization steps) is preferably 10 to 5,000 parts by mass, more preferably 50 to 3,000 parts by mass, even more preferably 100 to 2,000 parts by mass, and particularly preferably 120 to 1,000 parts by mass, per 100 parts by mass of the total amount of the monomer components (M1) and (M2).

[0071] (surfactant) Any appropriate surfactant may be used in the second polymerization step as long as it does not impair the effects of the present invention. The surfactants described in the first polymerization step can be used in the second polymerization step. The surfactant may be one type or two or more types. In order to further demonstrate the effects of the present invention, it is preferable that the surfactant contains a reactive surfactant.

[0072] When a surfactant is used in the second polymerization step, the amount of the 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, relative to 100 parts by mass of the total amount of the monomer components (M1) and (M2).

[0073] The total amount of surfactants used in the production method according to an 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, relative to 100 parts by mass of the total amount of monomer component (M1) and monomer component (M2).

[0074] A reactive surfactant is preferably used in at least one selected from the first polymerization step and the second polymerization step, i.e., at least one selected from the composition containing the monomer component (M1) in the first polymerization step and the composition containing the monomer component (M2) in the second polymerization step preferably contains a reactive surfactant.

[0075] In the first and second polymerization steps, a non-reactive surfactant may be used as long as it does not impair the effects of the present invention. However, it is preferable that a non-reactive surfactant is not used. That is, the composition containing the monomer component (M1) in the first polymerization step and the composition containing the monomer component (M2) in the second polymerization step preferably contain a reactive surfactant. Examples of non-reactive surfactants include anionic non-reactive surfactants such as sodium oleate; fatty acid soaps such as castor oil potassium soap; alkyl sulfate ester salts such as sodium lauryl sulfate and ammonium lauryl sulfate; alkyl benzene sulfonates such as sodium dodecyl benzene sulfonate; alkyl naphthalene sulfonates; alkanesulfonates; dialkyl sulfosuccinates; alkyl phosphate ester salts; naphthalene sulfonate-formalin condensates; polyoxyethylene alkyl phenyl ether sulfate ester salts; polyoxyethylene sulfonated phenyl ether phosphate; polyoxyethylene alkyl ether phosphate; and polyoxyethylene alkyl sulfate ester salts. Examples of the surfactant include nonionic reactive surfactants such as sialic acid tridecyl ether, polyoxyethylene isodecyl ether, polyoxyalkylene lauryl ether, polyether polyol, polyoxyethylene styrenated 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 appropriate radical polymerization initiator as long as 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 ranges are the same as those 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 selected from the first polymerization step and the second polymerization step, a water-soluble azo compound is preferably used as the polymerization initiator.

[0078] The amount of the 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, relative to 100 parts by mass of the total amount of the monomer components (M1) and (M2).

[0079] The total amount of polymerization initiators used in the production method according to an 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, relative to 100 parts by mass of the total amount of the monomer component (M1) and the monomer component (M2).

[0080] The polymerization temperature in the second polymerization step may be any suitable temperature suitable for emulsion polymerization, as long as it does not impair the effects of the present invention. Such a polymerization temperature is preferably 30°C to 120°C, and more preferably 50°C to 100°C. The polymerization temperature in the second polymerization step may be, for example, 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 for the second polymerization step can be any suitable time suitable for emulsion polymerization, as long as it does not impair the effects of the present invention. The polymerization time is preferably 1 hour to 48 hours, more preferably 1 hour to 24 hours, at the initial polymerization temperature.

[0082] <Other processes> After the second polymerization step, the particles may be washed, classified, dried, etc., if necessary. [Example]

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

[0084] <Volume average particle size> The volume-average particle diameter of the resin microparticles was measured using a laser diffraction / scattering particle size distribution analyzer (Beckman Coulter, "LS 13 320"). A dispersion of resin microparticles was subjected to measurement to obtain the volume-based particle size distribution of the resin microparticles and its standard deviation. The arithmetic mean diameter in the obtained volume-based particle size distribution was taken as the volume-average particle diameter of the resin microparticles. The measurement conditions for the laser diffraction / scattering particle size distribution analyzer were as follows: Sample dispersion module: Universal Liquid Module Medium: Ion-exchanged water Refractive index of medium: 1.333 Refractive index of sample: Refractive index of resin particles The refractive index of the resin particles was determined by averaging the refractive indices of the homopolymers of the monomers used in the production, weighted by the amount of each monomer used.

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

[0086] <Proportion of particles with a diameter of 10 μm or more> The proportion of particles with a particle size of 10 μm or more was measured using a Coulter Multisizer TM Measurements were performed using a Multisizer 4e (a measuring device manufactured by Beckman Coulter, Inc.). TM This shall be performed with an aperture calibrated in accordance with the 4e User's Manual. The aperture used for measurement is selected appropriately depending on the size of the resin microparticles to be measured. The current (aperture current) and gain are set appropriately depending on the size of the selected aperture. For example, if an aperture with a size of 50 μm is selected, the current (aperture current) is set to -800 and the gain is set to 4. The measurement sample was prepared by dispersing 0.1 g of resin particles in 10 ml of 0.1 wt % polyoxyethylene sorbitan monolaurate "Tween 20" aqueous solution using a touch mixer (Yamato Scientific Co., Ltd., "TOUCHMIXER MT-31") and an ultrasonic cleaner (Velvoclear Co., Ltd., "ULTRASONIC CLEANER VS-150") to prepare a dispersion. During the measurement, the beaker was gently stirred to prevent air bubbles from being introduced, and the measurement was stopped when 100,000 resin particles had been measured. The proportion of particles 10 μm or larger was confirmed in the volume-based particle size distribution obtained from the measurement results.

[0087] <Total content of ingredient A> (Measurement sample) The dispersion containing the resin microparticles was dried using a spray dryer (manufactured by Sakamoto Giken Co., Ltd., machine name: spray dryer, model: atomizer take-up method, model number: TRS-3WK) under the following conditions to prepare the measurement sample. (Spray dryer equipment conditions) Dispersion liquid containing resin particles supply rate: 25 mL / min Atomizer rotation speed: 12000 rpm Air volume: 2m 3 / min Inlet temperature (the inlet temperature of the inlet provided in the spray dryer through which the dispersion liquid containing resin fine particles is sprayed and introduced): 150°C Outlet temperature (outlet temperature of the outlet provided in the spray dryer from which dried particles are discharged): 70°C (Measurement method) The total content of component A was measured as follows. Approximately 1.0 g of the above-mentioned precisely weighed sample was heated at 500°C for 1 hour to incinerate it. 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. The test solution was subjected to ICP atomic emission spectrometry under the following conditions. The concentration of each measured element was determined from a calibration curve prepared in advance. The component amount of each measured element was calculated using the following formula. Component amount [ppm] = Measured element concentration [μg / mL] x 25 [mL] ÷ Sample amount [g] The total content (sum) of component A was calculated from the amount of each measured element. Here, elements whose measurement results were below the lower limit of quantification were not taken into consideration when calculating the total content of component A. In other words, the total content of component A was the sum of the amounts of elements above the lower limit of quantification. The lower limits of quantification for P and K were 0.5 ppm, and for the other elements, 0.3 ppm. (ICP measurement conditions) Measurement equipment: Shimadzu Corporation "ICPE-9000" multi-type ICP optical emission spectrometer Measured elements: Al, Ba, Ca, Cr, Cu, Fe, K, Mg, Mn, Na, P, S, Si, Sr, Zn Observation direction: Axial direction 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 Standard solutions for calibration curves: SPEX Corporation "XSTC-13" general-purpose mixed standard solution, 31 elements mixed (base 5% HNO3), approximately 10 mg / L each, and "XSTC-8" general-purpose mixed standard solution, 13 elements mixed (base H2O / trace HF), approximately 10 mg / L each. (ashing conditions) Measurement equipment: Microwave muffle furnace Phoenix large capacity type (manufactured by CEM) Ashing conditions: 500°C x 1 hour (sample weight = approx. 1.0 g)

[0088] <Total amount of eluted ion component B> (Measurement sample) The obtained resin microparticles were dried using a spray dryer under the same conditions as in the above <Total Content of Component A>, and this was used as a measurement sample. (Measurement method) The eluted ion component B was measured as follows. A 50 mL container was prepared, and approximately 50 mL of ion-exchanged water was poured into it and washed three times. Approximately 0.2 g of the measurement sample was precisely weighed into the washed 50 mL container. 1 mL of cleaning ethanol (Cleansolve P) was poured into the container and mixed well, and then 50 mL of ion-exchanged water was poured into the container 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 disc. This was used as the test solution for ion chromatography measurements. The standard solution was measured under the following measurement conditions to create a calibration curve. Next, the test solution was measured under the same conditions. The peak area value of each ion obtained from the chromatogram was used to determine the concentration of each measured ion in the measurement sample from the calibration curve. 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 ion component [ppm] = measured ion concentration [μg / mL] × 51 [mL] ÷ sample amount [g] The total amount (sum) of eluted ionic component B was calculated from the amount of eluted ionic component for each measured ion. Here, in calculating the total amount of eluted ionic component B, ions whose measurement results were below the lower limit of quantification were not taken into consideration. In other words, the total amount of eluted ionic component B was the sum of the amounts of eluted ionic components of ions above the lower limit of quantification. The lower limit of quantification was 2 ppm. (Ion chromatograph measurement conditions) Measuring device: Tosoh Corporation "IC-2001" Measurement ion: F - , Cl - , NO2 - , Br - , NO3 - , PO4 3- , SO4 2- Column: TOSOH "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 particles> (Measurement sample) The obtained resin microparticles were dried using a spray dryer under the same conditions as in the above <Total Content of Component A>, and this was used as a measurement sample. (Measurement method) The dielectric properties of the measurement sample were measured using an AET dielectric constant measuring device (ADMS01Nc series). Measurements were performed at a frequency of 10 GHz, at 23°C and a relative humidity of 51±1%. The relative permittivity and dielectric loss tangent of the resin microparticles were calculated based on perturbation theory using a resonator.

[0090] [Example 1] In a pressure-resistant polymerization reactor equipped with a stirrer, thermometer, and cooling mechanism, 240 parts by mass of ion-exchanged water and 0.03 parts by mass of Aqualon AR-1025 (Dai-ichi Kogyo Seiyaku Co., Ltd., 25% pure content) as a reactive surfactant were mixed to prepare a first aqueous phase. Next, 4 parts by mass of methyl methacrylate were added to the reactor, and nitrogen gas was blown in for 3 minutes. The reactor was then sealed and heated 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 as a polymerization initiator in 2 parts by mass of ion-exchanged water 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 vessel, 76 parts by weight of ion-exchanged water, 0.9 parts by weight of Aqualon AR-1025 as a reactive surfactant, and 0.36 parts by weight of 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]n hydrate as a polymerization initiator were mixed to prepare a second aqueous phase. Next, a mixture of 67 parts by weight of styrene and 9 parts by weight of divinylbenzene (NS Styrene Monomer, DVB-810) was added to the second aqueous phase, and the mixture was stirred at 8000 rpm for 10 minutes using a TK Homomixer (Primix Corporation) to obtain a monomer mixture. After the first polymerization step was completed, the monomer mixture was added to the reactor over a period of 3 hours. After the addition was complete, polymerization was continued at 60°C for 2 hours, and then the temperature was raised to 85°C and polymerization was continued 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 (openings 24 μm) screen to obtain a dispersion containing the resin fine particles of Example 1. The volume average particle diameter of the resin microparticles of Example 1 was 0.36 μm, and the coefficient of variation (CV value) of the volume average particle diameter was 14%. The resin microparticles of Example 1 had a particle ratio of particles having a particle diameter of 10 μm or more of 0% by volume. The measurement results of the total content of component A and the total amount of eluted ionic component B of the resin microparticles of Example 1 are shown in Table 1.

[0093] [Example 2] Resin fine particles of Example 2 were obtained in the same manner as in Example 1, except that the amount of Aqualon AR-1025 used in the first polymerization step was changed from 0.03 parts by mass to 2.5 parts by mass. The volume average particle diameter of the resin microparticles of Example 2 was 0.13 μm, and the coefficient of variation (CV value) of the volume average particle diameter was 19%. The resin microparticles of Example 2 had a particle ratio of particles having a particle diameter of 10 μm or more of 0% by volume. The measurement results of the total content of component A and the total amount of eluted ionic component B of the resin microparticles of Example 2 are shown in Table 1.

[0094] [Example 3] In a pressure-resistant polymerization reactor equipped with a stirrer, thermometer, and cooling mechanism, 240 parts by mass of ion-exchanged water and 0.01 parts by mass of Aqualon AR-1025 (Dai-ichi Kogyo Seiyaku Co., Ltd., 25% pure content) as a reactive surfactant were mixed to prepare a first aqueous phase. Next, 4 parts by mass of methyl methacrylate were added to the reactor, and nitrogen gas was blown in for 3 minutes. The reactor was then sealed and heated to 75°C. In a separate container, 0.04 parts by mass of 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] as a polymerization initiator was dissolved in 2 parts by mass of ion-exchanged water 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 vessel, 76 parts by weight of ion-exchanged water, 0.8 parts by weight of Aqualon AR-1025 as a reactive surfactant, and 0.36 parts by weight of 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] as a polymerization initiator were mixed to prepare a second aqueous phase. Next, a mixture of 54 parts by weight of styrene and 22 parts by weight of divinylbenzene (NS Styrene Monomer, DVB-810) was added to the second aqueous phase, and the mixture was stirred at 8000 rpm for 10 minutes using a TK Homomixer (Primix Corporation) to obtain a monomer mixture. After the first polymerization step was completed, the monomer mixture was added to the reactor over a period of 5 hours. After addition, the temperature was raised to 85°C and polymerization was carried out for 3 hours, and then 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 (openings 24 μm) screen to obtain a dispersion containing resin fine particles of Example 3. The volume average particle diameter of the resin microparticles of Example 3 was 0.58 μm, and the coefficient of variation (CV value) of the volume average particle diameter was 13%. The resin microparticles of Example 3 had a particle diameter of 10 μm or more of 0% by volume. The measurement results of the total content of component A and the total amount of eluted ionic component B of the resin microparticles of Example 3 are shown in Table 1.

[0097] [Example 4] The resin microparticles of Example 4 were obtained in the same manner as in Example 1, except that the reactive surfactant in the first polymerization step was changed from 0.03 parts by mass of Aqualon AR-1025 to 0.02 parts by mass of Eleminol JS-20 (manufactured by Sanyo Chemical Industries, Ltd., pure content 40%), and the reactive surfactant in the second polymerization step was changed from 0.9 parts by mass of Aqualon AR-1025 to 0.8 parts by mass of Eleminol JS-20 (manufactured by Sanyo Chemical Industries, Ltd., pure content 40%). The volume average particle diameter of the resin microparticles of Example 4 was 0.34 μm, and the coefficient of variation (CV value) of the volume average particle diameter was 13%. The resin microparticles of Example 4 had a particle ratio of particles having a particle diameter of 10 μm or more of 0% by volume. The measurement results of the total content of component A and the total amount of eluted ionic component B of the resin microparticles of Example 4 are shown in Table 1.

[0098] [Example 5] Resin microparticles of Example 5 were obtained in the same manner as in Example 1, except that in the second polymerization step, 9 parts by mass of divinylbenzene (NS Styrene Monomer, DVB-810) was changed to 9 parts by mass of neopentyl glycol dimethacrylate. The volume average particle diameter of the resin microparticles of Example 5 was 0.37 μm, and the coefficient of variation (CV value) of the volume average particle diameter was 14%. The resin microparticles of Example 5 had a particle ratio of particles having a particle diameter of 10 μm or more of 0% by volume. The measurement results of the total content of component A and the total amount of eluted ionic component B of the resin microparticles of Example 5 are shown in Table 1.

[0099] <Production Example 1> In a reactor equipped with a stirrer, thermometer, and cooling mechanism, 270 parts by weight of ion-exchanged water and 0.07 parts by weight of sodium styrene sulfonate as an emulsification aid were mixed to prepare an aqueous phase. Next, a mixture of 120 parts by weight of methyl methacrylate and 2.4 parts by weight of 1-octanethiol 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. Upon reaching 80°C, a polymerization initiator solution containing 0.05 parts by weight of potassium persulfate as a polymerization initiator dissolved in 10 parts by weight of ion-exchanged water was added. After that, nitrogen was purged again for 5 minutes, and the mixture was stirred at 80°C for 5 hours to allow for emulsion polymerization. The temperature was then raised to 100°C, maintained for 3 hours, and then cooled to prepare a resin particle-containing slurry. This was used as seed particles.

[0100] [Comparative Example 1] An aqueous phase was prepared by mixing 70 parts by weight of ion-exchanged water and 0.35 parts by weight of Eleminol JS-20 (a reactive surfactant) in a container. In a separate container, 61 parts by weight of styrene and 9 parts by weight of divinylbenzene (NS Styrene Monomer, DVB-810) were thoroughly mixed to prepare an oil phase. The oil phase was added to the aqueous phase and stirred at 8,000 rpm for 10 minutes using a TK Homomixer (Primix Corporation) to obtain a monomer mixture. A reactor equipped with a stirrer, thermometer, and cooling mechanism was charged with 220 parts by mass of ion-exchanged water and 33 parts by mass of the seed particles produced in Production Example 1. 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 ion-exchanged water. When the temperature inside the reactor reached 70°C, the polymerization initiator solution was charged. The monomer mixture was then charged into the reactor over 4 hours, and a polymerization reaction was carried out. 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 obtained dispersion was cooled and classified by passing it through a 400 Mesh screen, thereby obtaining a dispersion containing resin fine particles of Comparative Example 1. The resin fine particles of Comparative Example 1 had a volume average particle diameter of 0.38 μm, and the coefficient of variation of the volume average particle diameter was 15%.

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

[0102] [Table 1]

[0103] From the results in Table 1, the resin particulates obtained in Examples 1 to 5 had reduced total content of component A and total amount of eluted ionic component B, and had excellent dielectric properties.

[0104] The resin particles according to the embodiment of the present invention can be used for semiconductor members and the like.

Claims

1. the total content of component A 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. Resin fine particles. Component A: Al, Ba, Ca, Cr, Cu, Fe, K, Mg, Mn, Na, P, S, Si, Sr, and Zn Ion component B: fluoride ions, chloride ions, nitrite ions, bromide ions, nitrate ions, phosphate ions, and sulfate ions

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

3. a polymer (P) obtained by reaction of a composition containing a radical polymerizable monomer component (M), The resin particles according to claim 1 , wherein the monomer component (M) comprises a crosslinkable monomer (a) and an aromatic monofunctional monomer (b).

4. The resin fine particles according to claim 3 , wherein the crosslinkable monomer (a) comprises an aromatic crosslinkable monomer.

5. The resin fine particles according to claim 3 , wherein the composition contains a reactive surfactant (A).

6. The resin fine particles according to claim 1, having a volume average particle diameter of 0.05 μm or more and 2 μm or less.

7. 2. The resin fine particles according to claim 1, wherein the content of particles having a particle diameter of 10 μm or more is 0.01% by volume or less.

8. The resin fine particles according to claim 1 , which are in the form of a dry powder.

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

10. The resin fine particles according to claim 1 , which are used as an additive for electronic materials.

11. The resin fine particles according to claim 1 , which are used as an additive for optical materials.

12. The resin fine particles according to any one of claims 1 to 9, which are used as a paint additive.

13. The resin fine particles according to claim 1 , which are used as an ink additive.

14. A method for producing resin microparticles according to any one of claims 1 to 9, comprising: A two-stage polymerization consisting of a first polymerization step and a second polymerization step is carried out, In the first polymerization step, a radical polymerizable monomer component (M1) containing a monofunctional monomer (b1) is emulsion polymerized, In the second polymerization step, a radical polymerizable monomer component (M2) including a monofunctional monomer (b2) and a crosslinkable monomer (a) is emulsion-polymerized. A method for producing resin microparticles.

15. The method for producing resin microparticles according to claim 14, wherein the first polymerization step and the second polymerization step are carried out in a single reactor.

16. The method for producing resin microparticles according to claim 14, wherein a reactive surfactant is used in at least one selected from the first polymerization step and the second polymerization step.

17. The method for producing resin microparticles according to claim 14 , 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.

18. The method for producing resin microparticles according to claim 14, wherein a non-reactive surfactant is not used in the first polymerization step and the second polymerization step.

19. The method for producing resin microparticles according to claim 14 , wherein the monofunctional monomer (b2) in the second polymerization step includes an aromatic monofunctional monomer, and the crosslinkable monomer (a) includes an aromatic crosslinkable monomer.

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