Hollow resin particle and dispersion

Abstract

The hollow resin particles obtained in the embodiments of the present invention have a shell portion and a hollow portion surrounded by the shell portion. The shell portion comprises a polymer (P) obtained by reacting a monomer component (M) containing a crosslinking monomer. The crosslinking monomer content in the monomer component (M) is 40% to 100% by weight, and the average particle size is 0.1 μm to 1 μm. The thermal weight loss rate after heating at 350°C for 2 hours in a nitrogen atmosphere is less than 40%.

Description

[Technical Field]

[0001] This invention relates to a hollow resin particle and its uses. [Previous Technology]

[0002] In semiconductor components, in order to correspond to the high-frequency signals required for next-generation high-speed communications and to suppress transmission losses, it is necessary to have low dielectric constants or low dielectric loss tangents and to be thinner. Therefore, in order to achieve a low dielectric constant, a method of adding hollow resin particles composed of acrylic or styrene-based materials to semiconductor components is being investigated.

[0003] For example, regarding conventional hollow resin particles, a type of hollow resin particle has been reported, which is obtained by suspension polymerization of a polymerizable monomer containing a number of crosslinkable hydrocarbon monomers such as divinylbenzene with a hydrophobic solvent (Patent Document 1). However, in the semiconductor component market in recent years, research has been conducted on the miniaturization and high performance of electronic circuits. When using hollow resin particles to achieve the miniaturization of semiconductor components, it is necessary to reduce the size of the hollow resin particles.

[0004] Furthermore, regarding conventional hollow resin particles, a hollow polymer particle produced by seed polymerization has been reported (Patent Document 2). However, the hollow resin particles described in Patent Document 2 have a relatively low ratio of crosslinking monomers in the monomers being polymerized, raising concerns about their weak particle strength and fragility during processing. Additionally, due to the presence of acrylic acid, the dielectric loss tangent is high, resulting in insufficient heat resistance and making them unsuitable for the aforementioned applications. [Prior Art Documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2023-074651 [Patent Document 2] Japanese Patent Application Publication No. 2002-241448 [Summary of the Invention]

[0006] [Problem to be Solved by the Invention] When hollow resin particles are added to various semiconductor components, if the size of the hollow resin particles is unsuitable for the size of the semiconductor component, unevenness or other defects may occur in the substrate resin of the semiconductor component, potentially leading to a decrease in dielectric loss tangent or adhesion. Therefore, for the thinning of semiconductor components, hollow resin particles with an average particle size of less than 1 μm are required. Furthermore, conventional hollow resin particles may decompose when exposed to high temperatures for extended periods during substrate resin processing or use. Therefore, hollow resin particles with heat resistance are also required. Therefore, the present invention is made to solve the above-mentioned problems, and its main objective is to provide a hollow resin particle that has a small average particle size applicable to various components and excellent heat resistance unaffected by prolonged high-temperature environments. Furthermore, it provides an application for such a hollow resin particle. [Means for Solving the Problem]

[0007] [1] The hollow resin particles obtained in the embodiments of the present invention have a shell portion and a hollow portion surrounded by the shell portion, and the shell portion contains a polymer (P) obtained by reaction of a monomer component (M) containing a crosslinking monomer, wherein the crosslinking monomer content in the monomer component (M) is 40% to 100% by weight, the average particle size is 0.1 μm to 1 μm, and the thermal weight loss rate after heating at 350°C for 2 hours in a nitrogen atmosphere is less than 40%. [2] The hollow resin particles described in [1] above have a hollowness of 30% or more. [3] The hollow resin particles described in [1] or [2] above have a dielectric loss tangent of less than 0.0060 at a measurement frequency of 10 GHz. [4] The hollow resin particles described in [3] above have a dielectric loss tangent of less than 0.0030. [5] The hollow resin particles described in any one of [1] to [4] above, wherein the relative permittivity at a measurement frequency of 10 GHz is less than 2.0. [6] The hollow resin particles described in any one of [1] to [5] above, wherein the monomer component (M) contains a monofunctional monomer, and the content ratio of the monofunctional monomer in the monomer component (M) is 60% by weight or less. [7] The hollow resin particles described in any one of [1] to [6] above, when heated from 30°C to 300°C at 10°C / min in an air environment, have a thermal weight loss rate of 7.0% or less. [8] The hollow resin particles described in any one of [1] to [7] above are resin compositions that can be used in semiconductor components. [9] The dispersion obtained by the embodiments of the present invention contains the hollow resin particles described in any one of [1] to [8] above. [Effects of the Invention]

[0008] According to an embodiment of the present invention, a hollow resin particle is provided, having a shell portion and a hollow portion surrounded by the shell portion, and is applicable to various components with an average particle size of less than 1 μm, and has excellent heat resistance unaffected by long-term high-temperature environments. Furthermore, the use of such a hollow resin particle is also provided.

Implementation Method

[0009] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these embodiments.

[0010] When the term "(meth)acrylic acid" is used in this specification, it means "acrylic acid and / or methacrylic acid"; when the term "(meth)acrylate" is used, it means "acrylate and / or methacrylate"; when the term "(meth)acryl" is used, it means "acrylyl and / or methacryl".

[0011] 《1. Hollow Resin Particles》《1-1. Structure and Characteristics of Hollow Resin Particles》 The hollow resin particles obtained according to the embodiments of the present invention have a shell portion and a hollow portion surrounded by the shell portion, and the average particle size is 0.1 μm to 1 μm, and the thermal weight loss rate after heating at 350°C for 2 hours in a nitrogen atmosphere is less than 40%.

[0012] The term "hollow" here refers to the point that the effect of the present invention can be better demonstrated when the interior is filled with a substance other than resin, such as gas or liquid. It is more preferably the state of being filled with gas.

[0013] The hollow portion may be composed of a single hollow region, or it may be composed of a plurality of hollow regions or a porous structure. In the hollow resin particles obtained according to the embodiments of the present invention, the hollow portion is preferably a single hollow structure composed of a single hollow region. By having a single hollow portion, the resin component constituting the shell portion is relatively more abundant, and even if it coexists with and is mixed with inorganic particles in the resin composition, the shell portion can become less prone to breakage. Furthermore, by having a single hollow portion, the penetration of substrates and the like into the hollow portion can be effectively prevented.

[0014] By having an average particle size of 0.1 μm to 1 μm, the hollow resin particles can be used in resin compositions for a wide variety of applications. Hollow resin particles with such an average particle size are, for example, suitable for thinning semiconductor components. The average particle size of the hollow resin particles is preferably 0.1 μm to 0.9 μm, more preferably 0.15 μm to 0.8 μm, even more preferably 0.2 μm to 0.7 μm, and particularly preferably 0.3 μm to 0.6 μm. The effects of the present invention are more pronounced when the average particle size of the hollow resin particles is within the above range. When the average particle size of the hollow resin particles is less than 0.1 μm, the thickness of the shell portion becomes relatively thin, and therefore the hollow resin particles may not have sufficient strength. When the average particle size of the hollow resin particles is greater than 1 μm, the applications of resin compositions using the hollow resin particles are limited. Furthermore, when the average particle size of hollow resin particles is greater than 1 μm, there is a risk that the polymer produced by the polymerization of monomer components in suspension polymerization may not be easily separated from the solvent phase, thus making it difficult to form the shell.

[0015] The average particle size of the hollow resin particles obtained according to the embodiments of the present invention is preferably 100 nm to 900 nm, more preferably 200 nm to 800 nm, even more preferably 300 nm to 700 nm, and particularly preferably 400 nm to 600 nm. The effects of the present invention are further demonstrated when the average particle size of the hollow resin particles obtained according to the embodiments of the present invention is within the above-mentioned range.

[0016] Furthermore, the hollow resin particles obtained according to the embodiment of the present invention have a thermal weight loss rate (hereinafter referred to as "thermal weight loss rate at 350°C for 2 hours") of less than 40% after heating in a nitrogen environment at 350°C for 2 hours. Thus, because the hollow resin particles obtained according to the embodiment of the present invention have a low thermal weight loss rate after prolonged exposure to high temperatures, the decomposition of the particles obtained in a high-temperature environment is suppressed. Therefore, the hollow resin particles obtained according to the embodiment of the present invention have excellent heat resistance.

[0017] The hollow resin particles obtained according to the embodiments of the present invention preferably have a thermal weight loss rate of less than 35% after 2 hours at 350°C, more preferably less than 30%, even more preferably less than 25%, and most preferably less than 20%. The lower limit of the thermal weight loss rate after 2 hours at 350°C is preferably 0%.

[0018] The thermal weight loss rate (hereinafter referred to as "thermal weight loss rate at 300°C") of the hollow resin particles obtained according to the embodiments of the present invention when heated from 30°C to 300°C at a rate of 10°C / minute in an air environment is preferably 7.0% or less, more preferably 6.7% or less, even more preferably 6.0% or less, and particularly preferably 5.5% or less. The lower limit of the thermal weight loss rate at 300°C is preferably 0%.

[0019] The hollow resin particles obtained according to the embodiments of the present invention typically have a hollowness ratio of 30% or more, preferably more than 30% to 80%, more preferably 31% to 75%, even more preferably 33% to 73%, and particularly preferably 35% to 71%. Hollow resin particles with a hollowness ratio within the above range exhibit superior dielectric properties. Depending on the specific circumstances, the hollow resin particles obtained according to the embodiments of the present invention may have a hollowness ratio of 60% or less, 55% or less, 50% or less, and more preferably 45% or less.

[0020] The hollow resin particles obtained according to the embodiments of the present invention preferably have a relative permittivity of less than 2.0 at a frequency of 10 GHz, more preferably less than 1.9, even more preferably less than 1.8, and most preferably less than 1.7. If the relative permittivity at a frequency of 10 GHz is within the above range, the hollow resin particles obtained according to the embodiments of the present invention exhibit excellent low dielectric properties. For example, the lower limit of the relative permittivity at a frequency of 10 GHz for the hollow resin particles obtained according to the embodiments of the present invention is 1.1.

[0021] The hollow resin particles obtained according to the embodiments of the present invention preferably have a dielectric loss tangent of less than 0.0060 at a frequency of 10 GHz, more preferably less than 0.0055, even more preferably less than 0.0050, further preferably less than 0.0045, particularly preferably less than 0.0040, and most preferably less than 0.0030. When the dielectric loss tangent at a frequency of 10 GHz is within the above range, the hollow resin particles obtained according to the embodiments of the present invention exhibit excellent low dielectric properties. For example, the lower limit of the dielectric loss tangent at a frequency of 10 GHz for the hollow resin particles obtained according to the embodiments of the present invention is 0.0001.

[0022] The amount of metal residue in the hollow resin particles obtained according to the embodiments of the present invention is generally 30 ppm or less. If the amount of metal residue in the hollow resin particles exceeds 30 ppm, there is a risk that the excellent low dielectric properties may not be exhibited, or that the low dielectric properties may not be uniform. Furthermore, if the amount of metal residue in the hollow resin particles exceeds 30 ppm, it can also be a cause of corrosion. Preferably, the amount of metal residue in the hollow resin particles is 20 ppm or less, more preferably 10 ppm or less, and even more preferably 5 ppm or less.

[0023] 《1-2. Shell Part》 The shell part comprises a polymer (P) obtained by reacting a monomeric component (M) containing a crosslinking monomer, wherein the crosslinking monomer content in the monomeric component (M) is 40% to 100% by weight. By comprising a polymer (P) having such a structure in the shell part, the effects of the present invention can be demonstrated.

[0024] The polymer (P) may be only one type or two or more types.

[0025] The percentage of polymer (P) in the shell portion that can further demonstrate the effect of the present invention is preferably 60% to 100% by weight, more preferably 70% to 100% by weight, even more preferably 80% to 100% by weight, and especially preferably 90% to 100% by weight.

[0026] The monomer component (M) is preferably one that includes both crosslinking monomers and monofunctional monomers. Therefore, the polymer (P) is preferably obtained by polymerizing, for example, the monomer component (M) that includes both crosslinking monomers and monofunctional monomers, and has structural units derived from both crosslinking monomers and monofunctional monomers.

[0027] A polymer (P) can be defined as something obtained by the reaction of a monomeric component (M). This is because a polymer (P) becomes a polymer by the reaction of a monomeric component (M), so a polymer (P) cannot be directly identified by its structure. Furthermore, since there are almost impractical situations ("impossible / impractical situations"), it is reasonable to define a polymer (P) as a "matter" based on the definition of "obtained by the reaction of a monomeric component (M)".

[0028] Examples of crosslinking monomers include: polyfunctional (meth)acrylates such as ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and glycerol tri(meth)acrylate; polyfunctional acrylamide derivatives such as N,N'-methylenebis(meth)acrylamide and N,N'-ethylbis(meth)acrylamide; polyfunctional allyl derivatives such as diallylamine and tetraallyloxyethane; and aromatic crosslinking monomers such as divinylbenzene, divinylnaphthalene, diallyl phthalate, and divinylbiphenyl. To further demonstrate the effects of the present invention, aromatic crosslinking monomers are preferred, and divinylbenzene is more preferred. There may be only one type of crosslinking monomer, or there may be two or more types.

[0029] The content ratio of aromatic crosslinking monomers in the monomer component (M) is preferably 45% by weight or more, more preferably 50% by weight or more, even more preferably 55% by weight or more, preferably less than 100% by weight, more preferably 99% by weight or less, even more preferably 98% by weight or less, and may be 70% by weight or less depending on the situation. If the content ratio of aromatic crosslinking monomers in the monomer component (M) is within the above range, the effects of the present invention are more pronounced. If the content ratio of aromatic crosslinking monomers in the monomer component (M) is too low, the crosslinking density will be low, which may reduce the strength of the shell portion and the heat resistance of the particles.

[0030] Examples of monofunctional monomers include: aromatic monofunctional monomers such as styrene, α-methylstyrene, ethyl vinylbenzene, vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, vinylbiphenyl, and vinylnaphthalene; alkyl (meth)acrylates having 1 to 16 carbon atoms such as methacrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and cetyl (meth)acrylate; and hydrophilic monofunctional monomers as shown in formula (1) below. To further demonstrate the effects of the present invention, the monofunctional monomer is preferably selected from at least one of the group consisting of aromatic monofunctional monomers and hydrophilic monofunctional monomers. The monofunctional monomer preferably includes hydrophilic monofunctional monomers.

[0031]

[0032] In general formula (1), R1 represents H or CH3, R2 represents alkadiyl with 1 to 10 carbon atoms or alkenediyl with 2 to 10 carbon atoms, R3 represents single bond, alkadiyl with 1 to 10 carbon atoms, alkenediyl with 2 to 10 carbon atoms, or phenyl group, X represents single bond, ester bond, ether bond, or carbonyl group, n represents a number from 1 to 5, and n R2, X, and R3 groups are independent of each other.

[0033] The content of monofunctional monomers in the monomer component (M) is preferably 60% by weight or less, more preferably 55% by weight or less, and even more preferably 52% by weight or less, and may be 30% by weight or less, 25% by weight or less, or even 20% by weight or less, depending on the circumstances. The content of monofunctional monomers in the monomer component (M) is preferably 1% by weight or more, and more preferably 5% by weight or more.

[0034] Aromatic monofunctional monomers are preferably styrene and ethyl vinylbenzene. The monofunctional monomer may be only one type or two or more types.

[0035] The content ratio of aromatic monofunctional monomers in the monomer component (M) is preferably 60% by weight or less, more preferably 55% by weight or less, and even more preferably 52% by weight or less, and may be 30% by weight or less, 25% by weight or less, or even 20% by weight or less, depending on the situation. The content ratio of aromatic monofunctional monomers in the monomer component (M) is preferably 1% by weight or more, and more preferably 5% by weight or more. This allows for the production of hollow resin particles with excellent heat resistance.

[0036] In formula (1), R2 represents an alkyl group having 1 to 10 carbon atoms or an alkene group having 2 to 10 carbon atoms, wherein the alkyl group preferably has 2 to 6 carbon atoms, and more preferably 2 to 4 carbon atoms. The alkyl group can be any of a straight-chain, branched, or cyclic form. The alkene group preferably has 2 to 6 carbon atoms, and more preferably 2 to 4 carbon atoms. The alkene group can be any of a straight-chain, branched, or cyclic form.

[0037] Regarding R2, examples of alkyldiyl groups include: methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,2-diyl, propane-2,2-diyl, propane-1,3-diyl, 2-methylpropane-1,3-diyl, butane-1,3-diyl, butane-2,3-diyl, and butane-1,4-diyl. Examples of alkenyl groups include: ethylene-1,2-diyl, 1-propene-1,3-diyl, 2-butene-1,4-diyl, 1-methyl-1-butene-1,4-diyl, and 2-cyclohexene-1,4-diyl.

[0038] In general formula (1), R3 represents a single bond, an alkyl group having 1 to 10 carbon atoms, an alkene group having 2 to 10 carbon atoms, or a phenyl group. Preferably, the alkyl group has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms. The alkyl group can be linear, branched, or cyclic. Preferably, the alkene group has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms. The alkene group can be linear, branched, or cyclic.

[0039] Regarding R3, in the case of alkyldiyl groups, examples such as those mentioned above can be cited. Regarding R3, in the case of alkenediyl groups, examples such as those mentioned above can be cited.

[0040] In general formula (1), X represents a single bond, ester bond, ether bond, or carbonyl group. The ester bond system can be of the structure R2-O-CO-R3 or R2-CO-O-R3.

[0041] For example, the hydrophilic monofunctional monomers represented by general formula (1) include: 2-methacryloxyethyl succinic acid, 2-methacryloxyethyl hexahydrophthalic acid, 2-methacryloxyethyl maleic acid, 2-acryloxyethyl hexahydrophthalic acid, 2-acryloxyethyl succinic acid, and 2-acryloxyethyl phthalic acid.

[0042] For the hydrophilic monofunctional monomer shown in general formula (1), commercially available products may also be used. For example, commercially available products may be "Light Ester HO-MS(N)" manufactured by Kyoei Chemical Co., Ltd.

[0043] The content ratio of the hydrophilic monofunctional monomer in the monomer component (M) is preferably 10% by weight or less, more preferably 8.0% by weight or less, even more preferably 5.0% by weight or less, and particularly preferably 0.5% by weight to 5.0% by weight, in order to further enhance the effects of the present invention. If the content ratio of the hydrophilic monofunctional monomer in the monomer component (M) is within the above range, the effects of the present invention will be further enhanced.

[0044] The total content ratio of aromatic monofunctional monomers, aromatic crosslinking monomers and hydrophilic monofunctional monomers represented by general formula (1) in the monomer component (M) is preferably 80% to 100% by weight, more preferably 85% to 100% by weight, even more preferably 90% to 100% by weight, and especially preferably 95% to 100% by weight, in order to better demonstrate the effects of the present invention.

[0045] The monomer component (M) may contain any other suitable monomers in addition to crosslinking monomers and monofunctional monomers. There may be only one other monomer or two or more other monomers.

[0046] The monomer component (M) may include a compound (A) having an ether structure as shown in formula (2) and a free radical reactive group. Compound (A) reacts with the aforementioned crosslinking monomer or monofunctional monomer. When the monomer component (M) further includes compound (A), the polymer (P) includes the building blocks derived from the ether structure as shown in formula (2). The resin particles obtained according to the embodiments of the present invention exhibit the effects of the present invention by including such polymer (P).

[0047]

[0048] Regarding compound (A), any suitable compound may be used if it has the ether structure and free radical reactive group shown in formula (2) above, without impairing the effects of the present invention. For compound (A), polyphenylene ether is preferably an example of a compound that can further demonstrate the effects of the present invention. Polyphenylene ether is a reactive polyphenylene ether that reacts with the aforementioned crosslinking monomer or monofunctional monomer by means of a polymerization initiator, and is generally a modified polyphenylene ether having polymerizable double bonds at the ends of at least one of them. The modified polyphenylene ether preferably has polymerizable double bonds at both ends, and more preferably is a modified oligomer having low molecular weight difunctional groups based on polyphenylene ether. Here, "having difunctional groups" refers to functional groups having double bonds at both ends of the oligomer, or functional groups containing substituents with double bonds. From the point that it is easier to produce resin particles with softness and excellent heat resistance, it is preferable that the number average molecular weight Mn of the above-mentioned oligomers is 500 to 3500.

[0049] As a preferred example of such modified polyphenyl ether, the compounds shown in the following formula (3) can be cited.

[0050]

[0051] In formula (3), n1 and n2 are integers of 1 or more, and represent integers from 0 to 300 independently of each other, and L3 represents a divalent linker. L3 is preferably selected from the group consisting of alkyl, alkenyl, -O-, -CO-, -CS-, -SO-, and -SO2-, with alkyl being more preferred and isopropylidene (-C(CH3)2-) being even more preferred. For commercially available products of the compounds shown in formula (3), examples include the "Noryl (registered trademark)" series (Noryl (registered trademark) SA9000, etc.) (manufactured by SABIC). As mentioned above, the modified polyphenylene ether preferably has (meth)acrylic groups at both ends. That is, compound (A) is a polyphenylene ether that may have (meth)acrylic groups at both ends.

[0052] Another preferred example of modified polyphenyl ether is the compound shown in formula (4) below.

[0053]

[0054] In formula (4), n1 and n2 are integers from 0 to 300, with at least one of them being an integer greater than or equal to 1. Commercially available products of the compounds shown in formula (4) include, for example, the "OPE-2St" series (manufactured by Mitsubishi Gas Chemical) and the "DPPE-VBT50" (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.).

[0055] Other commercially available products of polyphenylene ethers include, for example, the "Iupiace (registered trademark)" series (manufactured by Mitsubishi Chemical Corporation) and the "Zylon (registered trademark)" series (manufactured by Asahi Kasei Corporation).

[0056] The housing portion may contain any other suitable components without impairing the effects of the present invention. For example, in addition to the polymer (P), the housing portion may also contain a non-crosslinked polymer. The non-crosslinked polymer may be only one type or may be two or more types. By including a non-crosslinked polymer, phase separation of polymeric droplets during suspension polymerization can be promoted, and uniform particles can be easily formed. As a result, excellent low dielectric properties or uniform low dielectric properties can be exhibited.

[0057] Regarding the non-crosslinked polymer, any suitable non-crosslinked polymer can be used without impairing the effects of the present invention. For such a non-crosslinked polymer, a preferred number-average molecular weight of 500 to 200,000 may be listed as, for example, at least one selected from the group consisting of paraffin, polyolefins, and styrene-based polymers. The shell portion may comprise a hydrocarbon resin. When using a non-crosslinked polymer with a number-average molecular weight less than 500, phase separation may not easily occur, thus making it difficult to form the shell portion. When using a non-crosslinked polymer with a number-average molecular weight greater than 200,000, the viscosity of the oil droplets increases, resulting in a larger average particle size, which may sometimes make it difficult to achieve phase separation between the polymer and the solvent generated by the polymerization of monomer components in suspension polymerization, thus making it difficult to form the shell portion.

[0058] The hydrocarbon resin may be only one type, or it may be two or more types. By including the hydrocarbon resin in the shell portion, it is easy to construct a particle structure having a shell portion and a hollow portion surrounded by the shell portion. Furthermore, by including the hydrocarbon resin in the shell portion, the effects of the present invention can be further demonstrated. The shell portion may contain 0 to 10 parts by weight of the hydrocarbon resin relative to 100 parts by weight of the polymer (P) and the hydrocarbon resin. In terms of further demonstrating the effects of the present invention, the ratio of the hydrocarbon resin to 100 parts by weight of the polymer (P) and the hydrocarbon resin is preferably 1 to 10 parts by weight, more preferably 1 to 8 parts by weight, even more preferably 2 to 8 parts by weight, particularly preferably 2 to 6 parts by weight, and most preferably 2 to 5 parts by weight. Alternatively, the hydrocarbon resin may be 1 to 5 parts by weight. If the ratio of the hydrocarbon resin is within the above range, the effects of the present invention can be further demonstrated. This allows for the creation of hollow resin particles with excellent dielectric properties and heat resistance.

[0059] Regarding hydrocarbon resins, any suitable compound may be used without impairing the effects of the present invention. Examples of hydrocarbon resins include: aliphatic / aromatic hydrocarbon resins, aromatic hydrocarbon resins, alicyclic hydrocarbon resins, and aliphatic hydrocarbon resins. The hydrocarbon resin is preferably selected from at least one of the group consisting of aliphatic / aromatic hydrocarbon resins, aromatic hydrocarbon resins, and aliphatic hydrocarbon resins; more preferably, it is selected from at least one of the group consisting of aliphatic / aromatic hydrocarbon resins and aromatic hydrocarbon resins; and even more preferably, it is an aliphatic / aromatic hydrocarbon resin. Based on the above, hollow resin particles with small average particle size and heat resistance can be achieved, and even hollow resin particles with excellent dielectric properties can be achieved. Therefore, when hollow resin particles are mixed with thermosetting resins to form a resin composition, even if the thermosetting resin containing the hollow resin particles is heated during molding or soldering, the hollow resin particles are not easily subjected to substantial changes, thus better exhibiting the dielectric properties desired for the resin composition. These hydrocarbon resins can be used alone or in combination of two or more.

[0060] Aliphatic / aromatic hydrocarbon resins refer to hydrocarbon resins copolymerized from aliphatic and aromatic hydrocarbons. Aliphatic / aromatic hydrocarbon resins are, for example, resins polymerized using styrene, vinyltoluene, indene, 1,3-pentadiene, etc. as main raw materials.

[0061] Aromatic hydrocarbon resins are resins polymerized using styrene, vinyltoluene, indene, etc. as main raw materials.

[0062] Alicyclic hydrocarbon resins are, for example, resins obtained by hydrogenating aliphatic / aromatic hydrocarbon resins or aromatic hydrocarbon resins.

[0063] The aliphatic hydrocarbon resin is a hydrocarbon resin obtained by polymerizing one or more aliphatic hydrocarbons with polymerizable unsaturated bonds.

[0064] In the case of paraffin wax, examples include: paraffin wax and liquid paraffin wax.

[0065] As far as polyolefins are concerned, examples include: polyethylene, polypropylene, polyalphaolefin, etc.

[0066] Examples of styrene-based polymers include: polystyrene, styrene-acrylonitrile copolymers, acrylonitrile-butadiene-styrene copolymers, and styrene-butadiene-styrene copolymers. Styrene-based polymers can be block copolymers or styrene-butadiene-styrene block copolymers.

[0067] The content of the non-crosslinked polymer in the housing portion is preferably 0% to 40% by weight, more preferably 1% to 30% by weight, and even more preferably 3% to 20% by weight, in order to better demonstrate the effects of the present invention. If the content of the non-crosslinked polymer in the housing portion is too high, there is a risk that the excellent low dielectric properties may not be exhibited, or that the uniform dielectric properties may not be exhibited.

[0068] "Method for Manufacturing Hollow Resin Particles" The hollow resin particles obtained according to the embodiments of the present invention can be manufactured by any suitable method without impairing the effects of the present invention.

[0069] The method for manufacturing hollow resin particles according to the embodiments of the present invention generally involves dispersing an oil phase containing a monomer component (M) with a crosslinking monomer and an organic solvent in an aqueous phase containing an aqueous medium and a surfactant, and then performing suspension polymerization. The monomer component (M) preferably contains a crosslinking monomer and a monofunctional monomer, more preferably it contains an aromatic crosslinking monomer and at least one selected from the group consisting of aromatic monofunctional monomers and hydrophilic monofunctional monomers.

[0070] The explanation regarding the monomer component (M) can be found in the aforementioned section on the shell.

[0071] The organic solvent may be one type or two or more types. Regarding the organic solvent, any suitable organic solvent may be used without impairing the effects of the present invention. Preferably, organic solvents with a boiling point below 100°C are listed. By using an organic solvent with a boiling point below 100°C, it is easier to remove solvent from the hollow portion of the obtained hollow resin particles, and manufacturing costs can be reduced.

[0072] Examples of organic solvents with a boiling point of less than 100°C include: heptane, hexane, cyclohexane, methyl acetate, ethyl acetate, methyl ethyl ketone, chloroform, and carbon tetrachloride.

[0073] The amount of organic solvent used can be any suitable amount without impairing the effects of the present invention. Such an amount is, for example, 10 to 60 parts by weight relative to 100 parts by weight of monomer component (M).

[0074] The oil phase preferably contains a polymerization initiator. The polymerization initiator may be one type or two or more. Regarding the polymerization initiator, any suitable polymerization initiator may be used without impairing the effects of the present invention.

[0075] Examples of polymerization initiators include: cumene hydroperoxide, di-tert-butyl peroxide, diisopropylphenyl peroxide, benzoyl peroxide, o-chlorobenzoyl peroxide, o-methoxybenzoyl peroxide, lauryl peroxide, 3,5,5-trimethylhexyl peroxide, dimethylbis(tert-butylperoxy)hexane, dimethylbis(tert-butylperoxy)hexyn-3, bis(tert-butylperoxyisopropyl)benzene, bis(tert-butylperoxy)trimethylcyclohexane, butyl-bis(tert-butylperoxy)valerate, 2-ethylhexane peroxy acid tert-butyl ester, dibenzoyl peroxide, p-menthane hydroperoxide, tert-butylperoxybenzoate, etc.; 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methyl... 2,2'-Azobis(2-isopropylbutyronitrile), 2,2'-Azobis(2,3-dimethylbutyronitrile), 2,2'-Azobis(2,4-dimethylbutyronitrile), 2,2'-Azobis(2-methylhexanonitrile), 2,2'-Azobis(2,3,3-trimethylbutyronitrile), 2,2'-Azobis(2,4,4-trimethylpentanonitrile), 2,2'-Azobis(2,4-dimethylpentanonitrile) Azo compounds include nitrile, 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile), 2,2'-azobis(4-ethoxy-2,4-dimethylpentanonitrile), 2,2'-azobis(4-n-butoxy-2,4-dimethylpentanonitrile), 1,1'-azobis(cyclohexane-1-formonitrile), 2-(aminomethoxyazo)isobutyronitrile, and 4,4'-azobis(4-cyanopentanoic acid).

[0076] The polymerization initiator may be a polymerization initiator with a 10-hour half-life temperature of 90°C or below.

[0077] The amount of polymerization initiator used is within the range that does not impair the effects of the present invention, and any suitable amount may be used. For such an amount, it is, for example, 0.1 to 5 parts by weight relative to 100 parts by weight of monomer component (M).

[0078] The oil phase system may contain non-crosslinked polymers. There may be only one type of non-crosslinked polymer or two or more types. The description of the non-crosslinked polymer system can be found in the section on "1-2. Shell Part" above.

[0079] In addition to the above-mentioned components, the oil phase system may contain any other suitable components without impairing the effects of the present invention. Such other components may be only one or more.

[0080] Examples of aqueous media include water and mixtures of water and lower alcohols (ethanol, isopropanol, etc., with 5 or fewer carbon atoms). Preferably, water is selected from at least one of the groups consisting of ion-exchanged water and distilled water.

[0081] The amount of aqueous medium used is within the range that does not impair the effects of the present invention, and any suitable amount can be used. Regarding such an amount, it is preferably 100 to 2000 parts by weight relative to 100 parts by weight of the oil phase, and more preferably 200 to 1000 parts by weight. By adjusting the amount of aqueous medium used to the above range, the dispersion stability of the monomers in polymerization is improved, and the formation of resin particle aggregates can be suppressed during polymerization.

[0082] The aqueous phase preferably contains a surfactant. Regarding the surfactant, any suitable surfactant may be used without impairing the effects of the present invention. There may be only one surfactant or two or more surfactants. Examples of such surfactants include: anionic surfactants, cationic surfactants, nonionic surfactants, and zwitterionic surfactants.

[0083] Examples of anionic surfactants include: sodium oleate; fatty acid soaps such as potassium castor oil soap; polysulfonates; polycarboxylate salts; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; alkyl aryl sulfonates; alkyl naphthalene sulfonates; alkane sulfonates; dialkyl sulfonates; dialkyl sulfosuccinates; alkyl phosphates; alkyl phosphate esters; sodium salts of β-naphthalene sulfonate formalin condensate and other naphthalene sulfonate formalin condensates or their salts; polyoxyethylene ethyl alkyl phenyl ether sulfates such as polyoxyethylene ethyl nonyl phenyl ether sulfates; polyoxyethylene ethyl sulfonated phenyl ether phosphates; polyoxyethylene ethyl alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate and polyoxyethylene ethyl lauryl ether sulfate; polyoxyethylene ethyl alkyl sulfates; polyoxyethylene ethyl alkyl phosphate sulfonates; glycerol borate fatty acid esters; polyoxyethylene ethyl glycerol fatty acid esters; phosphate ester surfactants; phosphite surfactants. Anionic surfactants can be one type or two or more. Furthermore, ammonium salts are preferred as the relative cationic groups of the anionic groups. Using such surfactants can reduce the amount of metal residue.

[0084] Examples of cationic surfactants include alkylamine salts such as laurylamine acetate and stearylamine acetate; and quaternary ammonium salts such as lauryltrimethylammonium chloride. There may be only one type of cationic surfactant, or there may be two or more types.

[0085] As for nonionic surfactants, examples include: (meth)acrylate sulfate surfactants (commercially available products, such as RMA-564, RMA-568, RMA-1114, etc. manufactured by Nippon Emulsifier Co., Ltd.); polyoxyalkyl branched decyl ethers; polyoxyethyl tridecyl ether, polyoxyethyl isodecanyl ether, polyoxyethyl lauryl ether, polyoxyethyl oleyl cetyl ether, etc.; polyoxyethyl naphthyl ether, polyoxyethyl phenyl ether, etc.; polyoxyalkyl alkyl aryl ethers; polyoxyalkyl alkyl aryl ethers; polyether polyols; polyoxyethyl styrene phenyl ether; polyoxyethyl polyoxypropylene glycol; isostearic acid polyoxyethyl glycerol; polyoxyethyl fatty acid esters; sorbitan fatty acid esters; polyoxysorbitan fatty acid esters; polyoxyethyl alkylamines; glycerol fatty acid esters; ethylene-propylene block polymers. Nonionic surfactants can be one type or two or more.

[0086] Examples of zwitterionic surfactants include lauryl dimethylamine oxide, alkyl diaminoethyl glycine hydrochloride, sodium lauryl aminopropionate, and alkyl betaine. There may be only one type of zwitterionic surfactant, or there may be two or more types.

[0087] Regarding the surfactant, a vinyl-containing reactive surfactant can be used. There may be only one vinyl-containing reactive surfactant, or there may be two or more. If a vinyl-containing reactive surfactant is used, it can be incorporated into the polymer (P), thus, in suspension polymerization, the surfactant can be effectively present on the particle surface, and the interfacial activity effect can be enhanced. Therefore, excellent interfacial activity effects can be obtained, the aggregation or agglomeration of particles can be suppressed during manufacturing, the generation of non-standard particles can be reduced, and more uniform low-dielectric properties can be exhibited.

[0088] Examples of reactive surfactants containing vinyl groups include anionic surfactants containing vinyl groups and nonionic surfactants containing vinyl groups.

[0089] Examples of anionic surfactants containing vinyl groups include: ammonium polyoxyethylene-1-(allyloxymethyl)alkyl ether sulfate, ammonium polyoxyethylene-styrene-propylene-phenyl ether sulfate, ammonium polyoxyethylene-alkylalkenyl ether sulfate, α-sulfonyl-ω-(1-alkoxymethyl-2-(2-propenyloxy)ethoxy)-poly(oxy-1,2-ethanediyl)ammonium, polyoxypropylene-allyl ether phosphate, and bis(polyoxyethylene-phenyl ether)methacrylate sulfate. Furthermore, the relative cationic form of the anionic group is preferably an ammonium salt. By using such surfactants, the average particle size of hollow resin particles can be further reduced. Additionally, the amount of metal residue can be reduced.

[0090] For commercially available polyoxyethylene-1-(allyloxymethyl)alkyl ether ammonium sulfate, examples include: the trade name "AQUALON KH-10" and the trade name "AQUALON KH-1025" (25% by weight aqueous solution of "AQUALON KH-10") manufactured by Daiichi Industrial Pharmaceutical Co., Ltd.

[0091] Commercially available products of polyoxyethylene styrene-propylene phenyl ether sulfate ammonium can be exemplified by, for example, the products manufactured by Daiichi Industrial Pharmaceutical Co., Ltd. under the trade names "AQUALON AR-10", "AQUALON AR-20", "AQUALON AR-3025" (25% aqueous solution of "AQUALON AR-30") and "AQUALON AR-1025" (25% aqueous solution of "AQUALON AR-10").

[0092] For commercially available polyoxyalkylene ether ammonium sulfate, an example can be cited: "LATEMUL PD-104" manufactured by Kao Corporation.

[0093] For commercially available α-sulfonyl-ω-(1-alkoxymethyl-2-(2-propenyloxy)ethoxy)-poly(oxy-1,2-ethanediyl)ammonium, examples include: "ADEKA REASOAP SR-10" and "ADEKA REASOAP SR-20" manufactured by ADEKA Co., Ltd.

[0094] As for commercially available polyoxypropyl allyl ether phosphate, examples include, for instance, the product "ADEKA REASOAP PP-70" manufactured by ADEKA Co., Ltd.

[0095] As for commercially available bis(polyoxyethylene ethyl phenyl ether) methacrylate sulfate, for example, is the product "ANTOX MS-60" manufactured by Japan Emulsifier Co., Ltd.

[0096] Examples of nonionic surfactants having vinyl groups include: polyoxyethylene styrene-propylene phenyl ether, polyoxyethylene-1-(allyloxymethyl)alkyl ether, and polyoxyethylene alkylalkenyl ether.

[0097] For commercially available polyoxyethylene styrene-propylene phenyl ether, examples include: the trade names "AQUALON AN-10", "AQUALON AN-20", "AQUALON AN-30", and "AQUALON AN-5065" manufactured by Daiichi Industrial Pharmaceutical Co., Ltd.

[0098] For commercially available polyoxyethylene-1-(allyloxymethyl)alkyl ethers, examples include: "AQUALON KN-10", "AQUALON KN-20", "AQUALON KN-30", "AQUALON KN-5065" manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., and "ADEKA REASOAP ER-10", "ADEKA REASOAP ER-20", "ADEKA REASOAP ER-30", "ADEKA REASOAP ER-40" manufactured by ADEKA Co., Ltd.

[0099] For commercially available polyoxyalkylene ethers, examples include: "LATEMUL PD-420", "LATEMUL PD-430" and "LATEMUL PD-450" manufactured by Kao Corporation.

[0100] The amount of surfactant used can be any suitable amount without impairing the effect of the present invention. With respect to such an amount, it is preferably 0.001 parts by weight to 5 parts by weight relative to 100 parts by weight of the oil phase, more preferably 0.005 parts by weight to 3 parts by weight, and even more preferably 0.01 parts by weight to 1 part by weight.

[0101] In addition to the above-mentioned components, the aqueous phase system may contain any other suitable components without impairing the effects of the present invention.

[0102] As for the method of mixing the oil phase and the aqueous phase, any suitable method may be used as long as suspension polymerization can be carried out without impairing the effect of the present invention.

[0103] The suspension is prepared by mixing an oil phase and an aqueous phase and stirring. Typically, the oil phase is dispersed in the aqueous phase. The dispersion of the oil phase in the aqueous phase can be achieved by any suitable dispersion method, provided that the oil phase exists in droplet form without impairing the effects of the invention. Commonly used dispersion methods include homogenization, such as ultrasonic homogenizers or high-pressure homogenizers.

[0104] Any suitable method may be used for suspension polymerization without compromising the effects of the present invention.

[0105] The polymerization temperature can be any suitable temperature as long as it is suitable for suspension polymerization and does not impair the effects of the present invention. Such a polymerization temperature is, for example, 30°C to 95°C.

[0106] The polymerization time can be any suitable time as long as it is suitable for suspension polymerization and does not impair the effects of the present invention. In this regard, a polymerization time of 1 hour to 20 hours is preferred.

[0107] It is preferable to perform a post-heating process after polymerization in order to obtain hollow resin particles with high finish.

[0108] The temperature at which post-heating is preferably performed after polymerization can be any suitable temperature without impairing the effects of the present invention. Preferably, the temperature for such post-heating is between 50°C and 120°C.

[0109] The subsequent heating time after polymerization can be any suitable time without impairing the effects of the present invention. Preferably, the subsequent heating time is 1 to 10 hours.

[0110] By the above polymerization, a slurry can be obtained, which is a dispersion containing microcapsule particles encapsulated with an organic solvent for use in the oil phase. Hollow resin particles can be obtained from the slurry obtained by suspension polymerization by distillation, solvent removal, washing, drying, classification, etc., as needed.

[0111] The hollow resin particles obtained according to embodiments of the present invention can be used as a dispersion as needed. Such a dispersion comprises the hollow resin particles obtained according to embodiments of the present invention and a dispersion medium, wherein the hollow resin particles obtained according to embodiments of the present invention are dispersed as a dispersed phase in the dispersion medium. For example, in the above manufacturing method, the dispersion of microcapsule particles containing organic solvent obtained after the polymerization step can be used directly, or it can be used as a solvent dispersion in which other dispersion media are substituted.

[0112] "Uses of Hollow Resin Particles" The hollow resin particles obtained according to embodiments of the present invention can be used in various applications. In terms of further utilizing the effects of the present invention, the hollow resin particles obtained according to embodiments of the present invention are suitable for semiconductor components, and are generally suitable for use in resin compositions for semiconductor components. Furthermore, in addition to the above-mentioned applications in resin compositions for semiconductor components, the hollow resin particles obtained according to embodiments of the present invention can also be used in coating compositions, heat-insulating resin compositions, light-diffusing resin compositions, light-diffusing films, and other applications that utilize the effects of the present invention.

[0113] 《Resin Composition for Semiconductor Components》 The hollow resin particles obtained according to the embodiments of the present invention have small particle size and heat resistance. For example, they are suitable for use in resin compositions for semiconductor components, in terms of the low dielectric properties that can be exhibited in thin-layer semiconductor components.

[0114] The resin composition system for semiconductor components obtained according to an embodiment of the present invention comprises hollow resin particles obtained according to an embodiment of the present invention. Such a resin composition system for semiconductor components is, for example, suitable for use as a sealing material for semiconductor wafers.

[0115] The term "semiconductor component" refers to a component that constitutes a semiconductor, such as a semiconductor package or a semiconductor module. In this specification, the term "resin composition for semiconductor components" refers to a resin composition used in semiconductor components.

[0116] A semiconductor packaging system is a component consisting of at least one of the following: an IC chip as an essential component, a molding resin, an underfill material, a molding underfill material, a die bond material, a prepreg for a semiconductor package substrate, a metal foil laminate for a semiconductor package substrate, and an additive material for a printed circuit board for a semiconductor package.

[0117] A semiconductor module is a device that uses a semiconductor package as an essential component and is constructed using at least one of the following components: prepreg for printed circuit boards, metal foil laminate for printed circuit boards, additive material for printed circuit boards, solder resist, coating film, electromagnetic wave shielding film, and bonding sheet for printed circuit boards.

[0118] 《Coating Composition》 The hollow resin particles obtained according to the embodiments of the present invention can impart an excellent appearance to the coating film contained therein, and are therefore suitable for use in coating composition.

[0119] Such a coating composition system comprises hollow resin particles obtained according to an embodiment of the present invention.

[0120] The coating composition preferably includes at least one selected from binder resins and UV-curing resins. The binder resin may be only one type or may be two or more types. The UV-curing resin may be only one type or may be two or more types.

[0121] Regarding the adhesive resin, any suitable adhesive resin may be used without impairing the effects of the present invention. Examples of such adhesive resins include: resins soluble in organic solvents or water, and emulsified aqueous resins dispersible in water. Specific examples of adhesive resins include: acrylic resins, alkyd resins, polyester resins, polyurethane resins, chlorinated polyolefin resins, and amorphous polyolefin resins.

[0122] Regarding the UV-curable resin, any suitable UV-curable resin may be used without impairing the effects of the present invention. Examples of such UV-curable resins include: polyfunctional (meth)acrylate resins and polyfunctional ethyl carbamate acrylate resins, with polyfunctional (meth)acrylate resins being preferred, and more preferably polyfunctional (meth)acrylate resins having three or more (meth)acrylic groups per molecule. For polyfunctional (meth)acrylate resins having three or more (meth)acrylic groups in one molecule, examples include: trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, 1,2,4-cyclohexanetetra(meth)acrylate, pentaglycerol triacrylate, neopentyltetra(meth)acrylate, neopentyltetra(meth)acrylate, dinepentyltetra(meth)acrylate, dinepentyltetra(meth)acrylate, dinepentyltetra(meth)acrylate, dinepentyltetra(meth)acrylate, dinepentyltetra(meth)acrylate, trinepentyltetra(meth)acrylate, and trinepentyltetra(meth)acrylate.

[0123] When the coating composition includes at least one selected from binder resin and UV-curing resin, the content ratio can be any suitable ratio depending on the purpose. Generally, relative to the total amount of at least one selected from binder resin (converted to solids in the case of emulsified waterborne resin) and UV-curing resin and hollow resin particles obtained according to the embodiments of the present invention, the hollow resin particles obtained according to the embodiments of the present invention are preferably 5% to 50% by weight, more preferably 10% to 50% by weight, and even more preferably 20% to 40% by weight.

[0124] When a UV-curable resin is used, it is preferable to use a photopolymerization initiator in conjunction. Regarding the photopolymerization initiator, any suitable photopolymerization initiator may be used to the extent that it does not impair the effects of the present invention. Examples of such photopolymerization initiators include: acetobenzene compounds, benzoin compounds, benzophenone compounds, phosphine oxides, ketals, α-hydroxyalkylphenols, α-aminoalkylphenols, anthraquinones, thioxanthones, azo compounds, peroxides (described in Japanese Patent Application Publication No. 2001-139663, etc.), 2,3-dialkyldione compounds, disulfide compounds, fluorinated amine compounds, aromatic strontium compounds, onium salts, borates, active halogen compounds, and α-acryloyl oxime esters.

[0125] The coating composition may contain a solvent. There may be only one solvent, or there may be two or more. When the coating composition obtained according to the embodiments of the present invention contains a solvent, the content ratio can be any suitable ratio depending on the purpose.

[0126] Regarding the solvent, any suitable solvent may be used without impairing the effects of the present invention. Preferably, the solvent is one that can dissolve or disperse the binder resin or UV-curable resin. Examples of suitable solvents for oil-based coatings include: hydrocarbon solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; and ether solvents such as dialkylene, ethylene glycol diethyl ether, and ethylene glycol monobutyl ether. Examples of suitable solvents for water-based coatings include: water and alcohols.

[0127] The viscosity of the coating composition may be adjusted as needed, and it may be diluted. As for the diluent, any suitable diluent may be used depending on the purpose. The aforementioned solvents may be used as examples of such diluents. There may be only one diluent or two or more diluents.

[0128] The coating composition system may contain other components as needed, such as: coating conditioner, flow conditioner, ultraviolet absorber, light stabilizer, hardening catalyst, extender pigment, coloring pigment, metallic pigment, mica powder pigment, dye.

[0129] When forming a coating film using a coating composition, any suitable coating method may be used depending on the purpose. Examples of such coating methods include: spray gun coating, roller coating, brush coating, reverse roller coating, gravure coating, stencil coating, corner-cut roller coating, and spray coating.

[0130] When forming a coating film using a coating composition, any suitable forming method may be adopted depending on the purpose. Examples of such forming methods include: forming a coating film by coating any surface of a substrate, drying the coating film, and then hardening the coating film as needed to form a coating film. Examples of substrates include: metals, wood, glass, plastics (PET (polyethylene terephthalate), PC (polycarbonate), acrylic resin, TAC (triacetylated cellulose), etc.).

[0131] Thermal Insulating Resin Composition: The hollow resin particles obtained according to embodiments of the present invention can impart excellent thermal insulation properties to coatings containing these particles, and are therefore suitable for use in thermal insulating resin compositions. Coatings containing the hollow resin particles obtained according to embodiments of the present invention exhibit excellent reflectivity in the wavelength range from ultraviolet to near-infrared light.

[0132] Such a heat-insulating resin composition system comprises hollow resin particles obtained according to an embodiment of the present invention.

[0133] The heat-insulating resin composition preferably includes at least one selected from binder resins and UV-curing resins. For binder resins and UV-curing resins, the description of the aforementioned coating composition can be used as a reference.

[0134] The heat-insulating resin composition may contain a solvent. For the solvent system, the description of the aforementioned coating composition can be referred to.

[0135] The viscosity of the heat-insulating resin composition is adjusted as needed, so it can be diluted. For the purpose of using a diluent, the description of the aforementioned coating composition can be referenced.

[0136] The heat-insulating resin composition may contain other components as needed, such as: coating conditioner, flow conditioner, ultraviolet absorber, light stabilizer, hardening catalyst, extender pigment, coloring pigment, metallic pigment, mica powder pigment, dye.

[0137] The coating method and the forming method when forming a coating film using a heat-insulating resin composition can be referred to in the description of the aforementioned coating composition.

[0138] 《Light-diffusing resin composition》 The hollow resin particles obtained according to the embodiments of the present invention can impart excellent light diffusivity to the coating containing the particles, and are therefore suitable for use in light-diffusing resin compositions.

[0139] Such a light-diffusing resin composition system comprises hollow resin particles obtained according to an embodiment of the present invention.

[0140] The diffusing resin composition preferably includes at least one selected from binder resins and UV-curing resins. For binder resins and UV-curing resins, the description of the aforementioned coating composition can be used as a reference.

[0141] The light-diffusing resin composition may contain a solvent. For solvent systems, the description of the aforementioned coating composition can be referenced.

[0142] The light-diffusing resin composition may be diluted to adjust its viscosity as needed. For the purpose of using a diluent, the description of the aforementioned coating composition can be referenced.

[0143] The light-diffusing resin composition may contain other components as needed, such as: coating conditioner, flow conditioner, ultraviolet absorber, light stabilizer, hardening catalyst, extender pigment, coloring pigment, metallic pigment, mica powder pigment, dye.

[0144] The description of the aforementioned coating composition can be used as a reference for the coating method and the formation method when using a light-diffusing resin composition to form a coating film.

[0145] 《Light Diffusion Film》 The hollow resin particles obtained according to the embodiments of the present invention can impart excellent light diffusion properties to a film having a coating containing these particles, and are therefore also suitable for use in light diffusion films.

[0146] Such a light diffusion film system comprises hollow resin particles obtained according to an embodiment of the present invention.

[0147] The light diffusion film system comprises a light diffusion layer formed from the aforementioned light diffusion resin composition and a substrate. Furthermore, the light diffusion layer may or may not be the outermost layer of the light diffusion film. The light diffusion film system obtained according to the embodiments of the present invention may contain any other suitable layers depending on the purpose. Examples of such other layers include: a protective layer, a hard coating layer, a planarization layer, a high refractive index layer, an insulating layer, a conductive resin layer, a conductive metal microparticle layer, a conductive metal oxide microparticle layer, and a base coating layer.

[0148] Examples of substrates include: metal, wood, glass, plastic film, plastic sheet, plastic lens, plastic panel, cathode ray tube, fluorescent display tube, and liquid crystal display panel. Examples of plastics constituting plastic film, plastic sheet, plastic lens, and plastic panel include: PET (polyethylene terephthalate), PC (polycarbonate), acrylic resin, and TAC (triacetylsalicylic acid cellulose). [Example]

[0149] Hereinafter, embodiments are listed to specifically illustrate the present invention, but the present invention is not limited to these embodiments.

[0150] <Average Particle Size> The Z-mean particle size of hollow resin particles is determined using dynamic light scattering, and the measured Z-mean particle size is taken as the average particle size of the obtained hollow resin particles. Specifically, firstly, the obtained slurry-like hollow resin particles or particles are diluted with ion-exchanged water, and a laser light is irradiated onto an aqueous dispersion adjusted to 0.1% by weight. The change in the intensity of the scattered light scattered by the hollow resin particles over time is measured in microseconds. Then, the detected scattering intensity distribution of the hollow resin particles is applied to a normal distribution, and the Z-mean particle size of the hollow resin particles or particles is determined by a cumulative analysis method used to calculate the average particle size. The determination of the Z-mean particle size can be easily performed using a commercially available particle size analyzer. In the following examples and comparative examples, a particle size analyzer (Malvern Zetasizer Nano ZS) was used to determine the Z-mean particle size. Typically, commercially available particle size analyzers are equipped with data analysis software that automatically analyzes the measurement data and calculates the Z-mean particle size.

[0151] <Hollowness Ratio> The hollowness ratio of the hollow resin particles is obtained from the apparent density of the hollow resin particles. The apparent density of the hollow resin particles is determined by a vibratory densitometer (manufactured by Anton Paar, trade name "DMA1001"). Specifically, the hollow resin particles are mixed with a dispersion medium (manufactured by Toa Synthetic Co., Ltd., trade name "Awatori RentaroARE-100") with a hollow resin particle ratio of 2% by weight using a degassing mixer (manufactured by Thinky Co., Ltd., trade name "ARUFON UP-1020", density 1.027 g / cm3 (25°C)) to prepare an evaluation mixture. The evaluation mixture is filled into the measuring cell of the vibratory densitometer, the vibration number of the mixture in the measuring cell is measured, and the density of the mixture is calculated from the following formula (5). According to the following formula (6), the apparent density of the hollow resin particles containing air is calculated from the density of the mixture and the dispersion medium and the weight ratio of each component in the mixture. In formula (5), f represents the vibration number [Hz], M represents the weight of the measuring cell [g], V represents the volume of the measuring cell [cm3], ρ represents the density of the sample filling the measuring cell [g / cm3], and c represents the spring constant [N / mm]. In formula (6), ρp represents the apparent density of the hollow resin particles [g / cm3], ρd represents the density of the dispersion medium [g / cm3], xp represents the weight ratio of the hollow resin particles in the sample, and xd represents the weight ratio of the dispersion medium in the sample. The hollowness ratio of the hollow resin particles is calculated from the apparent density and the density of the shell using the following formula: Hollowness ratio [%] = 100 - (100 × apparent density [g / cm3]) / density of the shell [g / cm3]

[0152] <Observation of the Presence and Shape of Hollow Parts> For the hollow resin particles as dry powder, surface treatment was performed using a Meiwafosis "Osmium Coater Neoc-Pro" coating apparatus (10 Pa, 5 mA, 10 seconds). Then, the hollow resin particles were observed using TEM (transmission electron microscope, Hitachi High Technologies H-7600) to confirm the presence and shape of the hollow parts. At this time, the accelerating voltage was set to 80 kV, and the magnification was set to 5000x or 10,000x for imaging.

[0153] <Determination of Metal Residue Content> The metal residue content is determined as follows. (Test Sample) Accurately weigh 0.5 g of hollow resin particles into a cleaned 50 mL plastic container. Add 1 mL of washing ethanol and mix thoroughly. Then add 50 mL of deionized water and mix thoroughly. Perform ultrasonic washing and extraction for about 10 minutes, and then let it stand in a 60°C constant temperature bath for 60 minutes. Filter the slurry after standing through a 0.20 μm aqueous chromatography disc (Chromatodisk) as the test sample. (Determination Method) Determine the metal residue content in the test sample under the following conditions. The metal residue content is obtained from a pre-prepared calibration curve. The metal residue content is calculated from the following formula. Metal residue (ppm) = Concentration of the metal element to be measured (μg / mL) × 51 (mL) ÷ Sample volume (g). Also, the lower limit of quantitation (LOQ) is 1 ppm. If the result is below the LQ, it is taken as 1 ppm of the LQ. (ICP Measurement Conditions) Measurement Apparatus = Shimadzu Corporation "ICPE-9000" Multi-type ICP Luminescent Spectrophotometer Measured Elements = Ca, K, Li, Mg, Na Observation Direction = Axial Direction High Frequency Output = 1.20 kW Carrier Flow Rate = 0.7 L / min Plasma Flow Rate = 10.0 L / min Auxiliary Flow Rate = 0.6 L / min Exposure Time = 30 seconds Standard Solutions for Calibration Curve = SPEX Corporation "XSTC-13" Universal Mixed Standard Solution (31 elements mixed, with 5% HNO3 as matrix): approximately 10 mg / L each; "XSTC-8" Universal Mixed Standard Solution (13 elements mixed, with H2O / trace HF as matrix): approximately 10 mg / L each.

[0154] <Dielectric Properties of Hollow Resin Particles> The dielectric properties of the hollow resin particles were measured using a dielectric constant measuring device (ADMS01Nc series) manufactured by AET Corporation. The measurements were conducted at a frequency of 10 GHz, an ambient temperature of 23°C, and a relative humidity of 51 ± 1%. Based on the perturbation theory of resonators, the relative permittivity and dielectric loss tangent of the hollow resin particles were calculated.

[0155] <Determination of Thermogravimetric Analysis (TGA) Rate at 300°C to 300°C under Air Conditioning at a Heating Rate of 10°C / min> The thermogravimetric analysis (TGA) rate at 300°C was determined using a Hitachi Hi-Tech Science Co., Ltd. "NEXTA STA200RV" differential thermal calorimetry (DTA) apparatus. The sampling method and temperature conditions were as follows: 10.5 ± 0.5 mg of sample was seamlessly filled into the bottom of a platinum-plated testing container as the test sample. The TGA rate at 300°C was determined using alumina as a reference material at an air flow rate of 200 mL / min. The TG / DTA curve was obtained by heating the sample from 30°C to 300°C at a heating rate of 10°C / min. The residual weight of the sample at 300°C was determined using the analytical software attached to the apparatus from the obtained curve. The TGA rate at 300°C was calculated using the following formula. The thermal weight loss rate [%] at 300℃ = 100 × (weight of sample before heating - weight of sample residue at 300℃) / weight of sample before heating

[0156] <350℃ Long-Term Heat Resistance Test (Nitrogen Environment)> The thermogravimetric analysis (TGA) at 350℃ for 2 hours was performed using a Hitachi Hi-Tech Science Co., Ltd. "NEXTA STA200RV" differential thermal / thermogravimetric analysis device. The sampling method and temperature conditions were as follows: 10.5±0.5 mg of sample was filled seamlessly into the bottom of a platinum-plated testing container as the test sample. Using alumina as the reference material, the TGA at 350℃ for 2 hours was measured at a nitrogen flow rate of 200 mL / min. The TG / DTA curve was obtained by heating the sample from 30℃ to 350℃ at a heating rate of 10℃ / min and holding for 2 hours. The residual weight of the sample after holding at 350℃ for 2 hours was measured using the analysis software provided with the device. The TGA at 350℃ for 2 hours was calculated using the following formula. Here, the weight of the sample before the heat resistance test refers to the weight of the sample before heating. The weight loss rate [%] at 350℃ for 2 hours = 100 × (weight of sample before heat resistance test - weight of sample after heat resistance test) / weight of sample before heat resistance test

[0157] <Raw Materials Used> The raw materials used are as follows.

[0158] 〔Aromatic monofunctional monomer〕 ・Styrene

[0159] [Aromatic Crosslinking Monomers] • Divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Material Co., Ltd., content 81% by weight, 19% by weight, ethyl vinylbenzene (EVB)) (Examples 1 to 4, Examples 6 to 10, Comparative Examples 1 to 2) • Divinylbenzene (DVB) 960 (manufactured by Nippon Steel Chemical & Material Co., Ltd., content 96% by weight, 4% by weight, ethyl vinylbenzene (EVB)) (Example 5)

[0160] 〔Hydrophilic monofunctional monomer〕・2-Methylacryloxyethylsuccinic acid (manufactured by Kyoei Chemical Co., Ltd., trade name "LightEster HO-MS(N)")

[0161] 〔Other monomers〕・Reactive low molecular weight polyphenylene ether (manufactured by SABIC, trade name "Noryl (registered trademark) SA9000-111 resin")

[0162] 〔Reactive surfactants containing vinyl groups〕・Polyoxyethylene styrene-propylene phenyl ether sulfate ammonium salt (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., trade name "AQUALON AR-10")・Bis(polyoxyethylene phenyl ether) methacrylate sulfate ammonium salt (manufactured by Nippon Emulsifier Co., Ltd., trade name "ANTOX MS-60")・Polyoxyethylene styrene-propylene phenyl ether (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., trade name "AQUALON AN-5065")

[0163] 〔Non-crosslinked polymers〕 ・Paraffin wax (manufactured by Nucera Solutions, trade name "VYBAR260", number average molecular weight 2,600 to 4,000) ・Aliphatic / aromatic hydrocarbon resins (manufactured by TOSOH, trade name "Petrotack 90", number average molecular weight 900) ・Fully hydrogenated polybutadiene (manufactured by Nippon Soda, trade name "BI-3000", number average molecular weight 3,300) ・Styrene-butadiene-styrene block polymer (manufactured by Nippon Soda, trade name "1,2-SBS-P35", number average molecular weight 35,000)

[0164] [Organic solvent] • Heptane

[0165] 〔Polymerization Initiator〕・Lauryl Peroxide (manufactured by Nippon Oil Co., Ltd., trade name "PEROYL L")

[0166] 〔Aqueous medium〕・Ion exchange water

[0167] 〔Example 1〕 After adjusting the oil and water phases according to the composition shown in Table 1, the oil and water phases were mixed and dispersed for 5 minutes at a rotation speed of 7,000 rpm using a Polytron Homogenizer "PT10-35" (manufactured by Central Scientific Trading Co., Ltd.). Then, the mixture was emulsified using a high-pressure emulsifier NVL-AS200 (manufactured by Yoshida Machinery Co., Ltd.) at a processing pressure of 20 MPa to prepare a suspension. The obtained suspension was heated at 70°C for 5 hours, then heated to 90°C for 2 hours to polymerize. The slurry obtained by polymerization was distilled to remove organic solvents, and large-diameter particles were removed by classifying them using a 500-mesh (25 μm opening) metal mesh to obtain a slurry containing hollow resin particles. The obtained slurry was heated and dried to obtain hollow resin particles (1) as dried powder. TEM analysis confirmed that the hollow resin particles (1) were single hollow particles. The results are presented in Table 1. The amount of metal residue in the hollow resin particles (1) was below the lower limit of quantification.

[0168] 〔Example 2〕 Except for the changes in the composition of the oil phase and the composition of the aqueous phase as shown in Table 1, hollow resin particles (2) were obtained in the same manner as in Example 1. TEM measurements confirmed that the hollow resin particles (2) were single-hollow particles. The results are presented in Table 1. The amount of metal residue in the hollow resin particles (2) was below the lower limit of quantification.

[0169] 〔Example 3〕 Except for the change in the composition of the oil phase as shown in Table 1, hollow resin particles (3) were obtained in the same manner as in Example 1. TEM measurements confirmed that the hollow resin particles (3) were single-hollow particles. The results are presented in Table 1. The amount of metal residue in the hollow resin particles (3) was below the lower limit of quantification.

[0170] 〔Example 4〕 Except for the change in the composition of the oil phase as shown in Table 1, hollow resin particles (4) were obtained in the same manner as in Example 1. TEM measurements confirmed that the hollow resin particles (4) were single-hollow particles. The results are presented in Table 1. The amount of metal residue in the hollow resin particles (4) was below the lower limit of quantification.

[0171] 〔Example 5〕 Except for the changes in the composition of the oil phase and the composition of the aqueous phase as shown in Table 1, hollow resin particles (5) were obtained in the same manner as in Example 1. TEM measurements confirmed that the hollow resin particles (5) were single-hollow particles. The results are presented in Table 1. The amount of metal residue in the hollow resin particles (5) was below the lower limit of quantification.

[0172] 〔Example 6〕 Except for the changes in the composition of the oil phase and the composition of the aqueous phase as shown in Table 1, hollow resin particles (6) were obtained in the same manner as in Example 1. TEM measurements confirmed that the hollow resin particles (6) were single-hollow particles. The results are presented in Table 1. The amount of metal residue in the hollow resin particles (6) was below the lower limit of quantification.

[0173] 〔Example 7〕 Except for the changes in the composition of the oil phase and the composition of the aqueous phase as shown in Table 1, hollow resin particles (7) were obtained in the same manner as in Example 1. TEM measurements confirmed that the hollow resin particles (7) were single-hollow particles. The results are presented in Table 1. The amount of metal residue in the hollow resin particles (7) was below the lower limit of quantification.

[0174] 〔Example 8〕 Except for the changes in the composition of the oil phase and the composition of the aqueous phase as shown in Table 1, hollow resin particles (8) were obtained in the same manner as in Example 1. TEM measurements confirmed that the hollow resin particles (8) were single-hollow particles. The results are presented in Table 1. The amount of metal residue in the hollow resin particles (8) was below the lower limit of quantification.

[0175] 〔Example 9〕 Except for the changes in the composition of the oil phase and the composition of the aqueous phase as shown in Table 1, hollow resin particles (9) were obtained in the same manner as in Example 1. TEM measurements confirmed that the hollow resin particles (9) were single-hollow particles. The results are presented in Table 1. The amount of metal residue in the hollow resin particles (9) was below the lower limit of quantification.

[0176] 〔Example 10〕 Except for the changes in the composition of the oil phase and the aqueous phase as shown in Table 1, hollow resin particles (10) were obtained in the same manner as in Example 1. TEM measurements confirmed that the hollow resin particles (10) were single-hollow particles. The results are presented in Table 1. The amount of metal residue in the hollow resin particles (10) was below the lower limit of quantification.

[0177] 〔Comparative Example 1〕 Except for the change in the composition of the oil phase as shown in Table 1, the rest was the same as in Example 1, and it was not possible to obtain hollow resin particles that maintain the shell and the hollow portion surrounded by the shell.

[0178] [Comparative Example 2] Except for the change in the composition of the oil phase as shown in Table 1, hollow resin particles (C2) were obtained in the same manner as in Example 1. TEM measurements confirmed that the hollow resin particles (C2) were single-hollow particles. The results are presented in Table 1.

[0179] [Table 1]

[0180] <Performance Evaluation: Evaluation of Relative Permittivity / Dielectric Loss Tangent of the Particle-Added Membrane> A planetary stirrer (manufactured by KURABO Co., Ltd., "MAZERUSTAR KK-250") was used to degas and stir 0.425 g of particles (2) obtained in Example 2, 8.3 g of ethyl acetate, and 1.7 g of solvent-soluble polyimide KPI-MX300F (manufactured by Kawamura Sangyo Co., Ltd.) to prepare an evaluation mixture. The evaluation mixture was coated onto a 5 mm thick glass plate using a thin coater set to a wet thickness of 250 μm. The film was then heated at 60°C for 30 minutes, at 90°C for 10 minutes, at 150°C for 30 minutes, and at 200°C for 30 minutes to remove the ethyl acetate. After cooling to room temperature, a membrane containing particles was obtained. The relative permittivity and dielectric loss tangent of the obtained membrane were evaluated using the void resonance method (measurement frequency: 5.8 GHz). The reduction rate (%) of the measured values ​​for the relative permittivity and dielectric loss tangent for the particle-free film was calculated using the following formulas. The results are presented in Table 2. Reduction rate of relative permittivity [%] = 100 - (relative permittivity of the film containing particles (2)) / (relative permittivity of the film without particles) × 100 Reduction rate of dielectric loss tangent [%] = 100 - (dielectric loss tangent of the film containing particles (2)) / (dielectric loss tangent of the film without particles) × 100

[0181] [Table 2] A membrane containing particles (2) of Example 2 Relative permittivity reduction rate (%) 11.4 Reduction rate of dielectric loss tangent (%) 22.2 [Industrial Applicability]

[0182] The hollow resin particles obtained according to the embodiments of the present invention and the hollow resin particles obtained according to the manufacturing method of the embodiments of the present invention can be applied to various uses such as resin compositions for semiconductor components, coating compositions, heat-insulating resin compositions, light-diffusing resin compositions, and light-diffusing films.

Claims

1. A hollow resin particle having a shell portion and a hollow portion surrounded by the shell portion, wherein the shell portion comprises a polymer (P) obtained by reacting a monomer component (M) containing a crosslinking monomer and a monofunctional monomer, wherein the crosslinking monomer in the monomer component (M) comprises 40% to 100% by weight, and the average particle size is 0.1 μm to 1 μm, wherein the monofunctional monomer comprises a hydrophilic monofunctional monomer represented by the following general formula (1), wherein in the general formula (1), R1 represents H or CH3, R2 represents an alkyldiyl group having 1 to 10 carbon atoms or an alkenediyl group having 2 to 10 carbon atoms, R3 represents a single bond, an alkyldiyl group having 1 to 10 carbon atoms, an alkenediyl group having 2 to 10 carbon atoms, or an phenyl group, X represents a single bond, an ester bond, an ether bond, or a carbonyl group, n represents a number from 1 to 5, and n R2, X, and R3 are independent of each other. The proportion of hydrophilic monofunctional monomers in the monomer component (M) is from 0.5% to 5.0% by weight, and the thermal weight loss after heating at 350°C for 2 hours in a nitrogen atmosphere is less than 40%.

2. The hollow resin particles as described in claim 1, wherein the hollow percentage is 30% or more.

3. The hollow resin particles as described in claim 1 have a dielectric loss tangent of less than 0.0060 at a measurement frequency of 10 GHz.

4. Hollow resin particles as described in claim 3, wherein, The aforementioned dielectric loss tangent is below 0.0030.

5. Hollow resin particles as described in claim 1, wherein, The relative permittivity at the measured frequency of 10 GHz is less than 2.

0.

6. Hollow resin particles as described in claim 1, wherein, The content of the aforementioned monofunctional monomer in the monomer component (M) is less than 60% by weight.

7. Hollow resin particles as described in claim 1, wherein, In an air environment, the thermal weight loss rate when the temperature is increased from 30°C to 300°C at a rate of 10°C / minute is less than 7.0%.

8. Hollow resin particles as described in any one of claims 1 to 7, which are resin compositions used in semiconductor components.

9. A dispersion comprising the hollow resin particles described in claim 1.