Hollow resin particle and resin compositions for semiconductor components

Abstract

This invention provides hollow resin particles that, even when co-mixed with inorganic particles in a resin composition, exhibit excellent dielectric properties and are not easily pulverized. Furthermore, it provides uses for such hollow resin particles. According to an embodiment of the present invention, the hollow resin particle is a hollow resin particle having an outer shell and a hollow portion covered by the outer shell. The outer shell comprises an aromatic polymer (P1) and a non-crosslinked polymer (P2). The aromatic polymer (P1) is obtained by reacting a monomer component (M) comprising an aromatic monofunctional monomer (a) and an aromatic crosslinking monomer (b). Its hollowness is 20% to 45%, and the hollowness retention rate after dispersion test is more than 85%.

Description

[Technical Field]

[0001] This invention relates to hollow resin particles and their uses. [Previous Technology]

[0002] In recent years, with the increase in information processing volume and communication speed of various electronic machines, the implementation technologies of highly integrated semiconductor devices, high-density wiring, and multilayering are progressing rapidly. Regarding the resin composition of semiconductor components used in semiconductor devices, in order to improve the transmission speed of high-frequency signals and reduce signal transmission losses, it is required to use insulating resins with low relative permittivity and dielectric tangent.

[0003] In response to such requirements, a technology is reported that aims to achieve low relative dielectric constant and low dielectric tangent by mixing hollow resin particles having an outer shell and a hollow portion covered by the outer shell into an insulating resin, thereby introducing an air layer into the insulating resin.

[0004] As hollow resin particles, known examples include: hollow particles having a void retention rate of 80% or more during pressure testing, comprising an acrylic resin outer shell and a hollow portion surrounded by the outer shell (Patent Document 1); hollow particles having an acrylic resin outer shell and a hollow portion surrounded by the outer shell, with a void ratio of 50% or more and 90% or less (Patent Document 2); and hollow particles having an acrylic resin outer shell and a hollow portion surrounded by the outer shell, with a void ratio of 50% or more (Patent Document 3). [Prior Art Documents] [Patent Documents]

[0005] Patent Document 1: International Publication No. 2023 / 127624; Patent Document 2: International Publication No. 2021 / 112110; Patent Document 3: International Publication No. 2022 / 071275 [Summary of the Invention]

[0006] [Problem to be solved by the invention] Acrylic resins have high relative permittivity and dielectric tangent, which leads to deterioration of low dielectric properties. Therefore, the hollow particles described in Patent Documents 1 to 3 are difficult to apply to semiconductor devices that process high-frequency signals in recent years.

[0007] On the other hand, in resin compositions used for sealing materials of semiconductor wafers, inorganic particles such as silicon dioxide are filled into the insulating resin at a high ratio to improve performance. When such a resin composition contains hollow resin particles, during the mixing process to manufacture a molded article from the resin composition, the presence of inorganic particles harder than the resin causes the hollow resin particles to be crushed due to high mixing shear forces. If the hollow resin particles are crushed in this way, the desired low dielectric properties may not be obtained, or the flowability of the resin composition may deteriorate.

[0008] The objective of this invention is to provide hollow resin particles that, even when co-mixed with inorganic particles in a resin composition, exhibit excellent dielectric properties and are not easily pulverized. Furthermore, it provides applications for such hollow resin particles. [Means for Solving the Problem]

[0009] [1] The hollow resin particle according to an embodiment of the present invention is a hollow resin particle having an outer shell and a hollow portion covered by the outer shell, the outer shell comprising an aromatic polymer (P1) and a non-crosslinked polymer (P2), the aromatic polymer (P1) being obtained by reacting a monomer component (M) comprising an aromatic monofunctional monomer (a) and an aromatic crosslinking monomer (b), wherein the hollow fraction is 20% to 45% and the hollow fraction remaining after dispersion test is 85% or more. [2] In the hollow resin particle described above [1], the monomer component (M) may also comprise at least one selected from the group consisting of hydrophilic monofunctional monomers (c) and phosphate ester monomers (d). [3] In the hollow resin particle described above [1] or [2], the volume average particle diameter may be 2.0 μm to 15.0 μm. [4] The hollow resin particles described in any one of [1] to [3] above, wherein the aromatic monofunctional monomer (a) is selected from at least one of the group consisting of styrene and ethyl vinylbenzene. [5] The hollow resin particles described in any one of [1] to [4] above, wherein the aromatic crosslinking monomer (b) may be divinylbenzene. [6] The hollow resin particles described in any one of [2] to [5] above, wherein the hydrophilic monofunctional monomer (c) may be represented by general formula (1) or general formula (2). In general formula (1), R1 represents H or CH3, R2 represents H, alkyl, or phenyl, R3 represents an alkyldiyl group with 2 to 18 carbon atoms, m is the average addition mole of the oxyalkenyl group represented by R³–O, and represents a number from 1 to 100, and the m R3s are independent of each other. In general formula (2), R4 represents H or CH3, R5 represents an alkyldiyl group with 1 to 10 carbon atoms or an alkenediyl group with 2 to 10 carbon atoms, R6 represents a single bond, an alkyldiyl group with 1 to 10 carbon atoms, an alkenediyl group with 2 to 10 carbon atoms, or a phenylene 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 R5, X, and R6 are independent of each other. [7] The hollow resin particles described in any one of [1] to [6] above, wherein the content ratio of the aromatic crosslinking monomer (b) relative to the total amount of the aromatic monofunctional monomer (a) and the aromatic crosslinking monomer (b) above may be 10% to 60% by weight. [8] The hollow resin particles as described in any one of [2] to [7] above, wherein the content of the hydrophilic monofunctional monomer (c) may be 0.1% to 5.0% by weight relative to the total amount of the aromatic monofunctional monomer (a), the aromatic crosslinking monomer (b), the hydrophilic monofunctional monomer (c), and the phosphate ester monomer (d). [9] The hollow resin particles as described in any one of [1] to [8] above, wherein the non-crosslinking polymer (P2) may be selected from at least one of the groups consisting of olefin polymers and styrene polymers.

[10] The hollow resin particles described in any one of [1] to [9] above, wherein the content of the aromatic polymer (P1) in the outer shell portion may be 60% to 99% by weight.

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

[10] above, wherein the content of the non-crosslinked polymer (P2) in the outer shell portion may be 1% to 40% by weight.

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

[11] above are suitable for use in resin compositions for semiconductor components.

[13] The resin composition for semiconductor components according to an embodiment of the present invention comprises the hollow resin particles described in any one of [1] to

[11] above.

[14] The resin composition for semiconductor components described in

[13] above is suitable for use as a sealing material for semiconductor wafers. [Effects of the Invention]

[0010] According to embodiments of the present invention, it is possible to provide hollow resin particles that exhibit excellent low dielectric properties, even when co-mixed with inorganic particles in a resin composition. Furthermore, it is possible to provide applications for such hollow resin particles.

Implementation Method

[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 use of "(meth)acrylic acid" means "acrylic acid and / or methacrylic acid"; the use of "(meth)acrylate" means "acrylate and / or methacrylate"; the use of "(meth)allyl" means "allyl and / or methylallyl"; and the use of "(meth)acrolein" means "acrolein and / or methacrolein". Furthermore, the use of "acid (salt)" in this specification means "acid and / or its salt". Examples of salts include alkali metal salts and alkaline earth metal salts; specifically, examples include sodium salts and potassium salts.

[0013] Hollow Resin Particles According to an embodiment of the present invention, a hollow resin particle is a hollow resin particle having an outer shell and a hollow portion covered by the outer shell. The term "hollow" as used herein refers to a state where the interior is filled with a substance other than resin, for example, meaning a state filled with gas or liquid. From the viewpoint that the effects of the present invention can be more effectively demonstrated, it means a state filled with gas.

[0014] In the hollow resin particles according to an embodiment of the present invention, the hollow portion is a single hollow structure formed by a single hollow region, unlike the porous structure. Since the hollow portion is a single hollow portion, the resin component constituting the outer shell is relatively abundant, making it difficult to pulverize even when mixed with inorganic particles in the resin composition. Furthermore, since the hollow portion is a single hollow portion, it can effectively prevent the penetration of the hollow portion into the substrate, etc.

[0015] Regarding the hollow resin particles according to embodiments of the present invention, the hollowness ratio is typically 20% to 45%, or 22% to 43%, or 24% to 41%, or 25% to 40%. If the hollowness ratio of the hollow resin particles is within the above range, even when the hollow resin particles are co-mixed with inorganic particles in the resin composition, excellent dielectric properties that are not easily pulverized can be exhibited. If the hollowness ratio of the hollow resin particles is outside the above range, the co-mixing of hollow resin particles with inorganic particles in the resin composition may result in pulverization, and furthermore, may deteriorate the flowability of the resin composition.

[0016] Regarding the hollow resin particles according to embodiments of the present invention, the hollow residue rate after the dispersion test detailed below is typically 85% or more, or 86% or more, or 87% or more, or 88% or more, or 89% or more, or 90% or more. The upper limit of the aforementioned hollow residue rate is, for example, 100% or less. The dispersion test detailed below uses a model test where hollow resin particles and inorganic particles are co-mixed in a resin composition, indicating the extent to which the hollow portion of the hollow resin particles remains after this dispersion test. Therefore, the greater the hollow residue rate after the dispersion test, the better the dielectric properties, even when hollow resin particles and inorganic particles are co-mixed in the resin composition, as it exhibits resistance to pulverization.

[0017] Regarding the volume average particle diameter of the hollow resin particles according to embodiments of the present invention, 2.0 μm to 15.0 μm is preferred, and it can also be 2.5 μm to 12.0 μm, or 3.0 μm to 10.0 μm. If the volume average particle diameter of the hollow resin particles is less than 2.0 μm, the outer shell is relatively thin, and if it is co-mixed with inorganic particles in the resin composition, the outer shell may be crushed. If the average particle diameter of the hollow resin particles is larger than 15.0 μm, the polymer produced by the polymerization of monomer components in the suspension polymerization used to form the outer shell may be difficult to separate from the solvent, thus making the formation of the outer shell difficult.

[0018] Regarding the surface of the hollow resin particles according to an embodiment of the present invention, a non-porous shape is preferred. Regarding the specific surface area of ​​the hollow resin particles according to an embodiment of the present invention, 0.1 m² / g to 5 m² / g is preferred, and it can also be 0.3 m² / g to 3 m² / g. If the specific surface area of ​​the hollow resin particles according to an embodiment of the present invention is within the above range, when added to a resin composition, resin intrusion into the hollow portion can be suppressed.

[0019] Regarding the hollow resin particles according to an embodiment of the present invention, the relative permittivity (Dk) at a frequency of 10 GHz is preferably 2.1 or less, and may also be 2.0 or less, or may be 1.9 or less. If the relative permittivity (Dk) at a frequency of 10 GHz is within the above range, the hollow resin particles according to an embodiment of the present invention can exhibit excellent low dielectric properties.

[0020] Regarding the hollow resin particles according to an embodiment of the present invention, the dielectric tangent (Df) at a frequency of 10 GHz is preferably 0.0050 or less, and may also be 0.0045 or less, 0.0040 or less, 0.0035 or less, or 0.0030 or less. If the dielectric tangent (Df) at a frequency of 10 GHz is within the above range, the hollow resin particles according to an embodiment of the present invention can exhibit excellent low dielectric properties.

[0021] 《Outer Shell》 Regarding the outer shell, it is representative that it comprises an aromatic polymer (P1) and a non-crosslinked polymer (P2). By comprising an aromatic polymer (P1) and a non-crosslinked polymer (P2), the effects of the present invention can be achieved in the outer shell.

[0022] In terms of the content ratio of aromatic polymer (P1) in the outer shell, from the viewpoint that the effects of the present invention can be more effectively manifested, 60% to 99% by weight is preferred, and it can also be 70% to 97% by weight, 80% to 96% by weight, or 85% to 95% by weight.

[0023] In terms of the content ratio of the non-crosslinked polymer (P2) in the outer shell, from the viewpoint that the effects of the present invention can be more effectively manifested, 1% to 40% by weight is preferred, and it can also be 3% to 30% by weight, 4% to 20% by weight, or 85% to 95% by weight.

[0024] Regarding the outer casing, without impairing the effects of the present invention, it may also contain any suitable other components besides the aromatic polymer (P1) and the non-crosslinked polymer (P2). These other components may be only one type or may be two or more types.

[0025] As for aromatic polymers (P1), there may be only one type or there may be two or more types.

[0026] Regarding aromatic polymers (P1), a representative system is obtained by reacting a monomer component (M) containing an aromatic monofunctional monomer (a) and an aromatic crosslinking monomer (b).

[0027] In terms of the total content of the monomer component (M), the ratio of the total amount of aromatic monofunctional monomer (a) and aromatic crosslinking monomer (b) is preferably 50% to 100% by weight, from the viewpoint that the effects of the present invention can be more effectively manifested. It can also be 70% to 100% by weight, 80% to 100% by weight, 90% to 100% by weight, or 95% to 100% by weight.

[0028] Regarding the total amount of aromatic monofunctional monomer (a) and aromatic crosslinking monomer (b), from the viewpoint of more effectively demonstrating the effects of the present invention, the content ratio of aromatic monofunctional monomer (a) is preferably 40% to 90% by weight, or 45% to 85% by weight, or 50% to 80% by weight, or 55% to 80% by weight, or 60% to 80% by weight. If the content ratio of the above-mentioned aromatic monofunctional monomer (a) is too high, the strength of the shell portion may decrease due to the lower crosslinking density. If the content ratio of the above-mentioned aromatic monofunctional monomer (a) is too low, unreacted reactive sites may remain, which may negatively affect the full expression of the low dielectric properties.

[0029] Regarding the content ratio of the aromatic monofunctional monomer (a) and the aromatic crosslinking monomer (b), from the viewpoint of more effectively demonstrating the effects of the present invention, relative to the total amount of the aromatic monofunctional monomer (a) and the aromatic crosslinking monomer (b), 10% to 60% by weight is preferred, and it can also be 15% to 55% by weight, 20% to 50% by weight, or 20% to 45% by weight. If the content ratio of the aromatic crosslinking monomer (b) is too high, unreacted reactive sites will remain, which may negatively affect the full expression of the low dielectric properties. If the content ratio of the aromatic crosslinking monomer (b) is too low, the strength of the shell portion may decrease due to the lower crosslinking density.

[0030] The monomer component (M) may also include at least one selected from the group consisting of hydrophilic monofunctional monomers (c) and phosphate ester monomers (d). In other words, regarding the monomer component (M), in addition to aromatic monofunctional monomers (a) and aromatic crosslinking monomers (b), it may further include at least one selected from the group consisting of hydrophilic monofunctional monomers (c) and phosphate ester monomers (d).

[0031] In terms of the total content of aromatic monofunctional monomers (a), aromatic crosslinking monomers (b), hydrophilic monofunctional monomers (c), and phosphate ester monomers (d) in the total amount of monomer component (M), from the viewpoint that the effects of the present invention can be more effectively manifested, 50% to 100% by weight is preferred, and it can also be 70% to 100% by weight, 80% to 100% by weight, 90% to 100% by weight, or 95% to 100% by weight.

[0032] The monomer component (M) comprises at least one of the group consisting of hydrophilic monofunctional monomers (c) and phosphate ester monomers (d). From the viewpoint that the effects of the present invention can be more effectively manifested, the content ratio of hydrophilic monofunctional monomer (c) is preferably 0.1% to 5.0% by weight, or 0.3% to 4.0% by weight, or 0.4% to 3.0% by weight, or 0.5% to 2.0% by weight, relative to the total amount of aromatic monofunctional monomers (a), aromatic crosslinking monomers (b), hydrophilic monofunctional monomers (c), and phosphate ester monomers (d).

[0033] The monomer component (M) includes at least one selected from the group consisting of hydrophilic monofunctional monomers (c) and phosphate ester monomers (d). From the viewpoint that the effect of the present invention can be more effectively manifested, the content ratio of phosphate ester monomers (d) relative to the total amount of aromatic monofunctional monomers (a), aromatic crosslinking monomers (b), hydrophilic monofunctional monomers (c), and phosphate ester monomers (d) is preferably 0.01% to 5.00% by weight, or 0.05% to 3.00% by weight, or 0.08% to 1.00% by weight, or 0.10% to 0.50% by weight, or 0.12% to 0.45% by weight, or 0.14% to 0.45% by weight, or 0.16% to 0.45% by weight.

[0034] As for the aromatic monofunctional monomer (a), there may be only one type or there may be two or more types.

[0035] As an aromatic monofunctional monomer (a), if it is a monofunctional aromatic monomer, any suitable aromatic monofunctional monomer can be used without impairing the effects of the present invention. Examples of such aromatic monofunctional monomers (a) that can further enhance the effects of the present invention include: styrene, ethyl vinylbenzene, α-methylstyrene, vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, vinylbiphenyl, and vinylnaphthalene. From the perspective of further enhancing the effects of the present invention or from the perspective of reactivity, it is preferable that the aromatic monofunctional monomer (a) includes at least one selected from the group consisting of styrene and ethyl vinylbenzene.

[0036] As for the aromatic crosslinking monomer (b), there may be only one type or there may be two or more types.

[0037] As the aromatic crosslinking monomer (b), any suitable aromatic crosslinking monomer can be used without impairing the effects of the present invention. Examples of such aromatic crosslinking monomers (b) that can further enhance the effects of the present invention include: divinylbenzene, divinylnaphthalene, and diallyl phthalate. From the perspective of further enhancing the effects of the present invention or from the perspective of reactivity, divinylbenzene is preferred as the aromatic crosslinking monomer (b).

[0038] As for the hydrophilic monofunctional monomer (c), there may be only one type or there may be two or more types.

[0039] As the hydrophilic monofunctional monomer (c), any suitable hydrophilic monofunctional monomer may be used without impairing the effects of the present invention. From the viewpoint that the effects of the present invention can be more effectively manifested, the hydrophilic monofunctional monomer (c) is preferably represented by general formula (1) or general formula (2).

[0040]

[0041]

[0042] In general formula (1), R1 represents H or CH3.

[0043] In general formula (1), R2 represents H, alkyl or phenyl.

[0044] In general formula (1), R3 represents an alkyldiyl group with 2 to 18 carbon atoms, preferably with 2 to 8 carbon atoms, but it can also be an alkyldiyl group with 2 to 4 carbon atoms. As for the alkyldiyl group, it can be any of the following: straight-chain, branched, or cyclic.

[0045] As an alkyl dienyllium, examples 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.

[0046] In general formula (1), R3–O is an oxoalkylene group having 2 to 18 carbon atoms, preferably having 2 to 8 carbon atoms, but may also be an oxoalkylene group having 2 to 4 carbon atoms. Furthermore, when R3–O is selected from at least two of oxoethylene, oxopropylene, and oxobutenyl groups, the addition form of R3–O may be any form of random addition, bulk addition, or alternating addition. In addition, the addition form mentioned here means the form itself, and does not necessarily mean that it must be obtained by an addition reaction.

[0047] In general formula (1), as R3–O, from the viewpoint that the effects of the present invention can be more effectively manifested, it is selected from at least one of the group consisting of oxyvinyl, oxypropylene, and oxybutenyl (represented by oxytetramethylene).

[0048] In general formula (1), m represents the average addition mole number (referred to as "chain length") of the oxoalkylene group represented by R3–O. m can be a number from 1 to 100, or from 1 to 40, or from 2 to 30, or from 3 to 20, or from 4 to 18, or from 5 to 15. By using m within the above range, the effects of the present invention can be more effectively demonstrated.

[0049] In general formula (1), the m R3s are independent of each other. In general formula (1), R3–O can be two or more types, for example, the case formed by oxyethylene (C2H4O) and oxypropylene (C3H6O), where m is the sum of the average addition moles of the respective oxyalkylene groups. Specifically, for example, –(R3–O)m– is the case of –[(C2H4O)p(C3H6O)q]– (as mentioned above, the addition can be any of random addition, bulk addition, or alternating addition), where m = p + q.

[0050] As a hydrophilic monofunctional monomer (c) represented by general formula (1), examples include: methoxy polyethylene glycol methacrylate, ethoxy polyethylene glycol methacrylate, propoxy polyethylene glycol methacrylate, butoxy polyethylene glycol methacrylate, hexoxy polyethylene glycol methacrylate, octoxy polyethylene glycol polypropylene glycol methacrylate, lauroxy polyethylene glycol methacrylate, stearoxy polyethylene glycol methacrylate, phenoxy polyethylene glycol polypropylene glycol methacrylate, methoxy polyethylene glycol acrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, polyethylene glycol propylene glycol monomethacrylate, polyethylene glycol tetramethylene glycol monomethacrylate, propylene glycol polybutylene glycol monomethacrylate, monoethylene glycol monoacrylate, and polypropylene glycol monoacrylate.

[0051] As a hydrophilic monofunctional monomer (c) represented by general formula (1), commercially available products may also be used. For example, such commercially available products may be the "blemmer" series manufactured by Nippon Oil Co., Ltd.

[0052] In general formula (2), R4 represents H or CH3.

[0053] In general formula (2), R5 represents an alkyldiyl group with 1 to 10 carbon atoms or an alkenyl group with 2 to 10 carbon atoms. Preferably, the alkyldiyl group has 2 to 6 carbon atoms, but it can also have 2 to 4 carbon atoms. The alkyldiyl group can be linear, branched, or cyclic. Preferably, the alkenyl group has 2 to 6 carbon atoms, but it can also have 2 to 4 carbon atoms. The alkenyl group can be linear, branched, or cyclic.

[0054] Regarding R5, as an alkyl dienyllium, examples as described above can be listed. Regarding R5, as an alkened dienyllium, examples include: ethylene-1,2-diellium, 1-propylene-1,3-diellium, 2-butene-1,4-diellium, 1-methyl-1-butene-1,4-diellium, and 2-cyclohexene-1,4-diellium.

[0055] In general formula (2), R6 is a single bond, representing an alkyldiyl group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, or a phenylene group. Regarding the number of carbon atoms in the aforementioned alkyldiyl group, 2 to 6 carbon atoms are preferred, but 2 to 4 carbon atoms are also acceptable. The alkyldiyl group can be linear, branched, or cyclic. Regarding the number of carbon atoms in the aforementioned alkenyl group, 2 to 6 carbon atoms are preferred, but 2 to 4 carbon atoms are also acceptable. The alkenyl group can be linear, branched, or cyclic.

[0056] Regarding R6, as an alkyl diene, examples as described above can be cited. Regarding R6, as an alkened diene, examples as described above can be cited.

[0057] In general formula (2), X represents a single bond, ester bond, ether bond or carbonyl group. As for the ester bond, it can be an R5–O–CO–R6 structure or an R5–CO–O–R6 structure.

[0058] In general formula (2), n represents a number from 1 to 5, and the n R5, X, and R6 are mutually independent.

[0059] As a hydrophilic monofunctional monomer (c) represented by general formula (2), examples include: 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl maleate, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl succinic acid, and 2-acryloyloxyethyl phthalic acid.

[0060] As a hydrophilic monofunctional monomer (c) represented by general formula (2), commercially available products may also be used. For example, such commercially available products may be "light ester HO-MS(N)" manufactured by Kyoei Chemical Co., Ltd.

[0061] As for the phosphate ester monomer (d), there may be only one type or there may be two or more types.

[0062] As the phosphate ester monomer (d), any suitable phosphate ester monomer may be used without impairing the effects of the present invention. From the viewpoint of more effectively manifesting the effects of the present invention, it is preferable to use a compound with a phosphate ester structure and a free radical reactive group as the phosphate ester monomer (d). As a compound that can better manifest the effects of the present invention, compounds represented by general formula (3) are preferred.

[0063]

[0064] In formula (3), R7 represents a methyl or hydrogen atom.

[0065] In formula (3), a is 0 or 1, b is 0~300, c is 0 or 1, and d is 1~300. In formula (3), p represents 1~3.

[0066] In formula (3), R8 is a straight-chain or branched alkylene group having 1 to 50 carbon atoms, preferably a straight-chain or branched alkylene group having 1 to 40 carbon atoms, or a straight-chain or branched alkylene group having 1 to 30 carbon atoms, or a straight-chain or branched alkylene group having 1 to 25 carbon atoms, or a straight-chain or branched alkylene group having 1 to 20 carbon atoms, or a straight-chain or branched alkylene group having 1 to 15 carbon atoms, or a straight-chain or branched alkylene group having 1 to 10 carbon atoms, or a straight-chain or branched alkylene group having 1 to 8 carbon atoms, or a straight-chain or branched alkylene group having 1 to 6 carbon atoms, or a straight-chain or branched alkylene group having 1 to 4 carbon atoms.

[0067] In formula (3), R9 is a straight-chain or branched alkylene group having 1 to 50 carbon atoms, preferably a straight-chain or branched alkylene group having 1 to 40 carbon atoms, or a straight-chain or branched alkylene group having 1 to 30 carbon atoms, or a straight-chain or branched alkylene group having 1 to 25 carbon atoms, or a straight-chain or branched alkylene group having 1 to 20 carbon atoms, or a straight-chain or branched alkylene group having 1 to 15 carbon atoms, or a straight-chain or branched alkylene group having 1 to 13 carbon atoms, or a straight-chain or branched alkylene group having 1 to 10 carbon atoms, or a straight-chain or branched alkylene group having 1 to 8 carbon atoms.

[0068] In formula (3), for b, 0~100 is preferred, but it can also be 0~50, 0~10, 0~5, or 0 or 1.

[0069] In formula (3), as far as d is concerned, 1~100 is preferred, but it can also be 1~50, 1~30, 1~10, 1~5, or 1~3.

[0070] As a phosphate ester monomer (d), it may also be a product that is commercially available. Such a phosphate ester monomer (d) can be exemplified by, from a compatibility point of view, the product name "KAYAMER (registered trademark) PM-21" (manufactured by Nippon Kayaku Co., Ltd.).

[0071] The monomer component (M) may, without impairing the effects of the present invention, include any suitable monomer other than aromatic monofunctional monomers (a), aromatic crosslinking monomers (b), hydrophilic monofunctional monomers (c), and phosphate ester monomers (d). The other monomers may be only one type or may be two or more types.

[0072] The non-crosslinked polymer (P2) may be only one type or may be two or more types.

[0073] By including a non-crosslinked polymer (P2) in the outer shell, the effects of the present invention can be manifested. Furthermore, it can promote phase separation within the polymer droplets during suspension polymerization, making it easier to form uniform particles. As a result, it exhibits excellent low dielectric properties and uniform low dielectric properties.

[0074] As the non-crosslinked polymer (P2), any suitable non-crosslinked polymer (P2) may be used without impairing the effects of the present invention. As such a non-crosslinked polymer (P2), a non-crosslinked polymer without carboxyl groups is preferred, and examples include: paraffin wax, olefin polymers, styrene polymers, and (meth)acrylate polymers, preferably at least one selected from the group consisting of olefin polymers and styrene polymers.

[0075] Regarding the content ratio of the non-crosslinked polymer (P2) in the outer casing, from the viewpoint of more effectively demonstrating the effects of the present invention, 0% to 40% by weight is preferred, and it can also be 3% to 30% by weight or 5% to 20% by weight. If the content ratio of the non-crosslinked polymer (P2) in the outer casing is too high, it may be impossible to exhibit excellent low dielectric properties, or it may be impossible to exhibit uniform low dielectric properties.

[0076] In the case where the non-crosslinked polymer (P2) is an olefin polymer, from the viewpoint that the non-crosslinked polymer (P2) content in the above-mentioned outer shell portion is preferably 7% to 20% by weight, or 7% to 15% by weight, in order to more effectively demonstrate the effects of the present invention.

[0077] In the case where the non-crosslinked polymer (P2) is a styrene-based polymer, from the viewpoint that the non-crosslinked polymer (P2) content in the above-mentioned outer shell portion is preferably 5% to 15% by weight, or 5% to 12% by weight, in order to more effectively demonstrate the effects of the present invention.

[0078] As paraffin wax, examples include: solid paraffin wax and fluid paraffin wax.

[0079] Examples of olefin polymers include polyethylene, polypropylene, and polyα-olefin.

[0080] As a styrene-based polymer, examples include: polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, etc.

[0081] As (meth)acrylate polymers, examples include: poly(meth)acrylate, poly(meth)acrylate, poly(meth)acrylate, poly(meth)acrylate, poly(meth)acrylate, poly(meth)acrylate, styrene-poly(meth)acrylate copolymer, styrene-poly(meth)acrylate copolymer, styrene-poly(meth)acrylate copolymer, styrene-poly(meth)acrylate copolymer, styrene-poly(meth)acrylate copolymer, etc.

[0082] "Method for Manufacturing Hollow Resin Particles" With regard to the hollow resin particles according to embodiments of the present invention, they can be manufactured by any suitable method without impairing the effects of the present invention.

[0083] In the case of hollow resin particles according to embodiments of the present invention, a typical example is obtained by dispersing an oil phase containing an aromatic monofunctional monomer (a) and an aromatic crosslinking monomer (b), a non-crosslinking polymer (P2), and an organic solvent in an aqueous phase selected from the group consisting of a dispersing stabilizer and a surfactant in an aqueous medium, and then performing suspension polymerization.

[0084] The monomer component (M) may also include at least one selected from the group consisting of hydrophilic monofunctional monomers (c) and phosphate ester monomers (d). In other words, in addition to aromatic monofunctional monomers (a) and aromatic crosslinking monomers (b), the monomer component (M) may further include at least one selected from the group consisting of hydrophilic monofunctional monomers (c) and phosphate ester monomers (d).

[0085] In the oil phase, the mixing ratio of monomer component (M) to non-crosslinked polymer (P2) is preferably (60~99):(1~40) by weight, and can also be (70~97):(3~30), (80~96):(4~20), or (85~95):(5~15).

[0086] The organic solvent may be only one type or two or more types. Any suitable organic solvent may be used as the organic solvent without impairing the effects of the present invention. Organic solvents with a boiling point below 100°C are preferred as such organic solvents. By using an organic medium with a boiling point below 100°C as the organic solvent, it is easier to remove the medium from the hollow portion of the obtained hollow resin particles, thereby reducing manufacturing costs.

[0087] Examples of organic solvents with boiling points below 100°C include: heptane, hexane, cyclohexane, methyl acetate, ethyl acetate, methyl ethyl ketone, chloroform, carbon tetrachloride, etc.

[0088] Regarding the amount of organic medium used, any suitable amount can be used 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).

[0089] Regarding the oil phase, it is preferable to include a polymerization initiator. The polymerization initiator may be only one type, or it may be two or more types. Any suitable polymerization initiator may be used as the polymerization initiator without impairing the effects of the present invention.

[0090] As polymerization initiators, examples include: cumene hydroperoxide, secondary butyl peroxide, diisopropylbenzene peroxide, benzoyl peroxide, o-chlorobenzoyl peroxide, o-methoxybenzoyl peroxide, lauryl peroxide, 3,5,5-trimethylhexyl peroxide, dimethyl bis(secondary butyl peroxide)hexane, dimethyl bis(secondary butyl peroxide)hexyn-3, bis(secondary butyl peroxide isopropyl)benzene, bis(secondary butyl peroxide)trimethylcyclohexane, butyl-bis(secondary butyl peroxide)valerate, 2-ethylhexane peroxy acid secondary butyl, dibenzoyl peroxide, p-menthane hydroperoxide, secondary butyl peroxide benzoate, etc.; 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2-) Azo compounds including 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-trimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(4-ethoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(4-n-butoxy-2,4-dimethylvaleronitrile), 1,1'-azobis(cyclohexane-1-nitrile), 2-(aminomethoxyazo)isobutyronitrile, and 4,4'-azobis(4-cyanopentanoic acid).

[0091] As for the polymerization initiator, it can also be a polymerization initiator with a 10-hour half-life temperature below 90°C.

[0092] The amount of polymerization initiator used can be any suitable amount without impairing the effects of the present invention. Such an amount is, for example, 0.1 to 5 parts by weight relative to 100 parts by weight of monomer component (M).

[0093] Regarding the oil phase, in addition to the above-mentioned components, any other suitable components may be included without impairing the effects of the present invention. Such other components may be only one type or two or more types.

[0094] Examples of aqueous media include water and mixtures of water and lower alcohols (methanol, ethanol, isopropanol, etc., with 5 or fewer carbon atoms). Preferably, the water is selected from at least one type selected from the group consisting of ion-exchanged water and distilled water.

[0095] Regarding the amount of aqueous medium used, any suitable amount can be used without impairing the effects of the present invention. Such an amount, relative to 100 parts by weight of the oil tank, is, for example, 100 to 2000 parts by weight, or 200 to 1000 parts by weight. By adjusting the amount of aqueous medium used to the above range, the dispersion stability of the monomers during polymerization is improved, and the formation of resin particle agglomerates can be suppressed during polymerization.

[0096] As a dispersion stabilizer, any suitable dispersion stabilizer can be used without impairing the effects of the present invention. There may be only one type of dispersion stabilizer, or there may be two or more types. Examples of such dispersion stabilizers include: phosphates such as calcium phosphate, magnesium phosphate, aluminum phosphate, and zinc phosphate; pyrophosphates such as calcium pyrophosphate, magnesium pyrophosphate, aluminum pyrophosphate, and zinc pyrophosphate; poorly water-soluble inorganic compounds such as calcium carbonate, magnesium carbonate, magnesium oxide, colloidal silica, calcium hydroxide, aluminum hydroxide, calcium metasilate, calcium sulfate, barium sulfate, and colloidal silica; and water-soluble polymers such as polyvinylpyrrolidone, partially saponified polyvinyl alcohol, polyacrylic acid, carboxymethyl cellulose, and methyl cellulose. Even among these, it is preferable to use substances that dissolve in water after acid decomposition (e.g., calcium carbonate, calcium phosphate, magnesium hydroxide, magnesium pyrophosphate, and calcium pyrophosphate), as the dispersion stabilizer can be easily removed after polymerization.

[0097] Regarding the amount of dispersant stabilizer used, any suitable amount can be used without impairing the effects of the present invention. Such an amount, which ensures the fluidity of the suspension and excellent dispersibility of droplets of the raw material mixture in the suspension, is, for example, 0.1 to 20 parts by weight, or 0.5 to 10 parts by weight, relative to 100 parts by weight of the oil phase.

[0098] As a surfactant, any suitable surfactant may be used without impairing the effects of the present invention. There may be only one surfactant, or there may be two or more. Examples of such surfactants include: anionic surfactants, cationic surfactants, nonionic surfactants, and zwitterionic surfactants.

[0099] Examples of anionic surfactants include: sodium oleate; fatty acid soaps such as castor oil soap; polysulfonates; polycarboxylate salts; alkyl sulfate salts such as sodium dodecyl sulfate and ammonium dodecyl sulfate; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; alkyl aryl sulfonates; alkyl naphthalene sulfonates; alkyl sulfonates; dialkyl sulfonates; dialkyl sulfosuccinates; alkyl phosphates; alkyl phosphate salts; sodium salts of β-naphthalene sulfonate formaldehyde condensates and their salts; polyoxyethylene alkylphenyl ether sulfate salts such as polyoxyethylene nonylphenyl ether sulfate salts; polyoxyethylene sulfonated phenyl ether phosphate; polyoxyethylene alkyl ether sulfates such as sodium polyoxyethylene dodecyl ether sulfate and ammonium polyoxyethylene dodecyl ether sulfate; polyoxyethylene alkyl sulfate salts; polyoxyethylene alkyl phosphate sulfonates; glyceryl borate fatty acid esters; and polyoxyethylene glyceryl fatty acid esters. Anionic surfactants may be one type or two or more types.

[0100] Examples of cationic surfactants include: alkylamine salts such as laurylamine acetate and stearamine acetate; and quaternary ammonium salts such as lauryltrimethylammonium chloride. Cationic surfactants may be one type or two or more types.

[0101] Examples of nonionic surfactants include: (meth)acrylate sulfate surfactants (commercially available products, such as RMA-564, RMA-568, RMA-1114, etc. manufactured by Nippon Emulsifier Co., Ltd.); polyoxyethylene branched decyl ethers; polyoxyethylene tridecyl ether, polyoxyethylene isodecane ether, polyoxyethylene dodecyl ether, polyoxyethylene oleyl alcohol cetyl ether, etc.; polyoxyethylene naphthalene ether, polyoxyethylene phenyl ether, etc.; polyoxyethylene alkyl aryl ether; polyoxyethylene alkyl aryl ether; polyether polyol; polyoxyethylene styrene phenyl ether; polyoxyethylene polyoxypropylene glycol; polyoxyethylene isostearate glyceryl ester; polyoxyethylene fatty acid ester; dehydrated sorbitan fatty acid ester; polyoxysorbitan fatty acid ester; polyoxyethylene alkylamine; glyceryl fatty acid ester; oxyethylene-oxypropylene block polymers. Nonionic surfactants may be one type or two or more types.

[0102] Examples of zwitterionic surfactants include lauryl dimethylamine oxide, phosphate ester surfactants, and phosphite ester surfactants. A zwitterionic surfactant may be a single type or two or more types.

[0103] As a surfactant, a vinyl-containing reactive surfactant can also be used. There can be only one vinyl-containing reactive surfactant, or two or more. If a vinyl-containing reactive surfactant is used, since it can be incorporated into the aromatic polymer (P1), the surfactant in suspension polymerization can be effectively distributed on the particle surface, improving the interfacial activity. Therefore, excellent interfacial activity can be obtained, suppressing the aggregation and bonding of particles during manufacturing, reducing the byproducts of non-standard particles, and exhibiting more uniform low dielectric properties.

[0104] Examples of reactive surfactants containing vinyl groups include: anionic surfactants containing vinyl groups and nonionic surfactants containing vinyl groups.

[0105] Examples of anionic surfactants containing vinyl groups include: polyoxyethylene-1-(allyloxymethyl)alkyl ether sulfate ammonium, polyoxyethylene styrene-propylene phenyl ether sulfate ammonium, polyoxyalkylene ether sulfate ammonium, α-sulfonyl-ω-(1-alkoxymethyl-2-(2-propyleneoxy)ethoxy)-poly(oxy-1,2-ethylenedimethyl)ammonium, polyoxypropylene allyl ether phosphate, and bis(polyoxyethylene phenyl ether) methacrylate sulfate salt.

[0106] Commercially available products of polyoxyethylene-1-(allyloxymethyl)alkyl ether ammonium sulfate include, for example, the product manufactured by First Industrial Pharmaceutical Co., Ltd. under the trade name "Aqualon KH-10" and the product under the trade name "Aqualon KH-1025" (a 25% by weight aqueous solution of "Aqualon KH-10").

[0107] Commercially available products of polyoxyethylene styrene propylene phenyl ether sulfate ammonium can be listed as follows: "AqualonAR-10", "AqualonAR-20", and "AqualonAR-1025" (25% by weight aqueous solution of "AqualonAR-10") manufactured by First Industrial Pharmaceutical Co., Ltd.

[0108] Commercially available products of polyoxyalkylene ether ammonium sulfate include, for example, the product "LATEMULPD-104" manufactured by Kao Corporation.

[0109] Commercially available products of α-sulfonyl-ω-(1-alkoxymethyl-2-(2-propenoxy)ethoxy)-poly(oxy-1,2-ethylenediamine)ammonium can be listed as follows: "ADEKA REASOAP SR-10" and "ADEKA REASOAP SR-20" manufactured by ADEKA Corporation.

[0110] Commercially available products of polyoxypropylene allyl ether phosphate include, for example, "ADEKA REASOAP PP-70" manufactured by ADEKA Corporation.

[0111] Commercially available products as bis(polyoxyethylene phenyl ether) methacrylate sulfate salts include, for example, "ANTOX MS-60" manufactured by Japan Emulsifier Co., Ltd.

[0112] Examples of nonionic surfactants containing vinyl groups include: polyoxyethylene styrene-propylene phenyl ether, polyoxyethylene-1-(allyloxymethyl)alkyl ether, and polyoxyethylene-olefin ether.

[0113] Commercially available products of polyoxyethylene styrene-propylene phenyl ether include, for example, the products manufactured by First Industrial Pharmaceutical Co., Ltd. under the trade names "AqualonAN-10", "AqualonAN-20", "AqualonAN-30", and "AqualonAN-5065".

[0114] Commercially available products of polyoxyethylene-1-(allyloxymethyl)alkyl ethers include: "AqualonKN-10", "AqualonKN-20", "AqualonKN-30", "AqualonKN-5065" manufactured by Daiichi Industrial Pharmaceutical Co., Ltd., and "ADEKA REASOAP ER-10", "ADEKA REASOAP ER-20", "ADEKA REASOAP ER-30", "ADEKA REASOAP ER-40" manufactured by ADEKA Co., Ltd.

[0115] Commercially available products of polyoxyethylene alkenyl ethers include, for example, the products manufactured by Kao Corporation under the brand names "LATEMULPD-420", "LATEMULPD-430", and "LATEMULPD-450".

[0116] Regarding the amount of surfactant used, any suitable amount may be used without impairing the effects of the present invention. Such an amount may be, for example, 0.001 parts by weight to 5 parts by weight, 0.005 parts by weight to 3 parts by weight, or 0.01 parts by weight to 1 part by weight, relative to 100 parts by weight of the oil phase.

[0117] In addition to the above-mentioned components, any other suitable components may be included in the aqueous phase without impairing the effects of the present invention.

[0118] As a method for mixing the oil phase and the aqueous phase, if suspension polymerization can be carried out, any other suitable components may be included without impairing the effects of the present invention.

[0119] Regarding the preparation of the suspension, it is prepared by mixing and stirring the oil phase and the aqueous phase. Typically, the oil phase is dispersed in the aqueous phase. Regarding the dispersion of the oil phase into the aqueous phase, if the oil phase exists in the aqueous phase in droplet form, any suitable dispersion method can be used without impairing the effects of the present invention. As a representative example of such a dispersion method, a dispersion method using a homogenizer can be listed, such as an ultrasonic homogenizer or a high-pressure homogenizer.

[0120] As for the suspension polymerization method, any suitable dispersion method may be used without impairing the effects of the present invention.

[0121] Regarding the polymerization temperature, any suitable polymerization temperature can be used without impairing the effects of the present invention, provided that the temperature is suitable for suspension polymerization. For example, such a polymerization temperature is 30°C to 95°C.

[0122] Regarding the polymerization time, any suitable polymerization time can be used if a suspension polymerization time is appropriate, without impairing the effects of the present invention. A polymerization time of 1 hour to 20 hours is preferred.

[0123] The post-heating that is preferably performed after polymerization is a suitable treatment to obtain hollow resin particles with high degree of completion.

[0124] Regarding the temperature at which post-polymerization is preferably performed, any suitable temperature may be used without impairing the effects of the present invention. A temperature of 50°C to 120°C is preferred for such post-polymerization.

[0125] Regarding the post-heating time after polymerization, any suitable time can be used without impairing the effects of the present invention. A post-heating time of 1 to 10 hours is preferred.

[0126] Regarding the slurry obtained by suspension polymerization, hollow resin particles are obtained by distillation, solvent removal, washing, drying, and classification, as necessary.

[0127] Applications of Hollow Resin Particles According to embodiments of the present invention, hollow resin particles can be used in various applications. From the viewpoint of making better use of the effects of the present invention, hollow resin particles according to embodiments of the present invention are suitable for use in semiconductor materials; representatively, they can be suitably used in resin compositions for semiconductor materials. Furthermore, in addition to the above-mentioned applications in resin compositions for semiconductor materials, hollow resin particles 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, etc., for applications where the effects of the present invention can be utilized.

[0128] 《Resin Composition for Semiconductor Structures》 In terms of hollow resin particles according to embodiments of the present invention, since they can exhibit excellent dielectric properties that are not easily crushed even when mixed with inorganic particles in the resin composition, they are suitable for use in resin compositions for semiconductor structures.

[0129] The resin composition for semiconductor materials according to an embodiment of the present invention comprises hollow resin particles according to an embodiment of the present invention. Such a resin composition for semiconductor materials is, for example, suitable for use as a sealing material for semiconductor wafers.

[0130] Semiconductor component means a component that constitutes a semiconductor, such as a semiconductor package or a semiconductor module. In this specification, the term "resin composition for semiconductor component" means a resin composition used on a semiconductor component.

[0131] In the case of semiconductor packaging, IC chips are used as essential components, and at least one of the following components is selected from molding resin, underfill material, molding underfill material, die bond material, prepreg for semiconductor packaging substrate, metal cladding plate for semiconductor packaging substrate, and laminate material for printed circuit board for semiconductor packaging.

[0132] As for the semiconductor module, it is composed of semiconductor packaging as an essential component, and at least one of the following components is selected from: prepreg for printed circuit board, metal cladding laminate for printed circuit board, laminated material for printed circuit board, solder photoresist, cover film, electromagnetic wave shielding film, and bonding pad for printed circuit board.

[0133] 《Coating Composition》 In terms of hollow resin particles according to embodiments of the present invention, since they can impart an excellent appearance to the coating film containing them, they can be used in coating compositions.

[0134] Such a coating composition contains hollow resin particles according to embodiments of the present invention.

[0135] Regarding the composition of the coating, it is preferable to include at least one selected from an adhesive resin and a UV-curing resin. The adhesive 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.

[0136] As 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. Specifically, examples of adhesive resins include acrylic resins, alkyd resins, polyester resins, polyurethane resins, chlorinated polyolefin resins, and amorphous polyolefin resins.

[0137] As the UV-curable resin, any suitable adhesive resin can be used without impairing the effects of the present invention. Examples of such UV-curable resins include: polyfunctional (meth)acrylate resins and polyfunctional polyurethane acrylate resins, with polyfunctional (meth)acrylate resins being preferred, and polyfunctional (meth)acrylate resins having three or more (meth)acrylic groups in one molecule being even more preferred. As a polyfunctional (meth)acrylate resin 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, neopentyltetroxide tetra(meth)acrylate, neopentyltetroxide tri(meth)acrylate, dinepentyltetroxide pentaacrylate, dinepentyltetroxide tetra(meth)acrylate, dinepentyltetroxide hexa(meth)acrylate, trinepentyltetroxide triacrylate, and trinepentyltetroxide hexaacrylate.

[0138] Regarding the coating composition, it includes at least one selected from adhesive resin and UV-curing resin. The content ratio can be any suitable ratio depending on the purpose. Typically, relative to the total amount of at least one selected from adhesive resin (in the case of emulsion-type waterborne resin, converted to solids content) and UV-curing resin, and hollow resin particles according to embodiments of the present invention, hollow resin particles according to embodiments of the present invention are preferably 5% to 50% by weight, or 10% to 50% by weight, or more preferably 20% to 40% by weight.

[0139] In the case of using UV-curable resins, it is preferable to use a photopolymerization initiator in conjunction with the resin. As the photopolymerization initiator, any suitable photopolymerization initiator can be used without impairing the effects of the present invention. Examples of such photopolymerization initiators include: acetophenones, benzoin compounds, benzophenones, phosphine oxides, ketals, α-hydroxyalkylphenyl ketones, α-aminoalkylphenyl ketones, anthraquinones, thioxanthones, azo compounds, peroxides (described in Japanese Patent Application Publication No. 2001-139663, etc.), 2,3-dialkyldione compounds, disulfides, fluorinated amine compounds, aromatic strontium compounds, onium salts, borates, active halogen compounds, and α-acryloyl oxime esters.

[0140] The coating composition may also contain a solvent. Regarding the solvent, there may be only one type, or there may be two or more types. In the case where the coating composition according to embodiments of the present invention contains a solvent, the content ratio can be any suitable ratio depending on the purpose.

[0141] As a solvent, any suitable solvent may be used without impairing the effects of the present invention. Preferably, such a solvent is one capable of dissolving or dispersing the adhesive resin or UV-curing resin. Examples of such 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 butyl ether. Examples of solvents for water-based coatings include: water and alcohols.

[0142] The coating composition may be diluted as necessary to adjust the viscosity. As a diluent, any suitable diluent may be used, depending on the purpose. The solvents mentioned above are listed as such diluents. There may be only one diluent, or there may be two or more diluents.

[0143] The coating composition may also contain other components as necessary, such as: coating surface conditioner, flow conditioner, ultraviolet absorber, light stabilizer, hardening catalyst, extender pigment, coloring pigment, metallic pigment, mica powder pigment, and dye.

[0144] In the case of forming a coating film using a coating composition, any suitable coating method can be adopted depending on the purpose. Examples of such coating methods include: spray coating, roller coating, brush coating, reverse roller coating, gravure coating, die coating, comma coating, and spray coating.

[0145] In the case of 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: preparing a coating film applied to any coating surface of a substrate, drying the coating film, and then, if necessary, hardening the coating film to form a coating film. Examples of substrates include: metals, wood, glass, and plastics (PET (polyethylene terephthalate), PC (polycarbonate), acrylic resin, TAC (triacetal cellulose), etc.).

[0146] 《Insulating Resin Composition》 According to embodiments of the present invention, hollow resin particles can impart excellent insulating properties to coatings containing them, making them suitable for use in insulating resin compositions. Coatings containing hollow resin particles according to embodiments of the present invention can exhibit excellent reflectivity in the wavelength range from ultraviolet to near-infrared.

[0147] Such a heat-insulating resin composition contains hollow resin particles according to embodiments of the present invention.

[0148] As for the heat-insulating resin composition, it is preferable to include at least one selected from adhesive resin and UV-curing resin. Regarding adhesive resin and UV-curing resin, the description of the aforementioned coating composition can be cited.

[0149] The heat-insulating resin composition may also contain a solvent. Regarding the solvent, please refer to the description of the aforementioned coating composition.

[0150] The heat-insulating resin composition may also be diluted as necessary to adjust the viscosity. The description of the aforementioned coating composition may be cited as a diluent.

[0151] The heat-insulating resin composition may also contain other components as necessary, such as: coating surface conditioner, flow conditioner, ultraviolet absorber, light stabilizer, hardening catalyst, extender pigment, coloring pigment, metallic pigment, mica powder pigment, dye.

[0152] For the coating method in which a heat-insulating resin composition is used to form a coating film, the description of the aforementioned coating composition can be cited as the forming method.

[0153] 《Light-diffusing resin composition》 In terms of hollow resin particles according to embodiments of the present invention, since they can impart excellent light diffusivity to the coating containing them, they can be used in light-diffusing resin compositions.

[0154] Such a light-diffusing resin composition contains hollow resin particles according to an embodiment of the present invention.

[0155] In the case of light-diffusing resin compositions, it is preferable to include at least one selected from adhesive resins and UV-curing resins. For information on adhesive resins and UV-curing resins, please refer to the description of the aforementioned coating compositions.

[0156] The light-diffusing resin composition may also contain a solvent. For information on solvents, please refer to the description of the aforementioned coating composition.

[0157] The light-diffusing resin composition may also be diluted as necessary to adjust the viscosity. The description of the aforementioned coating composition can be cited as a diluent.

[0158] The light-diffusing resin composition may also contain other components as necessary, such as: coating surface conditioners, flow conditioners, ultraviolet absorbers, light stabilizers, hardening catalysts, extender pigments, coloring pigments, metallic pigments, mica powder pigments, and dyes.

[0159] For coating methods in which a light-diffusing resin composition is used to form a coating film, the description of the aforementioned coating composition can be cited as a forming method.

[0160] 《Light Diffusion Film》 In terms of hollow resin particles according to embodiments of the present invention, since they can impart excellent light diffusivity to coatings containing them, they are suitable for use on light diffusive resin compositions.

[0161] Such a light diffusion film contains hollow resin particles according to an embodiment of the present invention.

[0162] The light diffusion film 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. Depending on the purpose, the light diffusion film according to an embodiment of the present invention may also include any other suitable layers. 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 particle layer, a conductive metal oxide particle layer, and a primer layer.

[0163] 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 (triacetin cellulose). [Examples]

[0164] Hereinafter, embodiments are provided to specifically illustrate the present invention, but the present invention is not limited to these embodiments. In addition, unless otherwise specified, "parts" means "parts by weight" and "%" means "% by weight".

[0165] <Volume Average Particle Diameter> The volume average particle diameter of the resin particles was measured using a measuring device commercially available from Beckman Coulter under the trade name "Coulter Multisizer 4e". The measurement was performed using the calibration aperture as specified in the Beckman Coulter Multisizer 4e user manual. Regarding the selection of the aperture used for measurement, a suitable aperture was selected as follows: if the assumed volume average particle diameter of the resin particles being measured is between 1 μm and 10 μm, an aperture with a size of 50 μm was selected; if the assumed volume average particle diameter of the resin particles being measured is between 30 μm and 10 μm larger, an aperture with a size of 100 μm was selected; and if the assumed volume average particle diameter of the resin particles is between 90 μm and 30 μm larger, an aperture with a size of 280 μm was selected. If the measured volume-average particle diameter differs from the assumed volume-average particle diameter, the measurement is performed again using an aperture with a suitable size. For an aperture of 50 μm, the Current (aperture current) is set to –800 and the Gain to 4. For an aperture of 100 μm, the Current (aperture current) is set to –1600 and the Gain to 2. For apertures of 280 μm and 400 μm, the Current (aperture current) is set to –3200 and the Gain to 1. As the sample for testing, 0.1 g of resin particles were dispersed in 10 mL of an aqueous solution of 0.1 wt% nonionic surfactant (Kao Corporation, trade name "Pelex SS-H") using a TOUCHMIXER (manufactured by Yamato Scientific, "TOUCHMIXER MT-31") and an ultrasonic cleaner (manufactured by VELVOCLEAR, "ULTRASONIC CLEANER VS-150"). For the Coulter Multisizer 4e test, a beaker filled with ISOTON II (registered trademark) (manufactured by Beckman Coulter, electrolyte for testing) was set up. While slowly stirring the contents of the beaker, the above-mentioned dispersion was added dropwise. The concentration meter reading on the Coulter Multisizer 4e was adjusted to 5%~10%, and the test began. During the test, the contents of the beaker were slowly stirred until no more colored bubbles were produced. The test was stopped when 100,000 resin particles were measured. The volume-average particle diameter of the resin particles is calculated using the arithmetic mean of the particle size distribution based on the volume of 100,000 particles. The coefficient of variation (CV) is obtained using the following formula.Coefficient of variation (CV) (%) = Standard deviation × 100 / (volume mean diameter of primary particles).

[0166] <Hollowness Ratio> The hollowness ratio of hollow resin particles is obtained from the apparent density of hollow resin particles. The apparent density of hollow resin particles is determined by a vibration densitometer (manufactured by Anton Paar, trade name "DMA1001"). Specifically, hollow resin particles and dispersion medium (manufactured by Toa Synthetic Co., Ltd., trade name "ARUFON UP-1020", density 1.027 g / cm3 (25℃)) are degassed and stirred using a degassing mixer to prepare an evaluation mixture with a hollow resin particle ratio of 2% by weight. The evaluation mixture is filled into the measuring unit of the vibration densitometer, and the density of the mixture is calculated by measuring the vibration frequency of the mixture in the measuring unit, according to the following formula (4). According to the following formula (5), the apparent density of hollow resin particles contained in the air is calculated from the density of the mixture and the dispersion medium and the weight ratio of each component in the mixture. The apparent density is calculated by combining the apparent density and the density of the outer shell. Hollowness ratio of hollow resin particles. In equation (4), f is the vibration frequency [Hz], M is the weight of the measuring unit [g], V is the volume of the measuring unit [cm3], ρ is the density of the sample filled in the measuring unit [g / cm3], and c represents the elastic coefficient [N / mm]. In equation (5), ρp is the apparent density of hollow resin particles [g / cm3], ρd is the density of the dispersion medium [g / cm3], xp is the weight ratio of hollow resin particles in the sample, and xd represents the weight ratio of the dispersion medium in the sample.

[0167] <Hollow Residue Rate After Dispersion Experiment> The dispersion experiment and the determination of the hollow residue rate of the hollow resin particles after the dispersion experiment were carried out as follows. The ratio of hollow resin particles was 8% by volume, silicon dioxide particles was 15% by volume, and the dispersion medium (ARUFON UP-1020) was changed to 77% by volume. The hollow resin particles and inorganic particles (manufactured by Denka Co., Ltd., silicon dioxide particles, trade name "FB-5SDX") and dispersion medium were measured relative to 100% by volume of this mixture. Zirconia beads with a diameter of 0.5 mm were added at 50% by volume and zirconia beads with a diameter of 5 mm at 20% by volume. After ball milling dispersion for 24 hours, the zirconia beads were removed to prepare the evaluation mixture. The evaluation mixture was filled into the measuring unit of a vibrating densitometer. By measuring the vibration frequency of the mixture in the measuring unit, the density of the mixture after the dispersion experiment was calculated by the above formula (4). Subsequently, the apparent density of the hollow resin particles is calculated from the density of the dispersion medium and the silicon dioxide particles and the weight ratio of each component in the mixture using the following formula (6). The hollowness ratio of the hollow resin particles is calculated from the apparent density and the density of the shell. The hollowness residual rate of the hollow resin particles is calculated using the following formula (7). In formula (6), ρp' is the apparent density of the hollow resin particles after the dispersion experiment [g / cm3], ρi is the density of the inorganic particles [g / cm3], and xi represents the weight ratio of the inorganic particles in the sample.

[0168] <Dielectric Properties> The dielectric properties of the hollow resin particles were measured using a dielectric constant measuring device (AET Corporation, ADMS01Nc series). At a frequency of 10 GHz, an ambient temperature of 23°C, and a relative humidity of 51±1%, the relative permittivity (Dk) and dielectric tangent (Df) of the hollow resin particles were calculated using a resonator based on perturbation theory.

[0169] <Observation of the internal structure of resin particles> Hollow resin particles were processed using a sample profile preparation device (manufactured by Nippon Electron Co., Ltd., product name "IB-19500CP") and observed using a scanning electron microscope (SEM) (manufactured by Hitachi High-Tech Co., Ltd., product name "SU-3800") at magnifications of 500 to 3000.

[0170] <Ingredients Used> The ingredients used are as follows.

[0171] [Aromatic monofunctional monomer (a)] ‧Styrene

[0172] [Aromatic Monofunctional Monomer (b)] ‧Divinylbenzene (DVB) 810 (Nippon Steel Chemical & Material Co., Ltd., 81% by weight containing 19% ethylvinylbenzene (EVB))

[0173] [Hydrophilic monofunctional monomer (c)] ‧Compounds corresponding to general formula (1): Polyethylene glycol propylene glycol monomethacrylate (manufactured by Nippon Oil Co., Ltd., trade name "BLEMMER 50PEP-300", in general formula (1), R1=CH3, R2=H, (R3-O)m=[(C2H4O)3.5(C3H6O)2.5], random addition form) ‧Compounds corresponding to general formula (2): 2-methylacryloxyethylsuccinic acid (manufactured by Kyoei Chemical Co., Ltd., trade name "Light Ester HO-MS (N)", in general formula (2), R4=CH3, R5=CH2CH2, R6=CH2CH2, X=–O–C(=O)–, n=1)

[0174] [Phosphate ester monomer (d)] ‧KAYAMER (registered trademark) PM–21 (manufactured by Nippon Kayaku Co., Ltd.)

[0175] [Non-crosslinked polymer (P2)] ‧Non-crosslinked polystyrene (non-crosslinked PS) ‧Polyolefin wax (manufactured by Nucera Solutions, trade name "VYBAR260")

[0176] [Organic solvent] ‧Heptane

[0177] [Surfactant] ‧Bis(polyoxyethylene phenyl ether) methacrylate sulfate (manufactured by Japan Emulsifier Co., Ltd., trade name "AntoxR MS-60")

[0178] [Polymerization Initiator] ‧2,2'-Azobis(2,4-dimethylvalerate) (ABN–V) ‧Azobisisobutyronitrile (AIBN)

[0179] [Aqueous Medium] ‧Ion Exchange Water

[0180] [Example 1] In a polymerizer equipped with a stirring device, thermometer, and cooling mechanism, 300 parts by weight of ion-exchanged water and 2.5 parts by weight of magnesium pyrophosphate as a dispersion stabilizer were provided to prepare an aqueous phase. On the other hand, aromatic monofunctional monomers (a), aromatic crosslinking monomers (b), hydrophilic monofunctional monomers (c), phosphate ester monomers (d), non-crosslinking polymers (P2), organic media, and polymerization initiators, as indicated in Table 1, were mixed evenly to prepare an oil phase. An oil phase was supplied to the aqueous phase in the polymerizer. Using a homogenizer (PRIMIX Co., Ltd., trade name "TK Homomixer MARKII 2.5"), the mixture was stirred at 8000 rpm for 10 minutes. Then, using a high-pressure emulsifier (NVR) (Yoshida Machinery Kogyo Co., Ltd., model "EM055-P20-0600-Exp"), emulsification was performed at an inlet processing pressure of 15 MPa and an outlet pressure of 1 MPa to prepare a dispersion of oil phase droplets in the aqueous phase. The polymerizer was then purged with nitrogen, and the dispersion was heated to 55°C. While stirring the dispersion at 55°C, the raw monomers were polymerized for 4 hours. In the above polymerization reaction, after 2 hours from the confirmed pyrolysis peak, the dispersion was heated to 80°C and held for 4 hours. After removing the organic solvent by distillation, the dispersion was cooled to obtain a slurry containing hollow resin particles. Hydrochloric acid was added to the obtained slurry to decompose magnesium pyrophosphate, and then the water was separated and reduced by vacuum filtration to prepare a filter cake containing hollow resin particles. The filter cake was dried in a vacuum oven at 80°C to obtain hollow resin particles (1). The results are shown in Table 1.

[0181] [Examples 2-10] Except for changing the various formulations as shown in Table 1, the same procedure as in Example 1 was performed to obtain hollow resin particles (2) to (10). Furthermore, regarding Examples 6, 7, and 10, as the preparation of the aqueous phase, in a polymerizer equipped with a stirring device, thermometer, and cooling mechanism, 300 parts by weight of ion-exchanged water, 2.5 parts by weight of magnesium pyrophosphate as a dispersion stabilizer, and the amount of bis(polyoxyethylene phenyl ether) methacrylate sulfate (manufactured by Nippon Emulsifier Co., Ltd., trade name "AntoxR MS-60") shown in Table 1 as a surfactant were prepared to produce the aqueous phase. The results are shown in Table 1.

[0182] [Comparative Examples 1-6] Except for changing the various formulations as shown in Table 1, the same procedure as in Example 1 was performed to obtain hollow resin particles (C1) to (C6). The results are shown in Table 1.

[0183] [Table 1][Industrial Utilization Potential]

[0184] The hollow resin particles according to 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 an outer shell and a hollow portion covered by the outer shell, wherein, The outer shell comprises an aromatic polymer (P1) and a non-crosslinked polymer (P2). The aromatic polymer (P1) is obtained by reacting a monomer component (M) comprising an aromatic monofunctional monomer (a) and an aromatic crosslinking monomer (b). The hollowness is 20% to 45%, and the hollowness retention rate after dispersion test is more than 85%.

2. Hollow resin particles as described in claim 1, wherein, The aforementioned monomeric component (M) comprises at least one of the group consisting of hydrophilic monofunctional monomers (c) and phosphate ester monomers (d).

3. The hollow resin particles as described in claim 1 have a volume average particle diameter of 2.0 μm to 15.0 μm.

4. Hollow resin particles as described in claim 1, wherein, The aforementioned aromatic monofunctional monomer (a) is selected from at least one of the group consisting of styrene and ethyl vinylbenzene.

5. Hollow resin particles as described in claim 1, wherein, The aforementioned aromatic crosslinking monomer (b) is divinylbenzene.

6. Hollow resin particles as described in claim 2, wherein, The aforementioned hydrophilic monofunctional monomer (c) is represented by general formula (1) or general formula (2). In general formula (1), R1 represents H or CH3, R2 represents H, alkyl, or phenyl, R3 represents alkyldiyl with 2 to 18 carbon atoms, m is the average addition mole of oxyalkenyl groups represented by R³–O and represents a number from 1 to 100, and m R3s are independent of each other. In general formula (2), R4 represents H or CH3, R5 represents alkyldiyl with 1 to 10 carbon atoms or alkenediyl with 2 to 10 carbon atoms, R6 represents a single bond, alkyldiyl with 1 to 10 carbon atoms, alkenediyl with 2 to 10 carbon atoms, or phenylene, X represents a single bond, ester bond, ether bond, or carbonyl group, n represents a number from 1 to 5, and n R5, X, and R6s are independent of each other.

7. Hollow resin particles as described in claim 1, wherein, The content of the aforementioned aromatic monofunctional monomer (a) and the aforementioned aromatic crosslinking monomer (b) is 10% to 60% by weight relative to the total amount of the aforementioned aromatic monofunctional monomer (a) and the aforementioned aromatic crosslinking monomer (b).

8. Hollow resin particles as described in claim 2, wherein, The content of the aforementioned hydrophilic monofunctional monomer (c) is 0.1% to 5.0% by weight relative to the total amount of the aforementioned aromatic monofunctional monomer (a), the aforementioned aromatic crosslinking monomer (b), the aforementioned hydrophilic monofunctional monomer (c), and the aforementioned phosphate ester monomer (d).

9. Hollow resin particles as described in claim 1, wherein, The aforementioned non-crosslinked polymer (P2) is selected from at least one of the groups consisting of olefin polymers and styrene polymers.

10. Hollow resin particles as described in claim 1, wherein, The aromatic polymer (P1) in the aforementioned outer shell portion contains 60% to 99% by weight.

11. Hollow resin particles as described in claim 1, wherein, The non-crosslinked polymer (P2) in the aforementioned outer shell portion contains 1% to 40% by weight.

12. Hollow resin particles as described in any one of claims 1 to 11, which are resin compositions for use in semiconductor components.

13. A resin composition for semiconductor components comprising hollow resin particles as described in any one of claims 1 to 11.

14. The resin composition for semiconductor components as described in claim 13, which is a sealant for semiconductor wafers.