Hollow resin particles and use thereof

Abstract

This invention provides a hollow resin particle that exhibits excellent dielectric properties, preventing pulverization, even when co-mixed with inorganic particles in a resin composition. Furthermore, uses of this hollow resin particle are provided. According to an embodiment of the 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), with a hollow fraction of 20% to 45% and a hollow fraction remaining after a dispersion test of 85% or more.

Description

Technical Field

[0001] This invention relates to hollow resin particles and their uses. Background 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 compositions used for semiconductor components 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] To address such requirements, the report presents a technique that seeks to reduce 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] Hollow resin particles are known, for example, hollow particles with a porosity of 80% or more during pressure testing, having a shell containing acrylic resin and a hollow portion surrounded by the shell (Patent Document 1); hollow particles with a porosity of 50% or more and 90% or less, having a shell containing acrylic resin and a hollow portion surrounded by the shell (Patent Document 2); and hollow particles with a porosity of 50% or more, having a shell containing acrylic resin and a hollow portion surrounded by the shell (Patent Document 3).

[0005] Previous technical documents

[0006] Patent documents

[0007] Patent Document 1: International Publication No. 2023 / 127624

[0008] Patent Document 2: International Publication No. 2021 / 112110

[0009] Patent Document 3: International Publication No. 2022 / 071275 Summary of the Invention

[0010] Problems solved by the invention

[0011] Acrylic resins, due to their high relative permittivity and dielectric tangent, suffer from deteriorated low dielectric properties. Therefore, the hollow particles described in Patent Documents 1-3 are unsuitable for semiconductor devices that process the high-frequency signals of recent years.

[0012] On the other hand, in resin compositions used as sealants for semiconductor chips, inorganic particles such as silica are filled into the insulating resin at a high ratio to improve performance. When such resin compositions contain hollow resin particles, during the mixing process to manufacture molded articles, the presence of inorganic particles harder than the resin can cause these 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 achieved, or the flowability of the resin composition may deteriorate.

[0013] The subject 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, uses of these hollow resin particles are provided.

[0014] Methods for solving problems

[0015] [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), the hollow fraction being 20% ​​to 45%, and the hollow fraction remaining after the dispersion test being 85% or more.

[0016] [2] Hollow resin particles as described in [1] above, wherein 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).

[0017] [3] The hollow resin particles described in [1] or [2] above have a volume average particle diameter of 2.0 μm to 15.0 μm.

[0018] [4] Hollow resin particles as 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.

[0019] [5] Hollow resin particles as described in any one of [1] to [4] above, wherein the aromatic crosslinking monomer (b) may be divinylbenzene.

[0020] [6] Hollow resin particles as 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).

[0021]

[0022] In general formula (1), R 1 Represents H or CH3, R 2 Indicates H, alkyl, or phenyl, R 3 The denoting alkadiyl group has 2 to 18 carbon atoms, where m is the average number of moles of oxoalkenyl groups added as R³-O, and represents a number from 1 to 100. The m R... 3 They are independent of each other.

[0023]

[0024] In general formula (2), R 4 Represents H or CH3, R 5 R represents an alkyldiyl group with 1 to 10 carbon atoms or an alkenyl group with 2 to 10 carbon atoms. 6 The symbol represents a single bond, an alkyl group with 1 to 10 carbon atoms, an alkenyl 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 R groups represent the number of R groups. 5 X, R 6 They are independent of each other.

[0025] [7] Hollow resin particles as described in any one of [1] to [6] above, wherein the content of the aromatic crosslinking monomer (b) may be 10% to 60% by weight relative to the total amount of the aromatic monofunctional monomer (a) and the aromatic crosslinking monomer (b).

[0026] [8] 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).

[0027] [9] Hollow resin particles as described in any one of [1] to [8] above, wherein the non-crosslinked polymer (P2) may be selected from at least one of the groups consisting of olefins and styrene.

[0028]

[10] Hollow resin particles as 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.

[0029]

[11] Hollow resin particles as 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.

[0030]

[12] Hollow resin particles as described in any one of [1] to

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

[0031]

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

[11] above.

[0032]

[14] The resin composition for semiconductor components described above

[13] is a sealant for semiconductor chips.

[0033] Invention Effects

[0034] According to embodiments of the present invention, hollow resin particles can be provided that exhibit excellent low dielectric properties, even when co-mixed with inorganic particles in a resin composition, and are not easily pulverized. Furthermore, applications of such hollow resin particles can be provided. Detailed Implementation

[0035] The following describes embodiments of the present invention, but the present invention is not limited to these embodiments.

[0036] 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.

[0037] Hollow Resin Particles

[0038] 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 term "hollow" as used herein refers to a state where the interior is filled with a substance other than resin, such as a state filled with gas or liquid. From the viewpoint of more effectively demonstrating the effects of the present invention, it means a state filled with gas.

[0039] 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 a porous structure. Because 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 co-mixed with inorganic particles in the resin composition. Furthermore, because the hollow portion is a single hollow portion, it effectively prevents the penetration of the hollow portion into the substrate, etc.

[0040] Regarding the hollow resin particles according to embodiments of the present invention, the hollowness ratio is typically 20% to 45%, but can also be 22% to 43%, 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 and resistance to pulverization 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.

[0041] Regarding the hollow resin particles according to embodiments of the present invention, the hollow particle retention rate after the dispersion test detailed later is typically 85% or more, and may also be 86% or more, 87% or more, 88% or more, 89% or more, or 90% or more. The upper limit of the aforementioned hollow particle retention rate is, for example, 100% or less. The dispersion test detailed later 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 higher the hollow particle retention rate after the aforementioned 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.

[0042] 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, but 2.5 μm to 12.0 μm or 3.0 μm to 10.0 μm are also acceptable. If the volume average particle diameter of the hollow resin particles is less than 2.0 μm, the outer shell may be pulverized if it is co-kneaded with inorganic particles in the resin composition due to its relatively thin thickness. If the average particle diameter of the hollow resin particles is larger than 15.0 μm, phase separation between the polymer generated from the monomer component polymerization in the suspension polymerization used to form the outer shell and the solvent may be difficult to achieve, thus making the formation of the outer shell more challenging.

[0043] 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 is preferred. 2 / g~5m 2 / g is preferred, but 0.3m is also acceptable. 2 / g~3m 2 / g. If the specific surface area of ​​the hollow resin particles according to the embodiments of the present invention is within the above range, when added to the resin composition, resin intrusion into the hollow portion can be suppressed.

[0044] 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 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.

[0045] Regarding the hollow resin particles according to embodiments of the present invention, a dielectric tangent (Df) of 0.0050 or less at a frequency of 10 GHz is preferred, but it can 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-mentioned range, the hollow resin particles according to embodiments of the present invention can exhibit excellent low dielectric properties.

[0046] "The Outer Shell"

[0047] In the case of the outer casing, it is typically composed of 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 casing.

[0048] Regarding the content 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.

[0049] Regarding the content 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 5% to 15% by weight.

[0050] 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.

[0051] As for aromatic polymers (P1), there can be only one type or two or more types.

[0052] In the case of aromatic polymers (P1), they are typically obtained by reacting a monomeric component (M) containing an aromatic monofunctional monomer (a) and an aromatic crosslinking monomer (b).

[0053] From the viewpoint that the total content of aromatic monofunctional monomers (a) and aromatic crosslinking monomers (b) in the total amount of monomer component (M) is preferably 50% to 100% by weight, but may also be 70% to 100% by weight, 80% to 100% by weight, 90% to 100% by weight, or 95% to 100% by weight.

[0054] 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 will remain, which may negatively affect the full expression of the low dielectric properties.

[0055] 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 crosslinking monomer (b) is preferably 10% to 60% by weight, or 15% to 55% by weight, or 20% to 50% by weight, or 20% to 45% by weight. If the content ratio of the above-mentioned 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 above-mentioned aromatic crosslinking monomer (b) is too low, the strength of the shell portion may decrease due to the lower crosslinking density.

[0056] 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).

[0057] From the viewpoint that 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) is preferably 50% to 100% by weight, but can also be 70% to 100% by weight, 80% to 100% by weight, 90% to 100% by weight, or 95% to 100% by weight.

[0058] The monomer component (M) comprises at least one selected from the group consisting of a hydrophilic monofunctional monomer (c) and a phosphate ester monomer (d). From the viewpoint that the effects of the present invention can be more effectively manifested by the content ratio of the hydrophilic monofunctional monomer (c) 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), it 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.

[0059] 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 content ratio of phosphate ester monomers (d) is more effective in demonstrating the effects of the present invention relative to the total amount of aromatic monofunctional monomers (a), aromatic crosslinking monomers (b), hydrophilic monofunctional monomers (c), and phosphate ester monomers (d), the preferred content ratio is 0.01 wt% to 5.00 wt%, but it can also be 0.05 wt% to 3.00 wt%, 0.08 wt% to 1.00 wt%, 0.10 wt% to 0.50 wt%, 0.12 wt% to 0.45 wt%, 0.14 wt% to 0.45 wt%, or 0.16 wt% to 0.45 wt%.

[0060] As for aromatic monofunctional monomers (a), there can be only one or more.

[0061] As the 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.

[0062] Regarding aromatic crosslinking monomers (b), there may be only one type or two or more types.

[0063] 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).

[0064] As for the hydrophilic monofunctional monomer (c), there can be only one type or two or more types.

[0065] As the hydrophilic monofunctional monomer (c), any suitable hydrophilic monofunctional monomer can 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) represented by general formula (1) or general formula (2) is preferred.

[0066]

[0067]

[0068] In general formula (1), R 1 It represents H or CH3.

[0069] In general formula (1), R 2 It represents H, alkyl, or phenyl.

[0070] In general formula (1), R 3 The alkyl group represents an alkyl group with 2 to 18 carbon atoms, preferably with 2 to 8 carbon atoms, but it can also be an alkyl group with 2 to 4 carbon atoms. The alkyl group can also be linear, branched, or cyclic.

[0071] 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.

[0072] In general formula (1), R 3 -O is an oxoalkylene group with 2 to 18 carbon atoms, preferably with 2 to 8 carbon atoms, but can also be an oxoalkylene group with 2 to 4 carbon atoms. Furthermore, regarding R... 3 -O refers to the case where at least two or more of the following are selected: oxyethylene, oxypropylene, and oxybutene. R 3 The addition form of -O can be any of the following: random addition, block addition, or alternating addition. Furthermore, the addition form mentioned here refers to the form itself, and does not necessarily mean that it must be obtained through an addition reaction.

[0073] In general formula (1), R is used as 3 -O, from the viewpoint that the effects of the present invention can be more effectively manifested, is selected from at least one of the groups consisting of oxyvinyl, oxypropylene, and oxybutenyl (representatively oxytetramethylene).

[0074] In general formula (1), m represents R 3 -O represents the average number of moles of oxyalkylene groups added (referred to as the "chain length"). 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 keeping m within the above ranges, the effects of the present invention can be more effectively demonstrated.

[0075] In general formula (1), m R 3 They are mutually independent. In general formula (1), R 3 -O represents two or more combinations, such as those formed from oxyethylene (C2H4O) and oxypropylene (C3H6O), where m is the total average molar number of each oxyalkylene group. Specifically, for example: -(R 3 -O) m -for-[(C2H4O)] p (C3H6O) q In the case of ]- (as mentioned above, the addition can be any of the following forms: random addition, block addition, or alternating addition), m = p + q.

[0076] Examples of hydrophilic monofunctional monomers (c) represented by general formula (1) 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.

[0077] 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 use the trade name "blemmer" manufactured by Nippon Oil Co., Ltd.

[0078] In general formula (2), R 4 It represents H or CH3.

[0079] In general formula (2), R 5 This refers to an alkyldiyl group with 1 to 10 carbon atoms or an alkenyl group with 2 to 10 carbon atoms. 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.

[0080] Regarding R 5 As an alkyl diol, examples such as those mentioned above can be cited. Regarding R... 5 Examples of alkylene dimethylbenzene ...

[0081] In general formula (2), R 6 A single bond indicates an alkyl 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 alkyl group, 2 to 6 carbon atoms are preferred, but 2 to 4 carbon atoms are also acceptable. The alkyl group can be linear, branched, or cyclic. Regarding the number of carbon atoms in the 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.

[0082] Regarding R 6 As an alkyl diol, examples such as those mentioned above can be cited. Regarding R... 6As an alkenyl group, examples such as those mentioned above can be cited.

[0083] In general formula (2), X represents a single bond, ester bond, ether bond, or carbonyl group. For ester bonds, it can be R. 5 -O-CO-R 6 The structure can also be R. 5 -CO-OR 6 The structure.

[0084] In general formula (2), n represents a number from 1 to 5, and n R 5 X, R 6 They are independent of each other.

[0085] Examples of hydrophilic monofunctional monomers (c) represented by general formula (2) 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.

[0086] 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.

[0087] Regarding phosphate ester monomers (d), there can be only one type or two or more types.

[0088] As the phosphate ester monomer (d), any suitable phosphate ester monomer can be used without impairing the effects of the present invention. From the viewpoint of more effectively demonstrating 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 demonstrate the effects of the present invention, compounds represented by general formula (3) are preferred.

[0089]

[0090] In equation (3), R 7 It represents a methyl or hydrogen atom.

[0091] In equation (3), a is 0 or 1, b is 0~300, c is 0 or 1, and d is 1~300. In equation (3), p represents 1~3.

[0092] In equation (3), R 8It 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, but it can also be a straight-chain or branched alkylene group having 1 to 30 carbon atoms, a straight-chain or branched alkylene group having 1 to 25 carbon atoms, a straight-chain or branched alkylene group having 1 to 20 carbon atoms, a straight-chain or branched alkylene group having 1 to 15 carbon atoms, a straight-chain or branched alkylene group having 1 to 10 carbon atoms, a straight-chain or branched alkylene group having 1 to 8 carbon atoms, 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.

[0093] In equation (3), R 9 It 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, but it can also be a straight-chain or branched alkylene group having 1 to 30 carbon atoms, a straight-chain or branched alkylene group having 1 to 25 carbon atoms, a straight-chain or branched alkylene group having 1 to 20 carbon atoms, a straight-chain or branched alkylene group having 1 to 15 carbon atoms, a straight-chain or branched alkylene group having 1 to 13 carbon atoms, 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.

[0094] In equation (3), for b, 0~100 is preferred, but it can also be 0~50, 0~10, 0~5, 0 or 1.

[0095] In formula (3), for d, 1~100 is preferred, but it can also be 1~50, 1~30, 1~10, 1~5, or 1~3.

[0096] As a phosphate ester monomer (d), commercially available products can also be used. Examples of such a phosphate ester monomer (d) include, from a compatibility point of view, the trade name "KAYAMER (registered trademark) PM-21" (manufactured by Nippon Kayaku Co., Ltd.).

[0097] 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). Other monomers may be only one type or two or more types.

[0098] The non-crosslinked polymer (P2) can be one type or two or more types.

[0099] The outer shell, by containing a non-crosslinked polymer (P2), enables the effects of the present invention to be realized. 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.

[0100] As the non-crosslinked polymer (P2), any suitable non-crosslinked polymer (P2) can 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. It is preferred to select at least one from the group consisting of olefin polymers and styrene polymers.

[0101] 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, but 3% to 30% by weight or 5% to 20% by weight is also acceptable. 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.

[0102] 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, and may also be 7% to 15% by weight.

[0103] In the case where the non-crosslinked polymer (P2) is styrene, from the viewpoint that the non-crosslinked polymer (P2) content in the above-mentioned outer shell is preferably 5% to 15% by weight, and may also be 5% to 12% by weight, in order to more effectively demonstrate the effects of the present invention.

[0104] Examples of paraffin wax include: solid paraffin wax and liquid paraffin wax.

[0105] Olefins are polymers, such as polyethylene, polypropylene, and polyalphaolefins.

[0106] Styrene is a polymer, and examples include: polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, etc.

[0107] As polymers, (meth)acrylates include, for example: 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, styrene-poly(meth)acrylate copolymer, etc.

[0108] "Manufacturing Methods of Hollow Resin Particles"

[0109] The hollow resin particles according to embodiments of the present invention can be manufactured by any suitable method without impairing the effects of the present invention.

[0110] 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.

[0111] 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).

[0112] In the oil phase, regarding the mixing ratio of monomer component (M) to non-crosslinked polymer (P2), the monomer component (M): non-crosslinked polymer (P2) ratio by weight is preferably (60~99):(1~40), but can also be (70~97):(3~30), (80~96):(4~20), or (85~95):(5~15).

[0113] The organic solvent can be one type or two or more. Any suitable organic solvent can 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. 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, thus reducing manufacturing costs.

[0114] Examples of organic solvents with boiling points below 100°C include: heptane, hexane, cyclohexane, methyl acetate, ethyl acetate, methyl ethyl ketone, chloroform, and carbon tetrachloride.

[0115] 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).

[0116] Regarding the oil phase, it is preferable to include a polymerization initiator. The polymerization initiator may be one type or two or more. Any suitable polymerization initiator may be used as the polymerization initiator without impairing the effects of the present invention.

[0117] Examples of organic peroxides used as polymerization initiators include: cumene hydroperoxide, sec-butyl peroxide, dicumene hydroperoxide, benzoyl peroxide, o-chlorobenzoyl peroxide, o-methoxybenzoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, dimethylbis(sec-butylperoxy)hexane, dimethylbis(sec-butylperoxy)hexyn-3, bis(sec-butylperoxyisopropyl)benzene, bis(sec-butylperoxy)trimethylcyclohexane, butyl-bis(sec-butylperoxy)valerate, 2-ethylhexaneperoxy acid sec-butyl, benzoyl peroxide, p-menthane hydroperoxide, sec-butylperoxybenzoate, etc.; 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2-isopropylbutyronitrile) Azo compounds including 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-(carbamoylazo)isobutyronitrile, and 4,4'-azobis(4-cyanopentanoic acid).

[0118] In terms of polymerization initiators, they can also be polymerization initiators with a 10-hour half-life temperature below 90°C.

[0119] The amount of polymerization initiator used can be any suitable amount without impairing the effects of the present invention. For example, such an amount is 0.1 to 5 parts by weight relative to 100 parts by weight of monomer component (M).

[0120] Regarding the oil phase, in addition to the aforementioned components, any other suitable components may be included without impairing the effects of the present invention. Such other components may be one or more.

[0121] 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 used is selected from at least one of the following groups: ion-exchanged water and distilled water.

[0122] 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 phase, 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.

[0123] 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, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, 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.

[0124] Regarding the amount of dispersant stabilizer used, any suitable amount can be used without impairing the effects of the present invention. Such an amount is to ensure the fluidity of the suspension while maintaining excellent dispersibility of droplets of the raw material mixture in the suspension, and 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.

[0125] As a 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 amphoteric surfactants.

[0126] 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; naphthalene sulfonate formaldehyde condensates such as sodium salt of β-naphthalene sulfonate formaldehyde condensate or its 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 can be one type or two or more types.

[0127] Examples of cationic surfactants include alkylamine salts such as laurylamine acetate and stearamine acetate; and quaternary ammonium salts such as lauryltrimethylammonium chloride. Cationic surfactants can be one type or two or more types.

[0128] Examples of nonionic surfactants include: (meth)acrylate sulfates (commercially available products, such as RMA-564, RMA-568, and RMA-1114 manufactured by a Japanese emulsifier company); polyoxyethylene branched decyl ethers; polyoxyethylene tridecyl ethers, polyoxyethylene isodecane ethers, polyoxyethylene dodecyl ethers, polyoxyethylene oleyl alcohol cetyl ethers, etc.; polyoxyethylene naphthalene ethers, polyoxyethylene phenyl ethers, etc.; polyoxyethylene alkylene ethers; polyoxyethylene alkyl aryl ethers; polyether polyols; polyoxyethylene styrene phenyl ethers; polyoxyethylene polyoxypropylene glycol; polyoxyethylene isostearate glyceryl esters; polyoxyethylene fatty acid esters; dehydrated sorbitan fatty acid esters; polyoxysorbitan fatty acid esters; polyoxyethylene alkylamines; glyceryl fatty acid esters; and oxyethylene-oxypropylene block polymers. Nonionic surfactants can be one type or two or more.

[0129] Examples of amphoteric surfactants include lauryl dimethylamine oxide, phosphate esters, and phosphites. Amphoteric surfactants can be one type or two or more.

[0130] As surfactants, vinyl-containing reactive surfactants can also be used. There can be only one vinyl-containing reactive surfactant or two or more. When using vinyl-containing reactive surfactants, since they can be incorporated into aromatic polymers (P1), the surfactants in suspension polymerization can be effectively distributed on the particle surface, improving surface activity. Therefore, excellent surface activity can be obtained, inhibiting particle aggregation and aggregation during manufacturing, reducing byproducts of non-standard particles, and exhibiting more uniform low-dielectric properties.

[0131] Examples of reactive surfactants containing vinyl groups include anionic surfactants containing vinyl groups and nonionic surfactants containing vinyl groups.

[0132] Examples of vinyl-containing anionic surfactants include: polyoxyethylene-1-(allyloxymethyl)alkyl ether ammonium sulfate, polyoxyethylene styrene-propylene phenyl ether ammonium sulfate, polyoxyalkylene ether ammonium sulfate, α-sulfonyl-ω-(1-alkoxymethyl-2-(2-propenoxy)ethoxy)-poly(oxy-1,2-ethylenedimethyl)ammonium, polyoxypropylene allyl ether phosphate, and bis(polyoxyethylene phenyl ether) methacrylate sulfate.

[0133] Commercially available products of polyoxyethylene-1-(allyloxymethyl)alkyl ether ammonium sulfate include, for example, "Aqualon KH-10" and "Aqualon KH-1025" (a 25% by weight aqueous solution of "Aqualon KH-10") manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.

[0134] Commercially available products of polyoxyethylene styrene-propylene phenyl ether sulfate ammonium can be exemplified by: "AqualonAR-10", "AqualonAR-20", and "AqualonAR-1025" (a 25% by weight aqueous solution of "AqualonAR-10") manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.

[0135] Commercially available products of polyoxyalkylene ether ammonium sulfate include, for example, the product "LATEMULPD-104" manufactured by Kao Corporation.

[0136] Commercially available products of α-sulfonyl-ω-(1-alkoxymethyl-2-(2-propenoxy)ethoxy)-poly(oxy-1,2-ethylenediamine)ammonium include, for example, "ADEKA REASOAP SR-10" and "ADEKA REASOAP SR-20" manufactured by ADEKA Inc.

[0137] Commercially available products of polyoxypropylene allyl ether phosphate include, for example, "ADEKA REASOAP PP-70" manufactured by ADEKA Inc.

[0138] Commercially available products as bis(polyoxyethylene phenyl ether) methacrylate sulfate salts include, for example, "ANTOX MS-60" manufactured by Japan Emulsifier Co., Ltd.

[0139] Examples of nonionic surfactants containing vinyl groups include: polyoxyethylene styrene-propylene phenyl ether, polyoxyethylene-1-(allyloxymethyl)alkyl ether, and polyoxyethylene olefin ether.

[0140] Commercially available products of polyoxyethylene styrene-propylene phenyl ether include, for example, those manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd. under the trade names "AqualonAN-10", "AqualonAN-20", "AqualonAN-30", and "AqualonAN-5065".

[0141] Commercially available products of polyoxyethylene-1-(allyloxymethyl)alkyl ethers include: those manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd. under the trade names "AqualonKN-10", "AqualonKN-20", "AqualonKN-30", and "AqualonKN-5065"; and those manufactured by ADEKA Co., Ltd. under the trade names "ADEKA REASOAP ER-10", "ADEKA REASOAP ER-20", "ADEKA REASOAP ER-30", and "ADEKA REASOAP ER-40".

[0142] Commercially available polyoxyethylene ethers include, for example, products manufactured by Kao Corporation under the trade names “LATEMULPD-420”, “LATEMULPD-430”, and “LATEMULPD-450”.

[0143] Regarding the amount of surfactant 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 phase, is, for example, 0.001 parts by weight to 5 parts by weight, or 0.005 parts by weight to 3 parts by weight, or 0.01 parts by weight to 1 part by weight.

[0144] 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.

[0145] 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 compromising the effects of the present invention.

[0146] Regarding the preparation of suspensions, preparation is achieved 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 as droplets, any suitable dispersion method can be used without impairing the effects of the present invention. Representative examples of such dispersion methods include those using a homogenizer, such as an ultrasonic homogenizer or a high-pressure homogenizer.

[0147] Regarding the suspension polymerization method, any suitable dispersion method may be used without impairing the effects of the present invention.

[0148] 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. Examples of such polymerization temperatures are 30°C to 95°C.

[0149] Regarding the polymerization time, any suitable polymerization time can be used if a suspension polymerization time is appropriate, without compromising the effects of the present invention. A polymerization time of 1 hour to 20 hours is preferred.

[0150] Post-heating, which is preferably performed after polymerization, is a suitable treatment to obtain hollow resin particles with high degree of completion.

[0151] Regarding the optimal temperature for post-polymerization heating, any suitable temperature can be used without impairing the effects of the present invention. A temperature of 50°C to 120°C is preferred for such post-polymerization heating.

[0152] Regarding the optimal post-polymerization heating time, any suitable time can be used without impairing the effects of the present invention. A post-polymerization heating time of 1 to 10 hours is preferred.

[0153] The slurry obtained by suspension polymerization may be subjected to distillation, solvent removal, washing, drying, and classification as necessary to obtain hollow resin particles.

[0154] Applications of Hollow Resin Particles

[0155] The hollow resin particles according to embodiments of the present invention can be used in various applications. From the viewpoint of making better use of the effects of the present invention, the hollow resin particles according to embodiments of the present invention are suitable for use in semiconductor materials, and representatively, they can be suitably used in resin compositions for semiconductor materials. In addition, besides the above-mentioned uses as resin compositions for semiconductor materials, the 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.

[0156] "Resin Compositions for Semiconductor Materials"

[0157] The hollow resin particles according to embodiments of the present invention exhibit excellent dielectric properties, even when mixed with inorganic particles in a resin composition, and are not easily pulverized, making them suitable for use in resin compositions for semiconductor materials.

[0158] The semiconductor material resin composition according to an embodiment of the present invention comprises hollow resin particles according to an embodiment of the present invention. Such a semiconductor material resin composition is, for example, suitable for use as a sealing material for semiconductor chips.

[0159] Semiconductor components refer to components that constitute a semiconductor, such as semiconductor packages or semiconductor modules. In this specification, resin compositions for semiconductor components refer to resin compositions used on semiconductor components.

[0160] In the case of semiconductor packaging, IC chips are an essential component, 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.

[0161] In the case of semiconductor modules, semiconductor packaging is an essential component, and at least one of the following components is selected from: prepreg for printed circuit boards, metal cladding laminate for printed circuit boards, laminated material for printed circuit boards, solder photoresist, cover film, electromagnetic wave shielding film, and bonding pad for printed circuit boards.

[0162] "Coating Compositions"

[0163] The hollow resin particles according to embodiments of the present invention are suitable for use in coating compositions because they can impart an excellent appearance to the coating film containing them.

[0164] Such coating compositions contain hollow resin particles according to embodiments of the present invention.

[0165] The coating composition preferably includes at least one selected from an adhesive resin and a UV-curing resin. The adhesive resin may be one type or two or more types. The UV-curing resin may be one type or two or more types.

[0166] As the adhesive resin, any suitable adhesive resin can 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.

[0167] 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)acryloyl groups in one molecule being even more preferred. As a polyfunctional (meth)acrylate resin having three or more (meth)acryloyl groups in one molecule, examples include: trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, 1,2,4-cyclohexanetetra(meth)acrylate, pentaglycerol triacrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol triacrylate, and tripentaerythritol hexaacrylate.

[0168] Regarding the coating composition, it includes at least one selected from an adhesive resin and a UV-curing resin, and the content ratio can be any suitable ratio depending on the purpose. Typically, relative to the total amount of at least one selected from the adhesive resin (in the case of an emulsion-type aqueous resin, expressed as solids) and the UV-curing resin, and the hollow resin particles according to an embodiment of the present invention, the hollow resin particles according to an embodiment 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.

[0169] When using UV-curable resins, it is preferable to use a photopolymerization initiator in conjunction with the resin. 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 sulfonium compounds, onium salts, borates, active halogen compounds, and α-acyl oxime esters.

[0170] The coating composition may also contain a solvent. The solvent may be one type or two or more. Regarding 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.

[0171] 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-curable resin. Examples of such solvents include: hydrocarbons such as toluene and xylene if the coating is oil; ketones such as methyl ethyl ketone and methyl isobutyl ketone if the coating is methyl ethyl ketone; esters such as ethyl acetate and butyl acetate if the coating is ethyl acetate; and ethers such as dialkylene, ethylene glycol diethyl ether, and ethylene glycol butyl ether if the coating is water. Examples of such solvents include: water and alcohols.

[0172] The coating composition may be diluted as necessary to adjust its viscosity. 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 two or more diluents.

[0173] The coating composition may also contain other components as necessary, such as: coating surface conditioners, flow conditioners, ultraviolet absorbers, light stabilizers, curing catalysts, extender pigments, coloring pigments, metallic pigments, mica powder pigments, and dyes.

[0174] When using a coating composition to form a coating film, 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.

[0175] Regarding the formation of a coating film using a coating composition, any suitable formation method can be employed depending on the purpose. Examples of such methods include: preparing a coating film applied to any coating surface of a substrate, drying the coating film, and then curing the coating film as necessary to form a coating film. Examples of substrates include: metals, wood, glass, and plastics (PET (polyethylene terephthalate), PC (polycarbonate), acrylic resin, TAC (triacetyl cellulose), etc.).

[0176] "Insulating Resin Compositions"

[0177] The hollow resin particles according to embodiments of the present invention can impart excellent thermal insulation properties to coatings containing them, making them suitable for use in thermally insulating resin compositions. Coatings containing the hollow resin particles according to embodiments of the present invention can exhibit excellent reflectivity across a wavelength range from ultraviolet to near-infrared.

[0178] Such a heat-insulating resin composition comprises hollow resin particles according to embodiments of the present invention.

[0179] Regarding the heat-insulating resin composition, it is preferable to include at least one selected from adhesive resin and UV-curing resin. For information on adhesive resin and UV-curing resin, please refer to the description of the aforementioned coating composition.

[0180] The heat-insulating resin composition may also contain a solvent. For information on solvents, please refer to the description of the aforementioned coating compositions.

[0181] The heat-insulating resin composition may also be diluted as necessary to adjust the viscosity. The description of the aforementioned coating composition can be referenced as a diluent.

[0182] The heat-insulating resin composition may also contain other components, such as coating surface conditioners, flow conditioners, ultraviolet absorbers, light stabilizers, curing catalysts, extender pigments, coloring pigments, metallic pigments, mica powder pigments, and dyes, as necessary.

[0183] Regarding the coating method for forming a coating film using a heat-insulating resin composition, the description of the aforementioned coating composition can be cited as a forming method.

[0184] "Light-Diffusing Resin Compositions"

[0185] The hollow resin particles according to embodiments of the present invention are suitable for use in light-diffusing resin compositions because they can impart excellent light diffusing properties to coatings containing them.

[0186] Such a light-diffusing resin composition comprises hollow resin particles according to embodiments of the present invention.

[0187] Regarding the light-diffusing resin composition, it is preferable to include at least one selected from adhesive resin and UV-curing resin. For information on adhesive resin and UV-curing resin, please refer to the description of the aforementioned coating composition.

[0188] The light-diffusing resin composition may also contain a solvent. For details regarding the solvent, please refer to the description of the aforementioned coating composition.

[0189] The light-diffusing resin composition may also be diluted as necessary to adjust the viscosity. The description of the aforementioned coating composition can be referenced as a diluent.

[0190] The light-diffusing resin composition may also contain other components, such as coating surface conditioners, flow conditioners, ultraviolet absorbers, light stabilizers, curing catalysts, extender pigments, coloring pigments, metallic pigments, mica powder pigments, and dyes, as necessary.

[0191] Regarding the coating method for forming a coating film using a light-diffusing resin composition, the description of the aforementioned coating composition can be cited as a method for forming the film.

[0192] "Light Diffusion Film"

[0193] The hollow resin particles according to embodiments of the present invention are suitable for use in light-diffusing resin compositions because they can impart excellent light diffusivity to coatings containing them.

[0194] Such a light-diffusing film contains hollow resin particles according to an embodiment of the present invention.

[0195] The light-diffusing film comprises a light-diffusing layer formed from the aforementioned light-diffusing resin composition and a substrate. Furthermore, the light-diffusing layer may or may not be the outermost layer of the light-diffusing film. According to embodiments of the present invention, the light-diffusing film may also include 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 particle layer, a conductive metal oxide particle layer, and a primer layer.

[0196] Examples of substrates include: metals, wood, glass, plastic films, plastic sheets, plastic lenses, plastic panels, cathode ray tubes, fluorescent display tubes, and liquid crystal display panels. Examples of plastics that constitute plastic films, plastic sheets, plastic lenses, and plastic panels include: PET (polyethylene terephthalate), PC (polycarbonate), acrylic resin, and TAC (triacetyl cellulose).

[0197] Example

[0198] The present invention is described below with examples, but the present invention is not limited to these examples. In addition, unless otherwise specified, "parts" means "parts by weight" and "%" means "% by weight".

[0199] <Volume average particle diameter>

[0200] 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.

[0201] Regarding the selection of the pore size used for measurement, if the assumed volume average particle diameter of the resin particles being measured is between 1 μm and 10 μm, a pore size of 50 μm is selected; if the assumed volume average particle diameter is between 30 μm and 10 μm, a pore size of 100 μm is selected; and if the assumed volume average particle diameter is between 90 μm and 30 μm, a pore size of 280 μm is selected, etc., a suitable pore size is chosen. If the measured volume average particle diameter differs from the assumed volume average particle diameter, the pore size is changed to a more suitable size, and the measurement is performed again.

[0202] When selecting an aperture size of 50 μm, the Current (aperture current) is -800 and the Gain is set to 4. When selecting an aperture size of 100 μm, the Current (aperture current) is -1600 and the Gain is set to 2. When selecting aperture sizes of 280 μm and 400 μm, the Current (aperture current) is -3200 and the Gain is set to 1.

[0203] 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 (manufactured by Yamato Scientific, "TOUCHMIXER MT-31") using a TOUCHMIXER (manufactured by Daiwa Scientific, "TOUCHMIXER MT-31") and an ultrasonic cleaner (manufactured by VELVOCLEAR, "ULTRASONIC CLEANER VS-150")

[0204] For the measurement section using the Coulter Multisizer 4e, a beaker filled with ISOTON II (registered trademark) (manufactured by Beckman Coulter, electrolyte for measurement) was set up. While slowly stirring the contents of the beaker, the aforementioned dispersed liquid was added dropwise. The concentration meter reading on the Coulter Multisizer 4e's main screen was adjusted to 5%~10%, and the measurement began. During the measurement, the contents of the beaker were slowly stirred until no more colored bubbles were produced. The measurement ended when 100,000 resin particles were measured. The volume average particle diameter of the resin particles is the arithmetic mean of the particle size distribution based on the volume of 100,000 particles. The coefficient of variation (CV) is calculated using the following formula.

[0205] The variance (CV) (%) = standard deviation × 100 / (volume mean diameter of primary particles)

[0206] <Void Rate>

[0207] The hollowness ratio of hollow resin particles is obtained from their apparent density. The apparent density of hollow resin particles is measured using a vibration density meter (manufactured by Anton Paar, trade name "DMA1001").

[0208] Specifically, the hollow resin particles were mixed with a dispersion medium (manufactured by Toa Synthetic Co., Ltd., trade name "ARUFON UP-1020", density 1.027 g / cm³) at a ratio of 2% by weight. 3 (25°C) Deaeration and stirring were performed using a deaerator to prepare an evaluation mixture. The evaluation mixture was filled into the measuring unit of a vibratory densitometer, and the density of the mixture was 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 the hollow resin particles contained in the air was calculated from the density of the mixture and the dispersion medium and the weight ratio of each component in the mixture, and the hollowness of the hollow resin particles was calculated from the apparent density and the density of the shell.

[0209]

[0210] In equation (4), f is the vibration frequency [Hz], M is the weight of the measuring unit [g], and V is the volume of the measuring unit [cm]. 3 ], ρ is the density of the sample filled in the measuring unit [g / cm³] 3 ], c represents the elasticity number [N / mm].

[0211]

[0212] In equation (5), ρ pThe apparent density of hollow resin particles [g / cm³] 3 ], ρ d The density of the dispersion medium [g / cm³] 3 ], x p x represents the weight ratio of hollow resin particles in the sample. d This indicates the weight ratio of the dispersion medium in the sample.

[0213] <Hollow Residual Rate After Dispersion Experiment>

[0214] The dispersion experiment and the determination of the hollow resin particle retention rate after the dispersion experiment were carried out as follows.

[0215] The ratio of hollow resin particles was 8% by volume, silica particles 15% by volume, and dispersion medium (ARUFON UP-1020) was 77% by volume. The hollow resin particles, inorganic particles (manufactured by Denka Co., Ltd., silica 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 were added at 20% by volume. After ball milling dispersion for 24 hours, the zirconia beads were removed to prepare the mixture for evaluation.

[0216] The evaluation mixture is filled into the measuring unit of a vibratory densitometer. The density of the mixture after the dispersion experiment is calculated by measuring the vibration frequency of the mixture in the measuring unit. Then, the apparent density of the hollow resin particles is calculated from the weight ratio of the density of the dispersion medium and silica particles to each component in the mixture using the following formula (6). The hollowness 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).

[0217]

[0218] In equation (6), ρ p' The apparent density of the hollow resin particles after the dispersion experiment [g / cm³] 3 ], ρ i Density of inorganic particles [g / cm³] 3 ], x i This indicates the weight ratio of inorganic particles in the sample.

[0219]

[0220] <Dielectric Properties>

[0221] The dielectric properties of hollow resin particles were measured using a dielectric constant measuring device (manufactured by AET Corporation, ADMS01Nc is one example). At a frequency of 10 GHz, an ambient temperature of 23°C, and a relative humidity below 51 ± 1%, the relative permittivity (Dk) and dielectric tangent (Df) of the hollow resin particles were calculated using a resonator based on perturbation theory.

[0222] <Observation of the Internal Structure of Resin Particles>

[0223] Hollow resin particles were processed using a sample profile preparation device (manufactured by Nippon Electron Co., Ltd., trade name "IB-19500CP") and observed using a scanning electron microscope (SEM) (manufactured by Hitachi High-Tech Co., Ltd., trade name "SU-3800") at magnifications of 500 to 3000.

[0224] <Ingredients Used>

[0225] The raw materials used are as follows.

[0226] [Aromatic monofunctional monomer (a)]

[0227] ·styrene

[0228] [Aromatic monofunctional monomers (b)]

[0229] • Divinylbenzene (DVB) 810 (Nippon Steel Chemical & Material Co., Ltd., 81% by weight containing 19% ethyl vinylbenzene (EVB))

[0230] [Hydrophilic monofunctional monomer (c)]

[0231] • The compound 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), R 1 =CH3、R 2 =H、(R 3 -O) m =[(C2H4O) 3.5 (C3H6O) 2.5 (Random bonus form)

[0232] • The compound corresponding to general formula (2): 2-Methylacryloyloxyethylsuccinic acid (manufactured by Kyoei Chemical Co., Ltd., trade name "Light Ester HO-MS (N)"). In general formula (2), R 4 =CH3、R 5 =CH2CH2、R 6 =CH2CH2, X=-OC(=O)-, n=1)

[0233] [Phosphate ester monomers (d)]

[0234] KAYAMER (registered trademark) PM-21 (manufactured by Nippon Kayaku Co., Ltd.)

[0235] [Non-crosslinked polymer (P2)]

[0236] • Non-crosslinked polystyrene (non-crosslinked PS)

[0237] • Polyolefin wax (manufactured by Nucera Solutions, trade name "VYBAR260")

[0238] [Organic solvents]

[0239] ·Heptane

[0240] [surfactant]

[0241] • Bis(polyoxyethylene phenyl ether) methacrylate sulfate (manufactured by Japan Emulsifier Co., Ltd., trade name "AntoxR MS-60")

[0242] [Polymerization initiator]

[0243] ·2,2'-Azobis(2,4-dimethylvalerate) (ABN-V)

[0244] • Azobisisobutyronitrile (AIBN)

[0245] [Aqueous media]

[0246] · Ion-exchanged water

[0247] [Example 1]

[0248] 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 are provided to prepare an aqueous phase.

[0249] On the other hand, the 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 quantified in Table 1 are mixed evenly to prepare an oil phase.

[0250] An oil phase was supplied to the aqueous phase in the polymerizer and stirred for 10 minutes at 8000 rpm using a homogenizer (PRIMIX Co., Ltd., trade name "TK Homomixer MARKII2.5"). Then, emulsification was performed using a high-pressure emulsifier (NVR, Yoshida Machinery Co., Ltd., model "EM055-P20-0600-Exp") at an inlet processing pressure of 15 MPa and an outlet pressure of 1 MPa, resulting in 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.

[0251] 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.

[0252] 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).

[0253] The results are shown in Table 1.

[0254] [Examples 2-10]

[0255] Except for changing the various formulations as shown in Table 1, the process was carried out in the same manner as in Example 1 to obtain hollow resin particles (2) to (10). In addition, regarding Examples 6, 7, and 10, as the preparation of the aqueous phase, in a polymerizer equipped with a stirring device, a thermometer, and a 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 salt (manufactured by Nippon Emulsifier Co., Ltd., trade name "AntoxR MS-60") as a surfactant, as shown in Table 1, were provided to prepare the aqueous phase.

[0256] The results are shown in Table 1.

[0257] [Comparative Examples 1-6]

[0258] Except for changing the various formulations as shown in Table 1, the process was carried out in the same manner as in Example 1 to obtain hollow resin particles (C1) to (C6).

[0259] The results are shown in Table 1.

[0260] [Table 1]

[0261]

[0262]

[0263] Industrial utilization potential

[0264] 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 monomeric component (M) comprising an aromatic monofunctional monomer (a) and an aromatic crosslinking monomer (b). The hollow rate is 20%~45%. The hollow residue rate after the dispersion test is over 85%.

2. The hollow resin particles as described in claim 1, wherein, The monomer component (M) is at least one of the groups 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. The hollow resin particles as described in claim 1, wherein, The aromatic monofunctional monomer (a) is selected from at least one of the groups consisting of styrene and ethyl vinylbenzene.

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

6. The hollow resin particles as described in claim 2, wherein, The hydrophilic monofunctional monomer (c) is represented by general formula (1) or general formula (2). In general formula (1), R 1 Represents H or CH3, R 2 Indicates H, alkyl, or phenyl, R 3 This indicates an alkyldiyl group with 2 to 18 carbon atoms, where m is the average number of moles of oxyalkenyl groups added as R³-O and represents a number from 1 to 100. The m R... 3 Independent of each other In General Formula (2), R 4 represents H or CH3, R 5 represents an alkanediyl group having 1 to 10 carbons or an alkenediyl group having 2 to 10 carbons, R 6 represents a single bond, an alkanediyl group having 1 to 10 carbons, an alkenediyl group having 2 to 10 carbons, or a phenylene group, X represents a single bond, an ester bond, an ether bond, or a carbonyl group, n represents a number of 1 to 5, and R 5 , X, R 6 are independent of each other.

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

8. The hollow resin particles as described in claim 2, wherein, The content of the hydrophilic monofunctional monomer (c) is 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 claim 1, wherein, The non-crosslinked polymer (P2) is selected from at least one of the groups consisting of olefins and styrene.

10. The hollow resin particles as described in claim 1, wherein, The aromatic polymer (P1) in the outer shell is present in a ratio of 60% to 99% by weight.

11. The hollow resin particles as described in claim 1, wherein, The non-crosslinked polymer (P2) in the outer shell is present in a ratio of 1% to 40% by weight.

12. The hollow resin particles according to any one of claims 1 to 11, wherein they 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 claimed in claim 13, wherein it is a sealant for semiconductor chips.

Images