Hollow resin particles, method for producing same, and use thereof

Abstract

A hollow resin particle according to an embodiment of the present invention has a shell part and a hollow part surrounded by the shell part, and is characterized in that: the shell part contains a polymer (P) obtained by polymerizing a composition containing a monomer (M) containing a crosslinkable monomer and a monofunctional monomer; when a moisture absorption test is performed under a condition I of 50 DEG C, a relative humidity of 95%, and 5 days, the dielectric loss tangent Df1 at a measurement frequency of 10 GHz before the moisture absorption test and the dielectric loss tangent Df2 at a measurement frequency of 10 GHz after the moisture absorption test under the condition I satisfy the following formula: Df2-Df1 < = 0.01, and the dielectric loss tangent Df1 is less than 0.0017.

Description

TECHNICAL FIELD

[0001] The present application relates to a hollow resin particle, a method for producing the same, and a use thereof. BACKGROUND

[0002] In order to achieve the high speed of information processing using electronic devices, attempts have been made to lower the dielectric constant and the dielectric loss tangent of the insulating layer of a multilayer printed board. As one of them, research is being conducted to introduce voids to the resin layer by mixing hollow particles having a shell portion and a hollow portion surrounded by the shell portion in a thermosetting resin, thereby achieving a low dielectric constant and a low dielectric loss tangent.

[0003] As a conventional hollow resin particle, for example, a hollow resin particle obtained by suspension polymerization of divinylbenzene together with hexadecane is reported (Patent Literature 1). However, a hollow resin particle having a composition containing a large amount of divinylbenzene can cause a high relative dielectric constant and a high dielectric loss tangent due to a large amount of vinyl groups remaining inside the particle. In addition, since hexadecane has a high boiling point, it is easy to remain inside the hollow resin particle, which can cause deterioration of dielectric properties.

[0004] As a conventional hollow resin particle, a hollow particle obtained by suspension polymerization of a monomer having an acrylic multi-functional monomer represented by trimethylolpropane tri(meth)acrylate and an acrylic mono-functional monomer represented by methyl acrylate as main components together with a hydrophobic solvent is reported (Patent Literature 2). However, in general, the values of the dielectric constant and the dielectric loss tangent of an acrylic resin are high, and the heat resistance is insufficient. Therefore, the hollow particle described in Patent Literature 2 is not suitable for the purpose of achieving a low dielectric constant and a low dielectric loss tangent of the resin layer.

[0005] As a conventional hollow resin particle, for example, a hollow resin particle obtained by suspension polymerization of divinylbenzene together with a hydrophobic solvent is reported (Patent Literature 3). However, a hollow resin particle having a composition containing a large amount of divinylbenzene can cause a high dielectric loss tangent due to a large amount of vinyl groups remaining inside the particle. PRIOR ART DOCUMENTS PATENT LITERATURE

[0006] Patent Literature 1: Japanese Patent No. 4171489 Patent Literature 2: International Publication No. 2022-107641 Patent Literature 3: International Publication No. 2022-092076 SUMMARY PROBLEMS TO BE SOLVED BY THE INVENTION

[0007] The existing hollow resin particles absorb moisture in a high humidity environment, which can deteriorate the dielectric constant and dielectric loss tangent of a member in which the hollow resin particles are mixed. Therefore, there is a demand for a hollow resin particle that is not affected by a humidity environment. Thus, the present invention was achieved in order to solve the above problem, and the main object thereof is to provide a hollow resin particle having a shell portion and a hollow portion surrounded by the shell portion, which has excellent dielectric properties that are not affected by a humidity environment. In addition, the object of the present invention is to provide a method for producing such a hollow resin particle. Further, the object of the present invention is to provide a use of such a hollow resin particle. Means for solving the technical problem

[0008] [1] The hollow resin particle of the embodiment of the present invention is a hollow resin particle having a shell portion and a hollow portion surrounded by the shell portion, wherein the shell portion contains a polymer (P) obtained by polymerizing a composition containing a monomer (M) containing a crosslinkable monomer and a monofunctional monomer, and in the case where a moisture absorption test under Condition I of 50°C, 95% relative humidity, and 5 days is performed, the dielectric loss tangent Df1 at a measurement frequency of 10 GHz before the moisture absorption test and the dielectric loss tangent Df2 at a measurement frequency of 10 GHz after the moisture absorption test under Condition I satisfy Formula (1), and the dielectric loss tangent Df1 is less than 0.0017. Df2 - Df1 ≤ 0.01 (1) [2] The hollow resin particle according to the above [1], wherein the relative dielectric constant at a measurement frequency of 10 GHz can be less than 1.5. [3] The hollow resin particle according to the above [1] or [2], wherein the crosslinkable monomer can be an aromatic crosslinkable monomer. [4] The hollow resin particle according to the above [3], wherein the composition can contain a hydrocarbon resin (A), and in the case where the total amount of the monomer (M) and the hydrocarbon resin (A) is 100 parts by weight, the aromatic crosslinkable monomer can be 1 part by weight to 40 parts by weight. [5] The hollow resin particle according to any one of the above [1] to [4], wherein the composition can contain a hydrocarbon resin (A), and in the case where the total amount of the monomer (M) and the hydrocarbon resin (A) is 100 parts by weight, the hydrocarbon resin (A) can be 1 part by weight to 10 parts by weight. [6] The hollow resin particle according to any one of the above [1] to [5], wherein the monofunctional monomer can be at least one selected from the group consisting of styrene, α-methylstyrene, ethylvinylbenzene, vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, vinylbiphenyl, vinylnaphthalene, and acenaphthylene. [7] The hollow resin particle according to any one of the above [1] to [6], can have a 5% thermogravimetric reduction temperature of 270°C or higher when increasing the temperature at 10°C / minute in an air atmosphere. [8] The hollow resin particle according to any one of the above [1] to [7], can have a volume average particle diameter of 0.1 μm to 30 μm. [9] The hollow resin particle of the embodiment of the present application is a hollow resin particle having a shell portion and a hollow portion surrounded by the shell portion, wherein the shell portion contains a polymer (P) obtained by polymerizing a composition containing a monomer (M) containing a crosslinkable monomer and a monofunctional monomer, a dielectric loss tangent Df1 at a measurement frequency of 10 GHz before a hygroscopicity test under Condition II of 85°C, a relative humidity of 85%, and 5 days, and a dielectric loss tangent Df3 at a measurement frequency of 10 GHz after the hygroscopicity test under Condition II satisfy Formula (2), and the dielectric loss tangent Df1 is less than 0.0017. Df3 - Df1 ≤ 0.02 (2)

[10] The hollow resin particle according to any one of the above [1] to [9] can be used for a resin composition for a semiconductor member.

[11] The resin composition for a semiconductor member of the embodiment of the present application contains the hollow resin particle according to any one of the above [1] to

[10] .

[12] The method for producing a hollow resin particle of the embodiment of the present application is a method for reacting a monomer (M) containing a crosslinkable monomer and a monofunctional monomer and a hydrocarbon-based resin (A) in the presence of a non-reactive solvent in an aqueous medium, and when the total amount of the above monomer (M) and the above hydrocarbon-based resin (A) is 100 parts by weight, the above crosslinkable monomer is 1 part by weight to 40 parts by weight.

[13] The method for producing a hollow resin particle according to the above

[12] , wherein when the total amount of the above monomer (M) and the above hydrocarbon-based resin (A) is 100 parts by weight, the above hydrocarbon-based resin (A) can be 1 part by weight to 10 parts by weight. Effects of the Invention

[0009] According to the embodiment of the present application, it is possible to provide a hollow resin particle having a shell portion and a hollow portion surrounded by the shell portion, which has excellent dielectric properties that are not affected by a humidity environment. Furthermore, it is also possible to provide a method for producing such a hollow resin particle. Further, it is also possible to provide a use of such a hollow resin particle. BRIEF DESCRIPTION OF DRAWINGS

[0010] Figure 1is a SEM photograph of a cross section of the particle (1) obtained in Example 1. Figure 2 is a SEM photograph of a cross section of the particle (2) obtained in Example 2. Figure 3 is a SEM photograph of a cross section of the particle (3) obtained in Example 3. Figure 4 is a SEM photograph of a cross section of the particle (4) obtained in Example 4. Figure 5 is a SEM photograph of a cross section of the particle (5) obtained in Example 5. Figure 6 is a SEM photograph of a cross section of the particle (6) obtained in Example 6. Figure 7 is a SEM photograph of a cross section of the particle (7) obtained in Example 7. Figure 8 is a SEM photograph of a cross section of the particle (C1) obtained in Comparative Example 1. Figure 9 is a SEM photograph of a cross section of the particle (C2) obtained in Comparative Example 2. Figure 10 is a SEM photograph of a cross section of the particle (C3) obtained in Comparative Example 3. DETAILED DESCRIPTION

[0011] Hereinafter, embodiments of the present application will be described, but the present application is not limited to these embodiments.

[0012] In the present specification, when the expression "(meth)acrylic acid" appears, it means "acrylic acid and / or methacrylic acid"; when the expression "(meth)acrylate" appears, it means "acrylate and / or methacrylate"; when the expression "(meth)allyl" appears, it means "allyl and / or methallyl"; and when the expression "(meth)acryloyl" appears, it means "acryloyl and / or methacryloyl".

[0013] 1. Hollow resin particle 1-1. Structure and properties of the hollow resin particle The hollow resin particle of the embodiment of the present application is a hollow resin particle having a shell portion and a hollow portion surrounded by the shell portion. The hollow resin particle of the embodiment of the present application, in the case where a moisture absorption test under Condition I of 50°C, 95% relative humidity, and 5 days is performed, satisfies the following Equation (1) between the dielectric loss tangent tan δ at a measurement frequency of 10 GHz before the moisture absorption test Df1 and the dielectric loss tangent tan δ at a measurement frequency of 10 GHz after the moisture absorption test under Condition I Df2, and the dielectric loss tangent tan δ Df1 is less than 0.0017. Df2 - Df1 ≤ 0.01 (1)

[0014] Here, the hollow means a state where the inside is filled with a substance other than resin, such as a gas or a liquid, and, in terms of aspects in which the effects of the present application can be further exhibited, it is preferable to mean a state where it is filled with a gas.

[0015] The hollow portion can be constituted by one hollow region, or can be constituted by a plurality of hollow regions (porous structure). The hollow portion is preferably constituted by a porous structure.

[0016] The hollow resin particle of the embodiment of the present application, in which the dielectric loss tangent tan δ Df1 before the moisture absorption test and the dielectric loss tangent tan δ Df2 after the moisture absorption test under Condition I satisfy the above Equation (1) relationship, has a sufficiently small difference between Df2 and Df1, and thus an increase in the dielectric loss tangent tan δ caused by moisture absorption is suppressed. Furthermore, the hollow resin particle of the embodiment of the present application has excellent dielectric properties. According to the above constitution, deterioration of the dielectric properties caused by a humidity environment is reduced, and a hollow resin particle having excellent dielectric properties that are not affected by a humidity environment can be achieved. As a result, a resin composition using the hollow resin particle of the embodiment of the present application can exhibit excellent dielectric properties that are not affected by a humidity environment. As the excellent dielectric properties, for example, a low dielectric constant, a low dielectric loss tangent tan δ can be cited.

[0017] The lower limit value of the difference between Df2 and Df1 represented by Df2 - Df1 is, for example, 0 and above. The difference between Df2 and Df1 can be 0.005 and below, or 0.003 and below. The difference between Df2 and Df1 is preferably 0.002 and below, more preferably 0.001 and below, further preferably 0.0008 and below, particularly preferably 0.0007 and below.

[0018] The hollow resin particle of the embodiment of the present application preferably satisfies the following Equation (2) between the dielectric loss tangent tan δ Df1 and the dielectric loss tangent tan δ Df3 at a measurement frequency of 10 GHz after the moisture absorption test under Condition II of 85°C, 85% relative humidity, and 5 days, in the case where a moisture absorption test under Condition II is performed. Df3 - Df1 ≤ 0.02 (2)

[0019] According to another aspect of the present application, there is provided a hollow resin particle having a shell portion and a hollow portion surrounded by the shell portion, wherein the shell portion contains a polymer (P) obtained by polymerizing a composition containing a monomer (M) containing a crosslinkable monomer and a monofunctional monomer, and in a case where a moisture absorption test under Condition II is performed, a dielectric loss tangent Df1 at a measurement frequency of 10 GHz before the moisture absorption test and a dielectric loss tangent Df3 at a measurement frequency of 10 GHz after the moisture absorption test under Condition II satisfy Formula (2), and the dielectric loss tangent Df1 is less than 0.0017.

[0020] This hollow resin particle is suppressed in an increase in the dielectric loss tangent even under a condition in which the hollow resin particle is likely to absorb moisture. According to the above configuration, a hollow resin particle having excellent dielectric properties that are not affected by a humidity environment can be achieved. Thus, a resin composition using the hollow resin particle of the embodiment of the present application can exhibit excellent dielectric properties that are not affected by a humidity environment.

[0021] In the present specification, the "dielectric loss tangent Df1 (before the moisture absorption test)" means the dielectric loss tangent of the hollow resin particle in a so-called initial state before the moisture absorption test, which is not placed in the environment of Condition I nor in the environment of Condition II. Thus, the above Formula (1) represents a relationship of an amount of change in the dielectric loss tangent of the hollow resin particle from an initial value due to the moisture absorption test under Condition I, and the above Formula (2) represents a relationship of an amount of change in the dielectric loss tangent of the hollow resin particle from an initial value due to the moisture absorption test under Condition II.

[0022] The lower limit value of the difference between Df3 and Df1, which is represented by Df3 - Df1, is, for example, 0 and above. The difference between Df3 and Df1 can be 0.01 and below, or 0.005 and below. The difference between Df3 and Df1 is preferably 0.004 and below, more preferably 0.003 and below, further preferably 0.002 and below, particularly preferably 0.001 and below.

[0023] The volume average particle diameter of the hollow resin particle of the embodiment of the present application is preferably from 0.1 μm to 100 μm, more preferably from 0.2 μm to 50.0 μm, further preferably from 0.3 μm to 30.0 μm, particularly preferably from 0.4 μm to 20.0 μm. The volume average particle diameter of the hollow resin particle of the embodiment of the present application can be from 0.1 μm to 30 μm. If the volume average particle diameter of the hollow resin particle of the embodiment of the present application is within the above range, the effect of the present application can be further exhibited. If the volume average particle diameter of the hollow resin particle of the embodiment of the present application is outside the above range and too small, the thickness of the shell portion becomes relatively thin, and thus it can not become a hollow resin particle having sufficient strength, and when the hollow resin particle is kneaded in a thermosetting resin, the thermosetting resin can penetrate into the inside of the hollow resin particle. If the average particle diameter of the hollow resin particle of the embodiment of the present application is outside the above range and too large, it can be difficult to cause phase separation between the polymer produced by polymerization of the monomer component and the solvent in suspension polymerization, and thus it can be difficult to form the shell portion.

[0024] The coefficient of variation (CV value) of the particle diameter of the hollow resin particle of the embodiment of the present application is preferably from 10% to 50%, more preferably from 15% to 45%, further preferably from 18% to 42%, particularly preferably from 20% to 40%. If the coefficient of variation (CV value) of the particle diameter of the hollow resin particle of the embodiment of the present application is within the above range, the effect of the present application can be further exhibited. If the coefficient of variation (CV value) of the particle diameter of the hollow resin particle of the embodiment of the present application is outside the above range and too small, when the hollow resin particle is kneaded in a thermosetting resin to produce a resin composition, the hollow resin particle can not be dispersed in the thermosetting resin, and for example, when a resin layer is produced from the resin composition, the thickness can be deviated. If the coefficient of variation (CV value) of the particle diameter of the hollow resin particle of the embodiment of the present application is outside the above range and too large, due to an increase in the amount of coarse particles, for example, when a resin layer is produced from the resin composition, it can be difficult to achieve thinning or the thickness can be deviated.

[0025] The hollow resin particle of the embodiment of the present application preferably has a 5% thermal weight reduction temperature of 300°C or higher, more preferably 320°C or higher, further preferably 340°C or higher, particularly preferably 360°C or higher, when heated at a rate of 10°C / minute in a nitrogen atmosphere. The upper limit of the 5% thermal weight reduction temperature in a nitrogen atmosphere is, in practice, preferably 500°C or lower. If the 5% thermal weight reduction temperature of the hollow resin particle of the embodiment of the present application is within the above range when heated at a rate of 10°C / minute in a nitrogen atmosphere, the hollow resin particle of the embodiment of the present application can exhibit excellent heat resistance. If the 5% thermal weight reduction temperature of the hollow resin particle of the embodiment of the present application is outside the above range and too low when heated at a rate of 10°C / minute in a nitrogen atmosphere, for example, when the hollow resin particle is kneaded with a thermosetting resin to produce a resin composition, heating for a curing reaction can cause the particle to be deformed, thereby losing the hollow portion, and thus the dielectric properties, such as low dielectric constant effect and low dielectric loss tangent effect, which should be exhibited in the resin composition due to the hollow resin particle, can possibly be reduced.

[0026] The hollow resin particle of the embodiment of the present application preferably has a 5% thermal weight reduction temperature of 270°C or higher, more preferably 280°C or higher, further preferably 290°C or higher, particularly preferably 300°C or higher, when heated at a rate of 10°C / minute in an air atmosphere. The upper limit of the 5% thermal weight reduction temperature in an air atmosphere is, in practice, preferably 500°C or lower. If the 5% thermal weight reduction temperature of the hollow resin particle of the embodiment of the present application is within the above range when heated at a rate of 10°C / minute in an air atmosphere, the hollow resin particle of the embodiment of the present application can exhibit excellent heat resistance. If the 5% thermal weight reduction temperature of the hollow resin particle of the embodiment of the present application is outside the above range and too low when heated at a rate of 10°C / minute in an air atmosphere, for example, when the hollow resin particle is kneaded with a thermosetting resin, heating for a curing reaction can cause the particle to be deformed, thereby losing the hollow portion, and thus the dielectric properties, such as low dielectric constant effect and low dielectric loss tangent effect, which should be exhibited in the resin composition due to the hollow resin particle, can possibly be reduced.

[0027] 1-2. Shell portion The shell portion contains a polymer (P) obtained by polymerizing a composition containing a monomer (M) containing a crosslinkable monomer and a monofunctional monomer. By the shell portion containing the polymer (P) having such a structure, the effects of the present application can be exhibited.

[0028] In the present specification, "polymerizing the composition (containing the monomer (M))" means polymerizing at least the monomer (M) in the composition. Thus, the present application includes a case where the above composition further contains a material which does not react with the monomer (M) (i.e., does not polymerize), and the shell portion contains the polymer (P) which is a polymer of the monomer (M) and the material. In the present specification, "reacting the monomer (M) with the hydrocarbon-based resin (A)" means reacting a composition containing the monomer (M) and the hydrocarbon-based resin (A), where "reacting the composition" means reacting at least the monomer (M) in the composition (i.e., polymerizing) as described above. Thus, for example, "reacting a composition containing the monomer (M) and the hydrocarbon-based resin (A)" can be polymerizing the monomer (M) in the presence of the hydrocarbon-based resin (A).

[0029] The polymer (P) can be only one, or two or more.

[0030] In terms of aspects in which the effects of the present application can be further exhibited, the content ratio of the polymer (P) in the shell portion is preferably 60% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, further preferably 80% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass.

[0031] The shell portion can contain any appropriate other component within a range not impairing the effects of the present application.

[0032] The polymer (P) is obtained by polymerizing a composition containing a monomer (M) containing a cross-linkable monomer and a monofunctional monomer. That is, the polymer (P) has a structural unit derived from the cross-linkable monomer and a structural unit derived from the monofunctional monomer.

[0033] In terms of aspects in which the effects of the present application can be further exhibited, the above composition preferably contains the hydrocarbon-based resin (A). That is, the shell portion is preferably a polymer (P) which is obtained by polymerizing a composition containing a monomer (M) containing a cross-linkable monomer and a monofunctional monomer and the hydrocarbon-based resin (A), has a structural unit derived from the cross-linkable monomer and a structural unit derived from the monofunctional monomer, and further contains the hydrocarbon-based resin (A) in addition to the polymer (P). Thus, the shell portion preferably further contains the hydrocarbon-based resin (A) in addition to the polymer (P).

[0034] As to the aspect in which the effect of the present application can be further exhibited, the hydrocarbon-based resin (A) is preferably 1 part by weight to 10 parts by weight, more preferably 1 part by weight to 8 parts by weight, further preferably 3 parts by weight to 8 parts by weight, particularly preferably 3 parts by weight to 5 parts by weight, in 100 parts by weight of the total amount of the monomer (M) and the hydrocarbon-based resin (A). Alternatively, the hydrocarbon-based resin (A) can be 1 part by weight to 5 parts by weight. Thus, it is possible to achieve a hollow resin particle having high heat resistance and excellent dielectric properties that are not affected by a humidity environment. If the content ratio of the hydrocarbon-based resin (A) exceeds the above range and is too large, it can be difficult to form the shell portion and the hollow portion surrounded by the shell portion.

[0035] As the hydrocarbon-based resin (A), any appropriate compound can be used without impairing the effect of the present application. The hydrocarbon-based resin (A) can include, for example, aliphatic / aromatic hydrocarbon resin, aromatic hydrocarbon resin, alicyclic hydrocarbon resin, aliphatic hydrocarbon resin. Here, the aliphatic / aromatic hydrocarbon resin means a hydrocarbon resin obtained by copolymerization of aliphatic hydrocarbon and aromatic hydrocarbon. The aliphatic / aromatic hydrocarbon resin is, for example, a resin obtained by polymerization of styrene, vinyltoluene, indene, isoprene, or the like as a main raw material. The aromatic hydrocarbon resin is, for example, a resin obtained by polymerization of styrene, vinyltoluene, indene, or the like as a main raw material. The alicyclic hydrocarbon resin is, for example, a resin obtained by hydrogenation of the aliphatic / aromatic hydrocarbon resin or the aromatic hydrocarbon resin. These hydrocarbon-based resins can be used alone or in combination of two or more. The hydrocarbon-based resin (A) is preferably at least one selected from the group consisting of aliphatic / aromatic hydrocarbon resin, aromatic hydrocarbon resin, and aliphatic hydrocarbon resin, more preferably at least one selected from the group consisting of aliphatic / aromatic hydrocarbon resin and aromatic hydrocarbon resin, further preferably aliphatic / aromatic hydrocarbon resin. According to the above, it is possible to achieve a hollow resin particle having excellent dielectric properties that are not affected by a humidity environment, and further to achieve a hollow resin particle having excellent heat resistance. Thus, when the hollow resin particle is mixed and present in a resin such as a thermosetting resin to make a resin composition, even if the thermosetting resin in which the hollow resin particle is mixed and present is heated when being subjected to molding processing or when using a solder, the hollow resin particle is less likely to substantially change, and thus it is possible to make the resin composition further exhibit desired dielectric properties.

[0036] As the crosslinkable monomer, for example, the following can be mentioned: multifunctional (meth)acrylates such as ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, glycerol tri(meth)acrylate, and the like; multifunctional acrylamide derivatives such as N,N'-methylenebis(meth)acrylamide, N,N'-ethylenebis(meth)acrylamide, and the like; multifunctional allyl derivatives such as diallylamine, tetraallyloxyethane, and the like; and aromatic crosslinkable monomers such as divinylbenzene, divinyl naphthalene, diallyl phthalate, and the like. In terms of further exhibiting the effects of the present application, as the crosslinkable monomer, an aromatic crosslinkable monomer is preferred, and divinylbenzene is more preferred. The crosslinkable monomer can be one type or two or more types.

[0037] As the monofunctional monomer, for example, the following can be mentioned: (meth)acrylic acid alkyl esters having 1 to 16 carbon atoms such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cetyl (meth)acrylate, and the like; aromatic monofunctional monomers such as styrene, a-methylstyrene, ethylvinylbenzene, vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, vinylbiphenyl, vinyl naphthalene, and the like; dicarboxylic acid ester monomers such as dimethyl maleate, diethyl fumarate, dimethyl fumarate, diethyl fumarate, and the like; maleic anhydride; N-vinylcarbazole; and (meth)acrylonitrile. In terms of further exhibiting the effects of the present application, the monofunctional monomer is preferably an aromatic monofunctional monomer. The monofunctional monomer is preferably at least one type selected from the group consisting of styrene, a-methylstyrene, ethylvinylbenzene, vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, vinylbiphenyl, vinyl naphthalene, and acenaphthylene, and more preferably styrene or ethylvinylbenzene. The monofunctional monomer can be one type or two or more types.

[0038] When the monomer (M) contains an aromatic crosslinkable monomer, the aromatic crosslinkable monomer is preferably 1 part by weight to 40 parts by weight, more preferably 1 part by weight to 35 parts by weight, further preferably 1 part by weight to 30 parts by weight, and particularly preferably 1 part by weight to 25 parts by weight, based on 100 parts by weight of the total amount of the monomer (M) and the hydrocarbon-based resin (A). In addition, the aromatic crosslinkable monomer is preferably 3 parts by weight to 40 parts by weight, more preferably 5 parts by weight to 40 parts by weight, further preferably 8 parts by weight to 40 parts by weight, and particularly preferably 10 parts by weight to 40 parts by weight. Thereby, it is possible to realize a hollow resin particle having excellent dielectric properties that are not affected by the humidity environment. If the content ratio of the aromatic crosslinkable monomer is too large beyond the above range, the dielectric properties of the hollow resin particle can deteriorate. If the content ratio of the aromatic crosslinkable monomer is too small beyond the above range, the particles can agglomerate in the manufacturing process, and thus it can not be possible to sufficiently obtain a hollow resin particle.

[0039] The reaction of the composition containing the monomer (M) and the hydrocarbon-based resin (A) can be performed by any appropriate reaction without impairing the effects of the present application. Such a reaction is, for example, a suspension polymerization reaction.

[0040] When the suspension polymerization reaction is performed, typically, the oil phase is added to the water phase, and the polymerization reaction is performed while the oil phase is suspended. The water phase and the oil phase can contain any appropriate solvent without impairing the effects of the present application. As such a solvent, for example, the water-based medium, the non-reactive solvent described later can be exemplified. The solvent can be only one, or two or more.

[0041] When the reaction of the composition containing the monomer (M) and the hydrocarbon-based resin (A) is performed, any appropriate additive (B) that does not belong to the monomer (M) or the hydrocarbon-based resin (A) can be used without impairing the effects of the present application. The additive (B) can be only one, or two or more. The additive (B) described here does not include the solvent such as the water-based medium, the non-reactive solvent, and the dispersion stabilizer described later.

[0042] The content ratio of the additive (B) with respect to the total amount of the monomer (M) and the hydrocarbon-based resin (A) is preferably 0% by mass to 40% by mass, more preferably 0% by mass to 30% by mass, further preferably 0% by mass to 20% by mass, particularly preferably 0% by mass to 10% by mass.

[0043] As the additive (B), any appropriate additive (B) that does not belong to the monomer (M) or the hydrocarbon-based resin (A) can be used without impairing the effects of the present application. As such an additive (B), for example, the non-crosslinkable polymer, the polymerization initiator, the surfactant, and other compounds can be exemplified.

[0044] By including the non-crosslinkable polymer as the additive (B), the phase separation of the polymer (P) generated along with the reaction from the solvent is promoted, and thus the formation of the shell can be promoted.

[0045] As the non-crosslinkable polymer, for example, at least one selected from the group consisting of a polyolefin, a styrene-based polymer, a (meth)acrylic-based polymer, and a styrene-(meth)acrylic-based polymer can be exemplified.

[0046] As the polyolefin, for example, polyethylene, polypropylene, poly-α-olefin, and the like can be exemplified. From the viewpoint of the solubility of the compound (A) and the monomer component containing the monomer (M), it is preferable to use a side chain crystalline polyolefin that uses a long-chain α-olefin as a raw material, a low-molecular-weight polyolefin or an olefin oligomer manufactured by a metallocene catalyst.

[0047] As the styrene-based polymer, for example, polystyrene, a styrene-acrylonitrile copolymer, an acrylonitrile-butadiene-styrene copolymer, and the like can be exemplified.

[0048] As the (meth)acrylic polymer, for example, poly(meth)acrylate, poly(meth)acrylate, poly(meth)acrylate, and the like can be exemplified.

[0049] As the styrene-(meth)acrylic polymer, for example, styrene-(meth)acrylate copolymer, styrene-(meth)acrylate copolymer, styrene-(meth)acrylate copolymer, and the like can be exemplified.

[0050] In the suspension polymerization reaction, from the viewpoint of being able to more stably produce the desired hollow resin particles, a surfactant can be used as the additive (B). In terms of being able to further exhibit the effects of the present application, as the surfactant, at least one selected from the group consisting of an amphoteric surfactant and an anionic surfactant is preferable, and at least an amphoteric surfactant is more preferable. Specifically, it is preferable to add at least one selected from the group consisting of an amphoteric surfactant and an anionic surfactant to the aqueous phase containing the aqueous medium, and more preferably, it is preferable to add at least an amphoteric surfactant to the aqueous phase containing the aqueous medium (only an amphoteric surfactant is added, or both an amphoteric surfactant and an anionic surfactant are added).

[0051] As the amphoteric surfactant, any appropriate amphoteric surfactant can be used within a range not impairing the effects of the present application. As such an amphoteric surfactant, a publicly known amphoteric surfactant that can be used in the production of resin particles can be used. As the amphoteric surfactant, for example, lauryl dimethyl amine oxide, lauryl dimethyl aminoethyl betaine, phosphate ester-based surfactants, phosphite ester-based surfactants can be exemplified. The amphoteric surfactant can be only one, or two or more.

[0052] As the anionic surfactant, any appropriate anionic surfactant can be used within a range not impairing the effects of the present application. As such an anionic surfactant, for example, fatty acid salts, polysulfonic acid salts, polycarboxylic acid salts, alkyl sulfate salts, alkyl aryl sulfonic acid salts, dialkyl sulfonic acid salts, dialkyl sulfosuccinic acid salts, alkyl phosphate salts, polyoxyethylene alkyl ether sulfate salts, polyoxyethylene alkyl aryl ether sulfate salts, naphthalene sulfonic acid formaldehyde condensates, polyoxyethylene alkyl phosphoric acid sulfonic acid salts, glycerol borate ester fatty acid esters, polyoxyethylene glycerol fatty acid esters can be exemplified. Specifically, for example, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, ammonium polyoxyethylene lauryl ether sulfate, polyoxyethylene nonyl phenyl ether sulfate, sodium salt of β-naphthalene sulfonic acid formaldehyde condensate can be exemplified. The anionic surfactant can be only one, or two or more.

[0053] The amount of the surfactant used is preferably in the range of 0.01 parts by weight to 0.3 parts by weight, more preferably in the range of 0.02 parts by weight to 0.2 parts by weight, relative to 100 parts by weight of the water-based medium.

[0054] As the other compound included as the additive (B), a compound having at least one selected from the group consisting of a phosphate structure and a radical-reactive group, preferably a compound having a phosphate structure and a radical-reactive group, can be used. As such a compound, a compound represented by formula (3) is preferable in terms of further exhibiting the effects of the present application. [Chemical Formula 1]

[0055] In formula (3), R 3 , R 5 is a linear or branched alkylene group having 1 to 30 carbon atoms, R 4 represents a methyl group or a hydrogen atom. In formula (3), m represents 1 to 300. In formula (3), n represents 1 to 3. In formula (3), a is 0 or 1, b is 0 to 300, and c is 0 or 1.

[0056] In formula (3), R 3 is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably a linear or branched alkylene group having 1 to 10 carbon atoms, further preferably a linear or branched alkylene group having 1 to 8 carbon atoms, particularly preferably a linear or branched alkylene group having 1 to 6 carbon atoms, most preferably a linear or branched alkylene group having 1 to 4 carbon atoms.

[0057] In formula (3), R 5 is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably a linear or branched alkylene group having 1 to 10 carbon atoms, further preferably a linear or branched alkylene group having 1 to 8 carbon atoms, particularly preferably a linear or branched alkylene group having 1 to 6 carbon atoms, most preferably a linear or branched alkylene group having 1 to 4 carbon atoms.

[0058] In formula (3), m is preferably 1 to 100, more preferably 1 to 50, further preferably 1 to 40, particularly preferably 1 to 30.

[0059] In formula (3), b is preferably 0 to 100, more preferably 0 to 50, further preferably 0 to 10, particularly preferably 0 to 5, most preferably 0 or 1.

[0060] As such a compound, a compound that can be obtained as a commercial product can also be used. As such a compound, for example, "KAYAMER (registered trademark) PM-21" (manufactured by Nippon Kayaku Co., Ltd.) can be cited from the viewpoint of compatibility.

[0061] In the reaction of the composition containing the monomer (M) and the hydrocarbon-based resin (A), any appropriate dispersing stabilizer (C) that does not belong to either the monomer (M) or the hydrocarbon-based resin (A) can be used within a range not impairing the effects of the present application. The dispersing stabilizer (C) can be only one or two or more.

[0062] The dispersing stabilizer (C) is preferably 0.5 parts by weight to 10 parts by weight with respect to 100 parts by weight of the water-based medium. The dispersing stabilizer (C) can be only one or two or more.

[0063] As the dispersing stabilizer (C), for example, polyvinyl alcohol, polycarboxylic acid, cellulose (hydroxyethyl cellulose, carboxymethyl cellulose, etc.), polyvinylpyrrolidone, sodium tripolyphosphate, and the like can be cited. In addition, as the dispersing stabilizer, calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, and the like; calcium pyrophosphate, magnesium pyrophosphate, aluminum pyrophosphate, zinc pyrophosphate, and the like; calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, colloidal silica, and the like can be cited. Among them, from the viewpoint of being easily removed from the hollow resin particles and not easily remaining on the surface of the hollow resin particles, it is preferable to use magnesium pyrophosphate.

[0064] 1-3. Relative dielectric constant and dielectric loss tangent of hollow resin particles In the electronic device, which is one of the uses of the hollow resin particles, the transmission loss of the radio wave transmitted for communication, which is heat-converted in the dielectric, is expressed as the product of the frequency, the square root of the relative dielectric constant, and the dielectric loss tangent. That is, the transmission signal is easily converted into heat in proportion to the frequency, and thus in order to suppress the transmission loss, the higher the frequency band, the lower dielectric properties are required for the material of the communication member (semiconductor member).

[0065] Therefore, the relative dielectric constant of the hollow resin particle of the embodiment of the present application is preferably 1.0 to 2.5, more preferably 1.0 to 2.3, further preferably 1.0 to 2.0 at a measurement frequency of 10 GHz. Herein, in the present specification, the term "relative dielectric constant of the hollow resin particle" means the relative dielectric constant of the hollow resin particle before the moisture absorption test. The relative dielectric constant before the moisture absorption test is the relative dielectric constant of the hollow resin particle (i.e., the hollow resin particle in the initial state) under the conditions in which the dielectric loss tangent Df1 is measured.

[0066] The dielectric loss tangent of the hollow resin particle of the embodiment of the present application is less than 0.0017 at a measurement frequency of 10 GHz. The dielectric loss tangent of the hollow resin particle of the embodiment of the present application is preferably 0 to 0.0016, more preferably 0 to 0.0015, further preferably 0 to 0.0014, particularly preferably 0 to 0.0013 at a measurement frequency of 10 GHz. Herein, in the present specification, the term "dielectric loss tangent of the hollow resin particle" means the dielectric loss tangent of the hollow resin particle before the moisture absorption test (i.e., the dielectric loss tangent Df1). If the relative dielectric constant and the dielectric loss tangent of the hollow resin particle of the embodiment of the present application are within the above ranges, the effect of the present application can be further exhibited.

[0067] The hollow resin particle of the embodiment of the present application preferably has a relative dielectric constant of less than 2.0 and a dielectric loss tangent of less than 0.0017 at a measurement frequency of 10 GHz, and more preferably has a relative dielectric constant of less than 1.5 and a dielectric loss tangent of less than 0.0017 at a measurement frequency of 10 GHz.

[0068] If the relative dielectric constant of the hollow resin particle of the embodiment of the present application exceeds 2.5, even if the hollow resin particle is mixed in the thermosetting resin, for example, a sufficient low dielectric constant effect cannot be obtained, and transmission loss can occur when used in a high frequency band, resulting in an increase in the heat generation amount of the member. In particular, if the relative dielectric constant of the hollow resin particle exceeds 2.05, the above-mentioned adverse situations are more likely to occur.

[0069] The relative dielectric constant of the hollow resin particle of the embodiment of the present application after the moisture absorption test under Condition I of 50°C, 95% relative humidity, and 5 days is preferably 1.0 to 2.5, more preferably 1.0 to 2.3, further preferably 1.0 to 2.0 at a measurement frequency of 10 GHz.

[0070] The hollow resin particle of the embodiment of the present application preferably has a dielectric loss tangent (dielectric loss tangent Df2) after the moisture absorption test under the above Condition I at a measurement frequency of 10 GHz of 0 to 0.005, more preferably 0 to 0.004, further preferably 0 to 0.003, particularly preferably 0 to 0.002. If the relative dielectric constant and the dielectric loss tangent of the hollow resin particle of the embodiment of the present application after the moisture absorption test under the above Condition I are within the above ranges, the effect of the present application can be further exhibited.

[0071] The hollow resin particle of the embodiment of the present application preferably has a relative dielectric constant after the moisture absorption test under Condition II at 85°C, 85% relative humidity, and for 5 days of 1.0 to 2.5, more preferably 1.0 to 2.3, further preferably 1.0 to 2.0, at a measurement frequency of 10 GHz.

[0072] The hollow resin particle of the embodiment of the present application preferably has a dielectric loss tangent (dielectric loss tangent Df3) after the moisture absorption test under the above Condition II at a measurement frequency of 10 GHz of 0 to 0.01, more preferably 0 to 0.005, further preferably 0 to 0.004, particularly preferably 0 to 0.003. If the relative dielectric constant and the dielectric loss tangent of the hollow resin particle of the embodiment of the present application after the moisture absorption test under the above Condition II are within the above ranges, the effect of the present application can be further exhibited.

[0073] The values of the relative dielectric constant and the dielectric loss tangent of the hollow resin particle of the embodiment of the present application are not limited to the above values. For example, in the case where the hollow resin particle of the embodiment of the present application is used for other applications than semiconductor components, the values of the relative dielectric constant and the dielectric loss tangent are not limited to the above values.

[0074] 1-4. Use of Hollow Resin Particle The hollow resin particle of the embodiment of the present application can be used for various applications. In terms of aspects in which the effect of the present application can be further utilized, the hollow resin particle of the embodiment of the present application is suitable for semiconductor components, and is suitably used for a resin composition for semiconductor components, for example. In addition, the hollow resin particle of the embodiment of the present application can be used for applications other than the above-described use for a resin composition for semiconductor components, such as a coating composition, a cosmetic, a paper coating composition, a heat insulating resin composition, a light diffusing resin composition, a light diffusing film, and the like.

[0075] <Resin Composition for Semiconductor Component> The hollow resin particle of the embodiment of the present application can be suitably used for a resin composition for a semiconductor member because it can achieve low dielectric constant, low dielectric loss tangent, and excellent heat resistance.

[0076] The resin composition for a semiconductor member of the embodiment of the present application contains the hollow resin particle of the embodiment of the present application.

[0077] The semiconductor member means a member constituting a semiconductor, and examples thereof include a semiconductor package and a semiconductor module. In the present specification, the resin composition for a semiconductor member means a resin composition for a semiconductor member.

[0078] The semiconductor package is constituted with at least one member selected from the group consisting of a molding resin, an underfill material, a mold underfill material, a die attach material, a prepreg for a semiconductor package substrate, a metal-clad laminate for a semiconductor package substrate, and a build-up material for a printed circuit board for a semiconductor package, with an IC chip as an essential constituent member.

[0079] The semiconductor module is constituted with at least one member selected from the group consisting of a prepreg for a printed circuit board, a metal-clad laminate for a printed circuit board, a build-up material for a printed circuit board, a solder resist material, a cover film, an electromagnetic wave shielding film, and an adhesive sheet for a printed circuit board, with a semiconductor package as an essential constituent member.

[0080] <Coating composition> The hollow resin particle of the embodiment of the present application can impart excellent appearance to a coating film containing it, and thus can be suitably used for a coating composition.

[0081] The coating composition of the embodiment of the present application contains the hollow resin particle of the embodiment of the present application.

[0082] The coating composition of the embodiment of the present application preferably contains at least one selected from the group consisting of a binder resin and a UV-curable resin. The binder resin can be only one or two or more. The UV-curable resin can be only one or two or more.

[0083] As the binder resin, any appropriate binder resin can be used without impairing the effects of the present application. As such a binder resin, examples thereof include a resin soluble in an organic solvent or water, and an emulsion-type water-based resin capable of being dispersed in water. Specifically, as the binder resin, examples thereof include an acrylic resin, an alkyd resin, a polyester resin, a polyurethane resin, a chlorinated polyolefin resin, and an amorphous polyolefin resin.

[0084] As the UV-curable resin, any appropriate UV-curable resin can be used within a range not impairing the effects of the present application. As such a UV-curable resin, for example, a multifunctional (meth)acrylate resin, a multifunctional urethane acrylate resin, preferably a multifunctional (meth)acrylate resin, more preferably a multifunctional (meth)acrylate resin having three or more (meth)acryloyl groups in one molecule can be exemplified. As the multifunctional (meth)acrylate resin having three or more (meth)acryloyl groups in one molecule, specifically, for example, trimethylolpropane tri(meth)acrylate, trimethyloloethane tri(meth)acrylate, 1,2,4-cyclohexane tetra(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol triacrylate, tripentaerythritol hexaacrylate can be exemplified.

[0085] When the coating composition of the embodiment of the present application contains at least one selected from the group consisting of the binder resin and the UV-curable resin, the content ratio thereof can be any appropriate content ratio according to the purpose. Typically, the hollow resin particles of the embodiment of the present application are preferably 5% by weight to 50% by weight, more preferably 10% by weight to 50% by weight, further preferably 20% by weight to 40% by weight, relative to the total amount of at least one selected from the group consisting of the binder resin (in the case of an emulsion type water-based resin, the solid content is converted) and the UV-curable resin and the hollow resin particles of the embodiment of the present application.

[0086] When the UV-curable resin is used, a photopolymerization initiator is preferably used in combination. As the photopolymerization initiator, any appropriate photopolymerization initiator can be used within a range not impairing the effects of the present application. As such a photopolymerization initiator, for example, acetophenone-based, benzoin-based, benzophenone-based, phosphine oxide-based, ketal-based, a-hydroxyalkyl phenone-based, a-aminoalkyl phenone, anthraquinone-based, thioxanthone-based, azo compound-based, peroxide-based (described in Japanese Patent Application Publication No. 2001-139663, etc.), 2,3-dialkyl diketone compound-based, disulfide-based, fluoramine compound-based, aromatic sulfonium salt-based, onium salt-based, borate, active halogen compound, a-acyloxime ester can be exemplified.

[0087] The coating composition of the embodiment of the present application can contain a solvent. The solvent can be only one or two or more. When the coating composition of the embodiment of the present application contains a solvent, the content ratio thereof can be any appropriate content ratio according to the purpose.

[0088] As the solvent, any appropriate solvent can be used within a range not impairing the effects of the present application. As such a solvent, a solvent capable of dissolving or dispersing the binder resin or the UV-curable resin is preferred. As such a solvent, if it is an oil-based paint, for example, a hydrocarbon-based solvent such as toluene, xylene, and the like; a ketone-based solvent such as butanone, methyl isobutyl ketone, and the like; an ester-based solvent such as ethyl acetate, butyl acetate, and the like; an ether-based solvent such as dioxane, ethylene glycol diethyl ether, ethylene glycol monobutyl ether, and the like can be exemplified, and if it is a water-based paint, for example, water, an alcohol, and the like can be exemplified.

[0089] The paint composition of the embodiment of the present application can be diluted as needed to adjust the viscosity. As the diluent, any appropriate diluent can be used as needed. As such a diluent, for example, the aforementioned solvents can be exemplified. The diluent can be only one, or two or more.

[0090] The paint composition of the embodiment of the present application can contain other components as needed, such as a surface adjusting agent, a flowability adjusting agent, an ultraviolet absorber, a light stabilizer, a curing catalyst, a extender pigment, a coloring pigment, a metallic pigment, a mica powder pigment, a dye.

[0091] When the paint composition of the embodiment of the present application is used to form a coating film, as the coating method thereof, any appropriate coating method can be used as needed. As such a coating method, for example, a spray coating method, a roll coating method, a brush coating method, a reverse roll coating method, a gravure coating method, a die coating method, a comma coating method, a spray coating method can be exemplified.

[0092] When the paint composition of the embodiment of the present application is used to form a coating film, as the forming method thereof, any appropriate forming method can be used as needed. As such a forming method, for example, a method in which a coating film is formed by coating any coating surface of a substrate to make a coated film, drying the coated film, and curing the coated film as needed can be exemplified. As the substrate, for example, a metal, wood, glass, plastic (PET (polyethylene terephthalate), PC (polycarbonate), an acrylic resin, TAC (triacetyl cellulose), and the like) can be exemplified.

[0093] <Thermal Insulating Resin Composition> The hollow resin particle of the embodiment of the present application can impart excellent thermal insulation to a coating film containing the same, and thus can be suitably used for a thermal insulating resin composition. The coating film containing the hollow resin particle of the embodiment of the present application can exhibit excellent reflectance in the wavelength range from ultraviolet light to near-infrared light.

[0094] The thermal insulating resin composition of the embodiment of the present application contains the hollow resin particle of the embodiment of the present application.

[0095] The thermally insulating resin composition of the embodiment of the present application preferably contains at least one selected from the group consisting of a binder resin and a UV-curable resin. As for the binder resin, the UV-curable resin, the aforementioned description for the coating composition can be applied.

[0096] The thermally insulating resin composition of the embodiment of the present application can contain a solvent. As for the solvent, the aforementioned description for the coating composition can be applied.

[0097] The thermally insulating resin composition of the embodiment of the present application can be diluted as necessary to adjust the viscosity. As the diluent, the aforementioned description for the coating composition can be applied.

[0098] The thermally insulating resin composition of the embodiment of the present application can contain other components as necessary, such as a coating surface adjuster, a flowability adjuster, a UV absorber, a light stabilizer, a curing catalyst, a extender pigment, a coloring pigment, a metallic pigment, a mica powder pigment, a dye.

[0099] As the coating method, the forming method when forming a coating film using the thermally insulating resin composition of the embodiment of the present application, the aforementioned description for the coating composition can be applied.

[0100] <Light-diffusing resin composition> The hollow resin particle of the embodiment of the present application can impart excellent light diffusivity to a coating film containing the same, and thus can be suitably used for a light-diffusing resin composition.

[0101] The light-diffusing resin composition of the embodiment of the present application contains the hollow resin particle of the embodiment of the present application.

[0102] The light-diffusing resin composition of the embodiment of the present application preferably contains at least one selected from the group consisting of a binder resin and a UV-curable resin. As for the binder resin, the UV-curable resin, the aforementioned description for the coating composition can be applied.

[0103] The light-diffusing resin composition of the embodiment of the present application can contain a solvent. As for the solvent, the aforementioned description for the coating composition can be applied.

[0104] The light-diffusing resin composition of the embodiment of the present application can be diluted as necessary to adjust the viscosity. As the diluent, the aforementioned description for the coating composition can be applied.

[0105] The light-diffusing resin composition of the embodiment of the present application can contain other components as necessary, such as a coating surface adjuster, a flowability adjuster, a UV absorber, a light stabilizer, a curing catalyst, a extender pigment, a coloring pigment, a metallic pigment, a mica powder pigment, a dye.

[0106] As a coating method, forming method when a coating film is formed using the light-diffusing resin composition of the embodiment of the present application, the aforementioned description for the coating composition can be applied.

[0107] <Light-diffusing film> The hollow resin particle of the embodiment of the present application can impart excellent light-diffusing properties to a film having a coating film containing the same, and thus can also be suitably used for a light-diffusing film.

[0108] The light-diffusing film of the embodiment of the present application contains the hollow resin particle of the embodiment of the present application.

[0109] The light-diffusing film of the embodiment of the present application contains a light-diffusing layer formed from the light-diffusing resin composition of the embodiment of the present application and a substrate. Note that the light-diffusing layer can be the outermost layer of the light-diffusing film, or can not be the outermost layer. The light-diffusing film of the embodiment of the present application can contain any appropriate other layer as needed. As such other layers, for example, a protective layer, a hard coat layer, a planarization layer, a high-refractive layer, an insulating layer, a conductive resin layer, a conductive metal fine particle layer, a conductive metal oxide fine particle layer, a primer layer can be cited.

[0110] As the substrate, for example, a metal, wood, glass, plastic film, plastic sheet, plastic lens, plastic panel, cathode ray tube, fluorescent display tube, liquid crystal display panel can be cited. As the plastic constituting the plastic film, plastic sheet, plastic lens, plastic panel, for example, PET (polyethylene terephthalate), PC (polycarbonate), acrylic resin, TAC (triacetyl cellulose) can be cited.

[0111] 2. Method for producing hollow resin particle The method for producing a hollow resin particle of the embodiment of the present application is a method in which a monomer (M) containing a crosslinkable monomer and a monofunctional monomer is reacted with a hydrocarbon-based resin (A) in the presence of a non-reactive solvent in an aqueous medium. That is, the polymerization of the monomer (M) is performed by reacting a composition containing the monomer (M) and the hydrocarbon-based resin (A) in the presence of a non-reactive solvent in an aqueous medium. At this time, the crosslinkable monomer is 1 part by weight to 40 parts by weight, based on 100 parts by weight of the total amount of the monomer (M) and the hydrocarbon-based resin (A).

[0112] According to the above production method, the hollow resin particle of the embodiment of the present application can be easily produced.

[0113] The method for producing a hollow resin particle of the embodiment of the present application is preferably a method in which the above monomer (M) contains an aromatic crosslinkable monomer, and the above aromatic crosslinkable monomer is 1 part by weight to 40 parts by weight, based on 100 parts by weight of the total amount of the above monomer (M) and the above hydrocarbon-based resin (A).

[0114] The hollow resin particles of the embodiments of the present application can be obtained by reacting a composition containing a monomer (M) containing a crosslinkable monomer and a monofunctional monomer, and a hydrocarbon-based resin (A) in the presence of a non-reactive solvent in an aqueous medium. Typically, the hollow resin particles of the embodiments of the present application can be produced by supplying a crosslinkable monomer, a monofunctional monomer, and a hydrocarbon-based resin (A) to a suspension polymerization reaction.

[0115] The suspension polymerization is typically suspension polymerization using an aqueous phase containing an aqueous medium, and an oil phase containing a monomer (M), a hydrocarbon-based resin (A), and a non-reactive solvent, and is preferably suspension polymerization in which the oil phase containing a monomer (M), a hydrocarbon-based resin (A), and a non-reactive solvent is added to the aqueous phase containing an aqueous medium, dispersed, and then heated.

[0116] As for the dispersion, any appropriate dispersion method can be used as long as the oil phase can exist in the aqueous phase in the form of droplets without impairing the effects of the present application. As such a dispersion method, a dispersion method using a homomixer or a homogenizer is typically used, and examples thereof include a POLYTRON homogenizer, an ultrasonic homogenizer, a high-pressure homogenizer, and the like.

[0117] The polymerization temperature can be any appropriate polymerization temperature as long as it is a temperature suitable for suspension polymerization, and any appropriate polymerization temperature can be used within a range that does not impair the effects of the present application. As such a polymerization temperature, 30°C to 90°C is preferred.

[0118] The polymerization time can be any appropriate polymerization time as long as it is a time suitable for suspension polymerization, and any appropriate polymerization time can be used within a range that does not impair the effects of the present application. As such a polymerization time, 1 hour to 48 hours is preferred.

[0119] The post-heating, which is preferably performed after the polymerization, is a process suitable for obtaining hollow resin particles with higher completion.

[0120] The temperature of the post-heating, which is preferably performed after the polymerization, can be any appropriate temperature within a range that does not impair the effects of the present application. As such a post-heating temperature, 70°C to 120°C is preferred.

[0121] The time of the post-heating, which is preferably performed after the polymerization, can be any appropriate time within a range that does not impair the effects of the present application. As such a post-heating time, 1 hour to 24 hours is preferred.

[0122] The ratio of the monomer (M) to the hydrocarbon-based resin (A) is preferably (99 parts by weight to 90 parts by weight) : (1 part by weight to 10 parts by weight), more preferably (99 parts by weight to 92 parts by weight) : (1 part by weight to 8 parts by weight), further preferably (97 parts by weight to 92 parts by weight) : (3 parts by weight to 8 parts by weight), particularly preferably (97 parts by weight to 95 parts by weight) : (3 parts by weight to 5 parts by weight), in terms of the total amount of the monomer (M) and the hydrocarbon-based resin (A) being 100 parts by weight. Alternatively, the ratio can be (99 parts by weight to 95 parts by weight) : (1 part by weight to 5 parts by weight). Thus, the hollow resin particles having excellent dielectric properties that are not affected by humidity environments can be obtained. If the content ratio of the hydrocarbon-based resin (A) exceeds the above range and is too large, it can be difficult to form the shell portion and the hollow portion surrounded by the shell portion. That is, the ratio of the hydrocarbon-based resin (A) is preferably 1 part by weight to 10 parts by weight, more preferably 1 part by weight to 8 parts by weight, in terms of the total amount of the monomer (M) and the aforementioned hydrocarbon-based resin (A) being 100 parts by weight.

[0123] The monomer (M) and the hydrocarbon-based resin (A) can be directly cited from 1. Hollow resin particles The 1-2. Shell portion The description in the item.

[0124] As the aqueous medium, for example, water, a mixed medium of water and a lower alcohol (methanol, ethanol, etc.), and the like can be cited.

[0125] The amount of use of the aqueous medium can be any appropriate amount within a range that does not impair the effects of the present application. The amount of use of such an aqueous medium is typically an amount that allows the reaction to proceed appropriately in a suspension polymerization reaction in which an oil phase is added to an aqueous phase to be suspended, and is preferably 100 parts by weight to 5000 parts by weight, more preferably 150 parts by weight to 2000 parts by weight, with respect to 100 parts by weight of the total amount of the compound (A), the monomer (M), the chain transfer agent (B), and the non-reactive solvent.

[0126] The non-reactive solvent is a solvent that does not chemically react with the monomer (M) or the hydrocarbon-based resin (A), and is preferably an organic solvent. The non-reactive solvent typically functions as a hollowing agent that imparts voids to the particles. As the non-reactive solvent, for example, heptane, hexane, toluene, cyclohexane, methyl acetate, ethyl acetate, butanone, chloroform, carbon tetrachloride, and the like can be cited. The boiling point of the non-reactive solvent is preferably lower than 100°C from the viewpoint of being easily removed from the hollow resin particles.

[0127] The non-reactive solvent as the hollowing agent can be a single solvent or a mixed solvent.

[0128] The amount of non-reactive solvent added is preferably 20 to 250 parts by weight relative to 100 parts by weight of the total amount of monomer (M) and hydrocarbon resin (A).

[0129] When reacting a composition comprising a monomer (M) and a hydrocarbon resin (A), any suitable additive (B) that is neither a monomer (M) nor a hydrocarbon resin (A) may be used, without impairing the effects of the present invention. Additive (B) may be one or two or more. The additive (B) referred to herein does not include solvents such as aqueous media and non-reactive solvents, or dispersants and stabilizers.

[0130] The proportion of additive (B) relative to the total amount of monomer (M) and hydrocarbon resin (A) is preferably 0% to 40% by weight, more preferably 0% to 30% by weight, further preferably 0% to 20% by weight, and particularly preferably 0% to 10% by weight.

[0131] As additive (B), any suitable additive that is neither a monomer (M) nor a hydrocarbon resin (A) may be used without impairing the effects of the present invention. Examples of such additives (B) include: non-crosslinked polymers, polymerization initiators, surfactants, and other compounds.

[0132] For non-crosslinked polymers, direct application is possible. 1. Hollow resin particles of 1-2. Shell The explanation in the item.

[0133] As a polymerization initiator, any suitable polymerization initiator may be used without impairing the effects of the present invention. Examples of such polymerization initiators include: organic peroxides such as lauroyl peroxide, benzoyl peroxide, o-chlorobenzoyl peroxide, o-methoxybenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, tert-butyl peroxide of 2-ethylhexanoate, and di-tert-butyl peroxide; and azo compounds such as 2,2'-azobisisobutyronitrile, 1,1'-azodicyclohexaneformitrile, and 2,2'-azobis(2,4-dimethylpentanonitrile).

[0134] The proportion of the polymerization initiator relative to the total amount of monomer (M) and hydrocarbon resin (A) is preferably in the range of 0.1% to 5% by weight. The polymerization initiator may be only one type, or two or more types.

[0135] Regarding surfactants, they can be directly cited. 1. Hollow resin particles of 1-2. Shell the description in the item.

[0136] As to the other compounds contained as the additive (B), the description in the item 1. Hollow resin particles the 1-2. Shell portion the description in the item.

[0137] In the reaction of the composition containing the monomer (M) and the hydrocarbon-based resin (A), any appropriate dispersing stabilizer (C) that does not belong to the monomer (M) nor the hydrocarbon-based resin (A) can be used within a range not impairing the effects of the present application. The dispersing stabilizer (C) can be only one, or two or more.

[0138] The dispersing stabilizer (C) is preferably 0.5 parts by weight to 10 parts by weight, relative to 100 parts by weight of the aqueous medium. The dispersing stabilizer (C) can be only one, or two or more.

[0139] As specific examples of the dispersing stabilizer (C), the description in the item 1. Hollow resin particles the 1-2. Shell portion the description in the item. Examples

[0140] Hereinafter, the present application will be specifically described by citing examples, but the present application is not limited to these examples.

[0141] <Measurement of volume average particle diameter, coefficient of variation (CV value) of particle diameter> The measurement of the volume average particle diameter of the particles was performed by the Coulter method in the following manner. The volume average particle diameter of the particles was measured by COULTER Multisizer (registered trademark) 4e (measuring device manufactured by BECKMAN COULTER Corporation). The measurement was performed using a pore diameter corrected according to the Multisizer 4e User Manual issued by BECKMAN COULTER Corporation. The pore diameter used in the measurement was appropriately selected depending on the expected volume average particle diameter of the particles to be measured. For example, when the expected volume average particle diameter was 0.2 μm to 6 μm, a pore diameter having a size of 10 μm was selected, when the expected volume average particle diameter was 0.4 μm to 12 μm, a pore diameter having a size of 20 μm was selected, and when the expected volume average particle diameter was 2.0 μm to 60 μm, a pore diameter having a size of 100 μm was selected. When the volume average particle diameter after the measurement was different from the expected volume average particle diameter, a pore diameter having an appropriate size was changed, and the measurement was performed again. As the sample used for the assay, a dispersion prepared by dispersing 0.1 g of particles in 10 mL of a 0.1 wt% nonionic surfactant aqueous solution using a touch mixer (YAMATO Scientific Co., Ltd., "TOUCHMIXER MT-31") and an ultrasonic cleaner (VELVO-CLEAR, "ULTRASONIC CLEANER VS-150"). During the assay, the mixture was slowly stirred in the beaker beforehand until no air bubbles were introduced, and the assay ended at the point when 100,000 particles were measured. It should be noted that the volume-average particle size is the arithmetic mean of the particle size distribution on a volume basis of 100,000 particles. The coefficient of variation (CV) of particle size is calculated using the following formula. The coefficient of variation of particle size (%) = (standard deviation of particle size distribution based on volume ÷ volume mean particle size) × 100 (%)

[0142] <Determination of 5% weight loss of temperature when heated at a rate of 10°C / min in air or nitrogen atmosphere> The 5% thermogravimetric reduction temperature was measured using a differential thermogravimetric analyzer (Hitachi Advanced Technology Co., Ltd., "NEXTASTA200RV"). The sampling method and temperature conditions are as follows. The sample for analysis was prepared by seamlessly filling the bottom of a platinum-plated measuring vessel with 10.5 ± 0.5 mg of sample. Using alumina as a reference material, the 5% thermal weight loss (TW) temperature was determined based on an air or nitrogen flow rate of 200 mL / min. The TG / DTA curve was obtained by heating the sample from 30°C to 800°C at a heating rate of 10°C / min. Using the analytical software provided with the apparatus, the temperature at which the 5% weight loss occurred was calculated from the obtained curve and taken as the 5% TW temperature.

[0143] <Observation of particle cross-section> The dried particles were mixed with the photocurable resin "D-800" (manufactured by NEC Corporation) and irradiated with ultraviolet light to obtain a cured product. The cured product was then cut with tweezers, and the cross-section was smoothed using a cutting machine. The sample was then coated using a sputtering device (manufactured by NEC Corporation, "Auto Fine Coater JFC-1300"). Next, the cross-section of the sample was photographed using a scanning electron microscope (manufactured by Hitachi High Technology Corporation, "SU1510"). The magnification was set to 3000x or 5000x for imaging.

[0144] <Dielectric properties of hollow resin particles before moisture absorption test> The dielectric properties of the hollow resin particles were measured using a dielectric constant measuring device (ADMS01Nc series) manufactured by AET Corporation. Measurements were conducted at a frequency of 10 GHz, an ambient temperature of 23°C, and a relative humidity of 51 ± 1%. Based on the perturbation theory of resonators, the relative permittivity and dielectric loss tangent (Df1) of the hollow resin particles before the moisture absorption test were calculated.

[0145] Dielectric properties of hollow resin particles after moisture absorption test at 50℃ and 95% relative humidity. First, a moisture absorption test was conducted by placing a specified amount of particles in a constant temperature and humidity chamber at a temperature of 50°C and a relative humidity of 95% for 5 days. Regarding the particles after the moisture absorption test, the dielectric properties were measured under the same conditions and methods as those described above for <Dielectric properties of hollow resin particles before moisture absorption test>. The relative permittivity and dielectric loss tangent (Df2) of the hollow resin particles after the moisture absorption test were calculated under an atmosphere of 50°C and 95% relative humidity.

[0146] Dielectric properties of hollow resin particles after moisture absorption test at 85℃ and 85% relative humidity. First, a moisture absorption test was conducted by placing a specified amount of particles in a constant temperature and humidity chamber with an atmosphere adjusted to 85°C and 85% relative humidity for 5 days. Regarding the particles after the moisture absorption test, the dielectric properties were measured under the same conditions and methods as those described above for <Dielectric properties of hollow resin particles before moisture absorption test>. The relative permittivity and dielectric loss tangent (Df3) of the hollow resin particles after the moisture absorption test were calculated under an atmosphere of 85°C and 85% relative humidity.

[0147] [Example 1] An oil phase was prepared using 87.1 g of mixed styrene (manufactured by DENKA Corporation), 39.0 g of divinylbenzene (DVB) 810 (Nippon Steel Chemical Materials Co., Ltd., content 81%, 19% of which is ethylvinylbenzene (EVB)), 130 g of heptane, 3.9 g of Petrotack 90 (aliphatic / aromatic hydrocarbon resin, manufactured by Tosoh Corporation), 3.9 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (ADVN, trade name "V-65", manufactured by Fujifilm and Wako Pure Chemical Co., Ltd.) as an additive, and 0.52 g of "KAYAMER (registered trademark) PM-21" (manufactured by Nippon Kayaku Co., Ltd.) as other additives. An oil phase was added to 1111 g of a 2.0 wt% aqueous dispersion of magnesium pyrophosphate as the aqueous phase. The dispersion was carried out using a POLYTRON homogenizer (Central Scientific Commerce, Inc., "PT10-35") at 7,000 rpm for 5 minutes. Then, emulsification was performed using a high-pressure emulsifier (Yoshida Machinery Kogyo Co., Ltd., "NVL-AS200") at a processing pressure of 20 MPa to prepare a suspension. The resulting suspension was polymerized by heating at 65°C for 5 hours. As a residual reaction treatment, the polymerization reaction was completed by heating at 80°C for 2 hours to obtain a slurry. Hydrochloric acid was added to the obtained slurry to decompose magnesium pyrophosphate. The solid components were separated by filtration and dehydration. After repeated washing with water for purification, the slurry was dried by heating to obtain particles as dry powder (1). The average particle size of the obtained particles (1) was 4.2 μm, and the coefficient of variation was 33.2%. A cross-sectional photograph of the obtained particles (1) is shown in [image missing]. Figure 1 The obtained particles (1) were confirmed to be hollow resin particles surrounded by a shell and composed of a porous structure. The formulation amount and various measurement results are shown in Table 1.

[0148] [Example 2] Except that the amount of styrene (manufactured by DENKA Corporation) was set to 89.7 g and the amount of Petrotack 90 (aliphatic / aromatic hydrocarbon resin, manufactured by Tosoh Corporation) was set to 1.3 g, the rest was carried out in the same manner as in Example 1, and particles (2) were obtained. The average particle size of the obtained particles (2) was 4.4 μm, and the coefficient of variation was 34.1%. A cross-sectional photograph of the obtained particles (2) is shown in [image missing]. Figure 2 The obtained particles (2) were confirmed to be hollow resin particles surrounded by a shell and composed of a porous structure. The formulation amount and various measurement results are shown in Table 1.

[0149] [Example 3] Except that the amount of styrene (manufactured by DENKA Corporation) was set to 84.5 g and the amount of Petrotack 90 (aliphatic / aromatic hydrocarbon resin, manufactured by Tosoh Corporation) was set to 6.5 g, the rest was carried out in the same manner as in Example 1 to obtain particles (3). The average particle size of the obtained particles (3) was 4.3 μm, and the coefficient of variation was 29.1%. A cross-sectional photograph of the obtained particles (3) is shown in [image missing]. Figure 3 The obtained particles (3) were confirmed to be hollow resin particles surrounded by a shell and composed of a porous structure. The formulation amount and various measurement results are shown in Table 1.

[0150] [Example 4] Except that the blending amount of styrene (DENKA SEIKA K.K.) was set to 74.1 g and the blending amount of divinylbenzene (DVB 810 (Nippon Shokubai Co., Ltd., content 81%, 19% being ethylvinylbenzene (EVB)) was set to 53.0 g, the rest was performed in the same manner as Example 1 to obtain particles (4). The average particle diameter of the obtained particles (4) was 4.5 μm and the coefficient of variation was 25.1%. The cross-sectional photograph of the obtained particles (4) is shown in Figure 4 . It was confirmed that the obtained particles (4) were hollow resin particles surrounded by a shell and having a hollow composed of a porous structure. The blending amount and various measurement results, etc. are shown in Table 1.

[0151] [Example 5] Except that Petcoal LX (aromatic hydrocarbon resin, manufactured by Tosoh Corporation) 3.9 g was used instead of Petrotack 90 (aliphatic / aromatic hydrocarbon resin, manufactured by Tosoh Corporation) 3.9 g, the rest was performed in the same manner as Example 1 to obtain particles (5). The average particle diameter of the obtained particles (5) was 3.9 μm and the coefficient of variation was 33.5%. The cross-sectional photograph of the obtained particles (5) is shown in Figure 5 . It was confirmed that the obtained particles (5) were hollow resin particles surrounded by a shell and having a hollow composed of a porous structure. The blending amount and various measurement results, etc. are shown in Table 1.

[0152] [Example 6] Except that VYBAR TM 260 (solid paraffin, manufactured by Nucera Solutions) 3.9 g was used instead of Petrotack 90 (aliphatic / aromatic hydrocarbon resin, manufactured by Tosoh Corporation) 3.9 g, the rest was performed in the same manner as Example 1 to obtain particles (6). The average particle diameter of the obtained particles (6) was 4.5 μm and the coefficient of variation was 31.3%. The cross-sectional photograph of the obtained particles (6) is shown in Figure 6 . It was confirmed that the obtained particles (6) were hollow resin particles surrounded by a shell and having a hollow composed of a porous structure. The blending amount and various measurement results, etc. are shown in Table 1.

[0153] [Example 7] An oil phase was prepared in the same manner as in Example 1. To 1111 g of a 2.0 wt% aqueous magnesium pyrophosphate dispersion as a water phase, the oil phase was added, and emulsification treatment was performed using a POLYTRON homogenizer (manufactured by Central Scientific Commerce, Inc., "PT10-35") at a rotation speed of 7,000 rpm for 5 minutes to prepare a suspension. Polymerization was performed by heating the obtained suspension at 65°C for 5 hours, and a residual reaction treatment was performed by heating at 80°C for 2 hours to complete the polymerization reaction, thereby obtaining a slurry. To the obtained slurry, hydrochloric acid was added to decompose the magnesium pyrophosphate, and the solid component was separated by filtration and dehydration, and then refined by repeated water washing, and then dried by heating to obtain particles (7) as a dry powder. The average particle diameter of the obtained particles (7) was 12.4 μm, and the coefficient of variation was 41.3%. A cross-sectional photograph of the obtained particles (7) is shown in Figure 7 . It was confirmed that the obtained particles (7) were hollow resin particles surrounded by a shell and having a hollow portion composed of a porous structure. The blending amount and various measurement results are shown in Table 1.

[0154] [Comparative Example 1] An oil phase was prepared by mixing methyl methacrylate 65.0 g, ethylene glycol dimethacrylate 65.0 g, heptane 130 g, 2,2'-azobis(2,4-dimethylvaleronitrile) (ADVN, trade name "V-65", manufactured by FUJIFILM Wako Pure Chemical Corporation) 1.3 g as an additive, and "KAYAMER (registered trademark) PM-21" (manufactured by Nippon Kayaku Co., Ltd.) 0.52 g as another additive. To 1111 g of a 2.0 wt% aqueous magnesium pyrophosphate dispersion as a water phase, the oil phase was added, and dispersion and emulsification treatment were performed using a Polytron homogenizer (manufactured by Central Scientific Commerce Inc., "PT10-35") at a rotation speed of 7,000 rpm for 5 minutes to prepare a suspension. Polymerization was performed by heating the obtained suspension at 55°C for 5 hours, and a residual reaction treatment was performed by heating at 80°C for 2 hours to complete the polymerization reaction, thereby obtaining a slurry. To the obtained slurry, hydrochloric acid was added to decompose the magnesium pyrophosphate, and the solid component was separated by filtration and dehydration, and then refined by repeated water washing, and then dried by heating to obtain particles (C1) as a dry powder. The average particle diameter of the obtained particles (C1) was 7.6 μm, and the coefficient of variation was 26.8%. A cross-sectional photograph of the obtained particles (C1) is shown in Figure 8The obtained particle (C2) was confirmed to be a hollow resin particle surrounded by a shell and having a hollow portion composed of a porous structure. The amounts of the components and various measurement results are shown in Table 1.

[0155] [Comparative Example 2] Except that the amount of styrene (DENKA Corporation) was set to 49.1 g and the amount of divinylbenzene (DVB 810 (Nippon Shokubai Co., Ltd., content 81%, 19% being ethylvinylbenzene (EVB)) was set to 77.0 g, the rest was performed in the same manner as in Example 1 to obtain a particle (C2). The average particle diameter of the obtained particle (C2) was 3.8 μm and the coefficient of variation was 28.6%. A cross-sectional photograph of the obtained particle (C2) is shown in Figure 9 The obtained particle (C2) was confirmed to be a hollow resin particle surrounded by a shell and having a hollow portion composed of a porous structure. The amounts of the components and various measurement results are shown in Table 1.

[0156] [Comparative Example 3] Except that the amount of styrene (DENKA Corporation) was set to 91.0 g and Petrotack 90 (aliphatic / aromatic hydrocarbon resin, manufactured by Tosoh Corporation) was not used, the rest was performed in the same manner as in Example 1 to obtain a particle (C3). The average particle diameter of the obtained particle (C3) was 4.2 μm and the coefficient of variation was 24.2%. A cross-sectional photograph of the obtained particle (C3) is shown in Figure 10 The obtained particle (C3) was confirmed to be a hollow resin particle surrounded by a shell and having a hollow portion composed of a porous structure. The amounts of the components and various measurement results are shown in Table 1.

[0157] [Table 1]

[0158] From the results of Table 1, it was found that the particles obtained in Examples 1 to 6 were hollow resin particles having excellent dielectric properties that were not affected by humidity environments.

[0159] [Performance Evaluation: Relative Dielectric Constant and Dielectric Loss Tangent of Particle-Added Film] A film to which the particle (1) obtained in Example 1 was added, a film to which the particle (6) obtained in Example 6 was added, and a film to which the particle (C1) obtained in Comparative Example 1 was added were produced, and the relative dielectric constant and the dielectric loss tangent of the films were evaluated. The resulting particles 0.425 g, ethyl acetate 8.3 g, and solvent-soluble polyimide KPI-MX300F (KURARAY INDUSTRIES CO., LTD.) 1.7 g were subjected to defoaming stirring using a planetary stirring defoaming machine (KURABO CO., LTD., "MAZERUSTAR KK-250"), and an evaluation mixture was prepared. The evaluation mixture was applied to a glass plate having a thickness of 5 mm using a coater set to a wet thickness of 250 μm, and then heated at 60°C for 30 minutes, at 90°C for 10 minutes, at 150°C for 30 minutes, and at 200°C for 30 minutes to remove ethyl acetate, and then cooled to room temperature, whereby a film containing each of the particles was obtained. The relative dielectric constant and dielectric loss tangent of the obtained film were evaluated using a cavity resonance method (measurement frequency: 5.8 GHz). The measurement results were expressed as a relative ratio (%) based on the measurement value of a film not containing particles being 100%. The results are shown in Table 2.

[0160] [Table 2]

[0161] From the results in Table 2, it was confirmed that the hollow resin particles provided by the present application have an effect of reducing the relative dielectric constant and dielectric loss tangent of a substrate, and are effective for achieving low dielectric constant and low dielectric loss tangent of semiconductor materials. Industrial applicability

[0162] The hollow resin particles of the embodiments of the present application and the hollow resin particles obtained by the production method of the embodiments of the present application can be used for semiconductor materials and the like.

Claims

1. A hollow resin particle having a shell and a hollow portion surrounded by the shell, wherein, The shell comprises a polymer (P) obtained by polymerizing a composition containing a monomer (M) comprising a crosslinking monomer and a monofunctional monomer. Under conditions I of hygroscopic test at 50°C, 95% relative humidity, and 5 days, the dielectric loss tangent Df1 at a measurement frequency of 10 GHz before the hygroscopic test and the dielectric loss tangent Df2 at a measurement frequency of 10 GHz after the hygroscopic test under conditions I satisfy equation (1), and the dielectric loss tangent Df1 is less than 0.0017. Df2-Df1 ≤ 0.01 (1)。 2. The hollow resin particles according to claim 1 have a relative permittivity of less than 1.5 at a measurement frequency of 10 GHz.

3. The hollow resin particles according to claim 1, wherein, The crosslinking monomer is an aromatic crosslinking monomer.

4. The hollow resin particles according to claim 3, wherein, The composition contains a hydrocarbon resin (A), and the aromatic crosslinking monomer is 1 to 40 parts by weight, based on a total amount of 100 parts by weight of the monomer (M) and the hydrocarbon resin (A).

5. The hollow resin particles according to claim 1, wherein, The composition contains a hydrocarbon resin (A), and the hydrocarbon resin (A) is 1 to 10 parts by weight when the total amount of the monomer (M) and the hydrocarbon resin (A) is 100 parts by weight.

6. The hollow resin particles according to claim 1, wherein, The monofunctional monomer is selected from at least one group consisting of styrene, α-methylstyrene, ethylvinylbenzene, vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, vinylbiphenyl, vinylnaphthalene, and acenaphthene.

7. The hollow resin particles according to claim 1, wherein the 5% heat weight reduction temperature of the hollow resin particles when heated at 10°C / min in air atmosphere is 270°C or higher.

8. The hollow resin particles according to claim 1 have a volume average particle size of 0.1 μm to 30 μm.

9. A hollow resin particle having a shell and a hollow portion surrounded by the shell, wherein, The shell comprises a polymer (P) obtained by polymerizing a composition containing a monomer (M) comprising a crosslinking monomer and a monofunctional monomer. Under conditions II of hygroscopic test at 85°C, 85% relative humidity, and 5 days, the dielectric loss tangent Df1 at the measurement frequency of 10 GHz before the hygroscopic test and the dielectric loss tangent Df3 at the measurement frequency of 10 GHz after the hygroscopic test under conditions II satisfy equation (2), and the dielectric loss tangent Df1 is less than 0.0017. Df3-Df1 ≤ 0.02 (2)。 10. Hollow resin particles according to any one of claims 1 to 9, used in resin compositions for semiconductor components.

11. A resin composition for semiconductor components, comprising hollow resin particles according to claim 10.

12. A method for manufacturing hollow resin particles, comprising reacting a monomer (M) containing a crosslinking monomer and a monofunctional monomer with a hydrocarbon resin (A) in an aqueous medium in the presence of a nonreactive solvent, wherein the crosslinking monomer is 1 to 40 parts by weight when the total amount of the monomer (M) and the hydrocarbon resin (A) is 100 parts by weight.

13. The method for manufacturing hollow resin particles according to claim 12, wherein, When the total amount of the monomer (M) and the hydrocarbon resin (A) is 100 parts by weight, the hydrocarbon resin (A) is 1 to 10 parts by weight.

Images