JP2024044239A - Hollow resin particles and method for producing hollow resin particles - Google Patents

Abstract

[Problem] To provide hollow resin particles having a shell portion and a hollow portion surrounded by the shell portion, which can achieve a low dielectric constant and a low dielectric loss tangent and exhibit excellent heat resistance. Also provided is a method for easily producing such hollow resin particles. Furthermore, to provide uses of such hollow resin particles. [Solution] The hollow resin particles according to an embodiment of the present invention are hollow resin particles having a shell portion and a hollow portion surrounded by the shell portion, and the shell portion contains a polymer (P) having a polycyclic aromatic hydrocarbon structural unit. [Selected Figure] Figure 1

Description

The present invention relates to hollow resin particles and a method for producing hollow resin particles.

In order to increase the speed of information processing using electronic devices, attempts have been made to reduce the dielectric constant and dielectric loss tangent of the insulating layers of multilayer printed circuit boards. As part of this, hollow particles having a shell part and a hollow part surrounded by the shell part are mixed in the thermosetting resin, thereby introducing air space into the resin layer and lowering the dielectric constant and dielectric loss tangent. It is being considered.

Hollow resin particles used in such applications are required to have high heat resistance so that the hollow resin particles do not undergo substantial change even when heated, for example, during molding of the thermosetting resin in which the hollow resin particles are mixed or during use of solder.

Furthermore, when hollow resin particles are mixed with a thermosetting resin, with conventional hollow resin particles, there is a problem that the thermosetting resin penetrates into the hollow resin particles during kneading, making it impossible to maintain the air space inside the hollow resin particles.

It has been reported that conventional hollow resin particles can be obtained by suspension polymerization of a monomer mainly composed of an acrylic polyfunctional monomer such as trimethylolpropane tri(meth)acrylate or dipentaerythritol hexaacrylate together with a hydrophobic solvent (Patent Document 1). However, acrylic resins have high values of dielectric constant and dielectric dissipation factor, and insufficient heat resistance. For this reason, the acrylic hollow resin particles described in Patent Document 1 are unsuitable for the purpose of lowering the dielectric constant and dielectric dissipation factor of the resin layer, or for the purpose of imparting high heat resistance to the resin layer.

It has been reported that conventional hollow resin particles can be obtained by suspension polymerization of a monomer mainly composed of an acrylic polyfunctional monomer such as trimethylolpropane tri(meth)acrylate and an acrylic monofunctional monomer such as methyl methacrylate together with a polar solvent containing a dispersion stabilizer to obtain porous hollow polymer particles (Patent Document 2). However, acrylic resins have high values of dielectric constant and dielectric loss tangent, and insufficient heat resistance. For this reason, like the acrylic hollow resin particles described in Patent Document 1, the porous hollow polymer particles described in Patent Document 2 are not suitable for the purpose of lowering the dielectric constant and dielectric loss tangent of the resin layer, or for the purpose of imparting high heat resistance to the resin layer. Furthermore, the shell surface layer of the porous hollow polymer particles is thin, and the thermosetting resin easily penetrates into the porous hollow polymer particles.

It has been reported that conventional hollow resin particles obtained by polymerizing a polyfunctional monomer and a monofunctional monomer are blended with a resin to produce an organic insulating material with excellent insulating properties, low dielectric constant, and low dielectric loss tangent. Specific monomers used include styrene, methyl methacrylate, divinylbenzene, and trimethylolpropane tri(meth)acrylate (Patent Document 3). However, the hollow resin particles described in Patent Document 3 use a styrene-based monomer in combination with an acrylic-based monomer with a high dielectric constant and dielectric loss tangent, so the resin layer does not have a sufficiently low dielectric constant and low dielectric loss tangent. Patent Document 3 also shows the 10% weight loss temperature measured by TG-DTA in a nitrogen atmosphere at a temperature rise rate of 10°C/min as a guideline for heat resistance, but the heat resistance is insufficient.

As conventional hollow resin particles, a shell is formed of either a polymer or copolymer of a crosslinkable monomer, or a copolymer of the crosslinkable monomer and a monofunctional monomer, and has a single-phase structure. Representatively, styrene-based hollow resin particles obtained by suspension polymerization of divinylbenzene with saturated hydrocarbons having 8 to 18 carbon atoms (more specifically, hexadecane) have been reported, and it has been reported that a resin composition containing the hollow resin particles and a thermosetting resin is suitable for the manufacture of multilayer printed circuit boards used in electronic devices and the like (Patent Document 4). However, since the hollow resin particles described in Patent Document 4 use saturated hydrocarbons having 8 to 18 carbon atoms (more specifically, hexadecane) in their manufacture, it is difficult to remove the solvent from the hollow parts by distillation or the like, and saturated hydrocarbons having 8 to 18 carbon atoms remain in the obtained styrene-based hollow resin particles, making it difficult to obtain styrene-based hollow resin particles in which the hollow parts are completely replaced with air. In addition, in order to obtain styrene-based hollow resin particles in which the hollow parts are completely replaced with air, production costs are incurred for the above-mentioned solvent removal. Furthermore, the styrene-based hollow resin particles described in Patent Document 4 have insufficient heat resistance.

As conventional hollow resin particles, hollow resin particles made of a polymer containing vinyl monomer units and phosphate ester monomer units and having a volume average particle diameter of 0.5 to 1000 μm have been reported (Patent Document 5). . However, similar to the hollow resin particles described in Patent Document 3, the hollow resin particles described in Patent Document 5 use a styrene monomer and an acrylic monomer with high dielectric constant and dielectric loss tangent, so the resin The dielectric constant and dielectric loss tangent of the layer are insufficiently low, and the heat resistance is also insufficient.

As conventional hollow resin particles, hollow resin particles having a shell portion formed of a polymer having urea bonds and/or urethane bonds and a hollow portion surrounded by the shell portion have been reported (Patent Document 6). . However, since the hollow resin particles described in Patent Document 6 are hollow resin particles of a urethane resin composition, the values of the dielectric constant and the dielectric loss tangent are high, and the heat resistance is insufficient.

Patent No. 6513273 Patent No. 4445495 Japanese Patent Application Publication No. 2000-313818 Patent No. 4171489 International Publication No. 2020/054816 Patent No. 6924533

The present invention has been made to solve the above-mentioned conventional problems, and its main purpose is to provide hollow resin particles having a shell part and a hollow part surrounded by the shell part, and to provide a hollow resin particle with a low dielectric constant and a low dielectric constant. The object of the present invention is to provide hollow resin particles that can achieve dielectric loss tangent and exhibit excellent heat resistance. Another object of the present invention is to provide a method for easily manufacturing such hollow resin particles.

[1] The hollow resin particle according to the embodiment of the present invention is a hollow resin particle having a shell part and a hollow part surrounded by the shell part, and the shell part has a polycyclic aromatic hydrocarbon structural unit. Contains a polymer (P) with
[2] In the hollow resin particles described in [1] above, the polycyclic aromatic hydrocarbon structural unit may be a structural unit represented by formula (1).
[3] In the hollow resin particles described in [1] or [2] above, the polymer (P) comprises a monomer (A) which is a polycyclic aromatic hydrocarbon having a polymerization-reactive group; ) and a monomer (M) that reacts with the polymer.
[4] In the hollow resin particles described in [3] above, the ratio of the monomer (A) to the monomer (M) is such that the total amount of the monomer (A) and the monomer (M) is 100 parts by weight. In this case, the weight part ratio (monomer (A):monomer (M)) may be (30 parts by weight to 70 parts by weight):(70 parts by weight to 30 parts by weight).
[5] In the hollow resin particles described in [3] or [4] above, the monomer (A) may be acenaphthylene.
[6] In the hollow resin particle according to any one of [3] to [5] above, the monomer (M) may contain a compound (B) having a phosphate ester structure and a radically reactive group. .
[7] In the hollow resin particles according to any one of [1] to [6] above, the hollow resin particles may have a volume average particle diameter of 0.1 μm to 100 μm.
[8] In the hollow resin particles described in [7] above, the volume average particle diameter may be 0.1 μm to 10 μm.
[9] In the hollow resin particle according to any one of [1] to [8] above, the hollow portion may consist of one hollow region.
[10] In the hollow resin particle according to any one of [1] to [8] above, the hollow portion may consist of a plurality of hollow regions.
[11] In the hollow resin particles according to any one of [1] to [10] above, the 5% weight loss temperature when the hollow resin particles are heated at a rate of 10°C/min in a nitrogen atmosphere is 300°C. It may be more than that.
[12] In the hollow resin particles according to any one of [1] to [11] above, the hollow resin particles may be used in a resin composition for semiconductor members.
[13] A method for producing hollow resin particles according to an embodiment of the present invention is a method for producing hollow resin particles having a shell portion and a hollow portion surrounded by the shell portion, the method comprising: a polycyclic aromatic particle having a polymerization-reactive group; 30 to 70 parts by weight of a monomer (A) that is a group hydrocarbon and 70 to 30 parts by weight of a monomer (M) that reacts with the monomer (A) (total amount of monomer (A) and monomer (M) (100 parts by weight) are reacted in an aqueous medium in the presence of a non-reactive solvent, and the monomer (M) contains a compound (B) having a phosphate ester structure and a radically reactive group.

According to an embodiment of the present invention, the hollow resin particle has a shell portion and a hollow portion surrounded by the shell portion, and can achieve a low dielectric constant and a low dielectric loss tangent, and can exhibit excellent heat resistance. , hollow resin particles can be provided. Furthermore, a method for easily manufacturing such hollow resin particles can be provided.

1 is a cross-sectional photographic diagram of particles (1) obtained in Example 1. 2 is a cross-sectional photographic diagram of particles (2) obtained in Example 2. FIG. 3 is a cross-sectional photographic diagram of particles (3) obtained in Example 3. FIG. FIG. 1 is a cross-sectional photograph of particle (4) obtained in Example 4. 3 is a cross-sectional photographic diagram of particles (5) obtained in Example 5. FIG. FIG. 1 is a cross-sectional photograph of particle (6) obtained in Example 6. FIG. 3 is a cross-sectional photographic diagram of particles (7) obtained in Example 7. FIG. 1 is a cross-sectional photograph of particle (8) obtained in Example 8. FIG. 1 is a cross-sectional photograph of particle (9) obtained in Example 9. 2 is a cross-sectional photographic diagram of particles (C1) obtained in Comparative Example 1. FIG. FIG. 1 is a cross-sectional photograph of a film produced using particles (8) obtained in Example 8.

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

In this specification, the term "(meth)acrylic" means "acrylic and/or methacrylic", the term "(meth)acrylate" means "acrylate and/or methacrylate", the term "(meth)allyl" means "allyl and/or methallyl", and the term "(meth)acrolein" means "acrolein and/or methacrolein". In addition, in this specification, the term "acid (salt)" means "acid and/or its salt". Examples of salts include alkali metal salts and alkaline earth metal salts, and specific examples include sodium salts and potassium salts.

≪≪1. Hollow resin particles≫≫
≪1-1. Structure and properties of hollow resin particles≫
The hollow resin particle according to the embodiment of the present invention is a hollow resin particle having a shell portion and a hollow portion surrounded by the shell portion. The term "hollow" as used herein refers to a state in which the interior is filled with a substance other than resin, such as gas or liquid, and is preferably filled with gas in order to further enhance the effects of the present invention. It means the state of being.

The hollow portion may consist of one hollow region or multiple hollow regions (porous structure).

The volume average particle diameter of the hollow resin particles according to the embodiment of the present invention is preferably 0.1 μm to 100 μm, more preferably 0.1 μm to 50 μm, still more preferably 0.1 μm to 30 μm, and particularly preferably is 0.1 μm to 20 μm. If the volume average particle diameter of the hollow resin particles according to the embodiment of the present invention is within the above range, the effects of the present invention can be more effectively exhibited. If the volume average particle diameter of the hollow resin particles according to the embodiment of the present invention is outside the above range and is too small, the thickness of the shell portion will be relatively thin, so there is a risk that the hollow resin particles will not have sufficient strength. Furthermore, when hollow resin particles are kneaded with a thermosetting resin, there is a risk that the thermosetting resin may invade inside the hollow resin particles. If the average particle diameter of the hollow resin particles according to the embodiment of the present invention is too large outside the above range, there is a risk that phase separation between the polymer and the solvent resulting from polymerization of the monomer components during suspension polymerization may become difficult to occur. This may make it difficult to form the shell portion.

The coefficient of variation (CV value) of the particle diameter of the hollow resin particles according to the embodiment of the present invention is preferably 10% to 50%, more preferably 15% to 45%, even more preferably 18% to 45%, and particularly preferably 20% to 45%. If the coefficient of variation (CV value) of the particle diameter of the hollow resin particles according to the embodiment of the present invention is within the above range, the effects of the present invention can be more effectively achieved. If the coefficient of variation (CV value) of the particle diameter of the hollow resin particles according to the embodiment of the present invention is too small outside the above range, the hollow resin particles are difficult to disperse in the thermosetting resin when kneaded with the thermosetting resin, and for example, when a resin layer is made from the resin composition, there is a risk of variation in thickness. If the coefficient of variation (CV value) of the particle diameter of the hollow resin particles according to the embodiment of the present invention is too large outside the above range, there is a risk of difficulty in forming a thin film or variation in thickness when, for example, a resin layer is made from the resin composition due to an increase in the amount of coarse particles.

The hollow resin particles according to the embodiment of the present invention preferably have a 5% weight loss temperature of 300°C or more, more preferably 320°C or more, even more preferably 340°C or more, and particularly preferably 360°C or more, when heated in a nitrogen atmosphere at 10°C/min. The upper limit of the 5% weight loss temperature is preferably 500°C or less in reality. If the 5% weight loss temperature of the hollow resin particles according to the embodiment of the present invention when heated in a nitrogen atmosphere at 10°C/min is within the above range, the hollow resin particles according to the embodiment of the present invention can exhibit excellent heat resistance. If the 5% weight loss temperature of the hollow resin particles according to the embodiment of the present invention when heated in a nitrogen atmosphere at 10°C/min is too small outside the above range, for example, when the hollow resin particles are kneaded with a thermosetting resin, the hollow resin particles are deformed by heating for the curing reaction, and the hollow portion is lost, which may reduce the low dielectric effect and low dielectric tangent effect.

≪1-2. Shell part≫
The shell portion contains a polymer (P) having a polycyclic aromatic hydrocarbon structural unit. When the shell portion contains a polymer (P) having such a structural unit, the effects of the present invention can be more effectively exhibited.

The number of polymers (P) may be one, or two or more.

The content ratio of the polymer (P) in the shell part is preferably 60% to 100% by weight, more preferably 70% to 100% by weight, in order to better express the effects of the present invention. More preferably, it is 80% to 100% by weight, particularly preferably 90% to 100% by weight.

The polycyclic aromatic hydrocarbon structural unit is at least one of the monomer units constituting the polymer (P) and is a monomer unit having a polycyclic aromatic hydrocarbon structure.

The content of polycyclic aromatic hydrocarbon structural units among the monomer units constituting the polymer (P) is preferably 60% by weight to 100% by weight, more preferably 70% by weight to 100% by weight, even more preferably 80% by weight to 100% by weight, and particularly preferably 90% by weight to 100% by weight, in order to further exert the effects of the present invention.

The shell portion may contain any other appropriate components as long as they do not impair the effects of the present invention.

As the polycyclic aromatic hydrocarbon structural unit, any appropriate polycyclic aromatic hydrocarbon structural unit may be adopted as long as it does not impair the effects of the present invention. In terms of being able to further exhibit the effects of the present invention, the polycyclic aromatic hydrocarbon structural unit is preferably a structural unit represented by formula (1).

The polymer (P) preferably contains a monomer (A) that is a polycyclic aromatic hydrocarbon having a polymerization-reactive group, and a monomer that reacts with the monomer (A), in order to further exhibit the effects of the present invention. This is a polymer obtained by the reaction of (M).

The number of monomers (A) may be one, or two or more.

The number of monomers (M) may be one, or two or more.

The ratio of monomer (A) to monomer (M) is preferably (30 parts by weight to 70 parts by weight): (70 parts by weight to 30 parts by weight), more preferably (35 parts by weight to 65 parts by weight): (65 parts by weight to 35 parts by weight), and even more preferably (40 parts by weight to 60 parts by weight): (60 parts by weight to 40 parts by weight). If the content of monomer (A) is too small outside the above range, for example, there is a risk that heat resistance will be insufficient. If the content of monomer (A) is too large outside the above range, for example, there is a risk that it will be difficult to form a shell portion and a hollow portion surrounded by the shell portion.

As the monomer (A), any suitable monomer may be employed as long as it is a monomer that can construct a polycyclic aromatic hydrocarbon structural unit through a polymerization reaction, as long as it does not impair the effects of the present invention. Examples of such monomers (A) include acenaphthylene compounds such as acenaphthylene, alkylacenaphthylenes, halogenated acenaphthylenes, and phenylacenaphthylenes. Examples of the alkylacenaphthylenes include 1-methylacenaphthylene, 3-methylacenaphthylene, 1-ethylacenaphthylene, 3-ethylacenaphthylene, and 1,2-dipropylacenaphthylene. . Examples of halogenated acenaphthylenes include 1-chloroacenaphthylene, 3-chloroacenaphthylene, 4-chloroacenaphthylene, 5-chloroacenaphthylene, 1-bromoacenaphthylene, and 3-bromoacenaphthylene. can be mentioned. Examples of the phenylacenaphthylenes include 1-phenylacenaphthylene, 3-phenylacenaphthylene, 4-phenylacenaphthylene, and 5-phenylacenaphthylene. The acenaphthylene compound may be a monofunctional acenaphthylene compound having one acenaphthylene structure in the molecule, as described above, or a polyfunctional acenaphthylene compound having two or more acenaphthylene structures in the molecule. In order to more effectively exhibit the effects of the present invention, such a monomer (A) is preferably a monomer that can construct a polycyclic aromatic hydrocarbon structural unit represented by formula (1) through a polymerization reaction. More preferred is acenaphthylene.

As the monomer (M), any appropriate monomer may be used as long as it reacts with the monomer (A) and does not impair the effects of the present invention. Examples of such monomers (M) include crosslinkable monomers and monofunctional monomers.

Examples of crosslinkable monomers include polyfunctional (meth)acrylic acid esters such as ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and glycerin tri(meth)acrylate; N,N'-methylenebis(meth)acrylate; Polyfunctional acrylamide derivatives such as acrylamide and N,N'-ethylenebis(meth)acrylamide; polyfunctional allyl derivatives such as diallylamine and tetraallyloxyethane; aromatic crosslinking monomers such as divinylbenzene, divinylnaphthalene, and diallyl phthalate; can be mentioned. As the crosslinking monomer, aromatic crosslinking monomers are preferable, and divinylbenzene is more preferable, since the effects of the present invention can be more effectively expressed. The number of crosslinkable monomers may be one, or two or more.

The proportion of the crosslinkable monomer used is preferably 25 to 75 parts by weight, more preferably 30 to 70 parts by weight, and even more preferably 35 to 65 parts by weight, per 100 parts by weight of monomer (A), in order to more effectively exhibit the effects of the present invention.

Examples of monofunctional monomers include alkyl (meth)acrylates having 1 to 16 carbon atoms such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and cetyl (meth)acrylate; styrene, α - Aromatic monofunctional monomers such as methylstyrene, ethylvinylbenzene, vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, vinylbiphenyl, vinylnaphthalene; dimethyl maleate, diethyl fumarate, dimethyl fuma dicarboxylic acid ester monomers such as diethyl fumarate; maleic anhydride; N-vinylcarbazole; (meth)acrylonitrile; As the monofunctional monomer, aromatic monofunctional monomers are preferable, and styrene and ethylvinylbenzene are more preferable, since they can more effectively exhibit the effects of the present invention. The number of monofunctional monomers may be one, or two or more.

The proportion of the monofunctional monomer to be used is preferably 0 to 30 parts by weight, more preferably 0 to 30 parts by weight, based on 100 parts by weight of monomer (A), in order to better express the effects of the present invention. The amount is 25 parts by weight, more preferably 0 to 20 parts by weight.

The monomer (M) may contain a compound (B) having a phosphate ester structure and a radically reactive group.

The number of compounds (B) having a phosphoric acid ester structure and a radically reactive group may be one, or two or more.

The number of phosphoric acid ester structures may be one, or two or more.

The phosphate structure is preferably represented by formula (2) in that the effects of the present invention can be more effectively exhibited.

In formula (2), R ¹ and R ² each independently represent an organic group or a hydrogen atom. The organic group that can be taken as R ¹ and R ² in formula (2) is a group containing a carbon atom, and may also contain an inorganic atom.

The organic group which can be taken by R ¹ and R ² in formula (2) is more preferably represented by formula (3) in that the effect of the present invention can be more effectively exhibited.

In formula (3), R ¹ and R ² each independently represent an organic group or a hydrogen atom. The organic group that R ¹ and R ² in formula (3) can take is a group containing a carbon atom and may contain an inorganic atom. In formula (3), R ³ is a linear or branched alkylene group having 1 to 30 carbon atoms, and m is 1 to 300.

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, even more 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, and most preferably a linear or branched alkylene group having 1 to 4 carbon atoms.

In formula (3), m is preferably 1 to 100, more preferably 1 to 50, even more preferably 1 to 40, and particularly preferably 1 to 30.

The phosphoric acid ester structure may be a phosphoric acid monoester structure (both R ¹ and R ² are hydrogen atoms), or a phosphoric diester structure (one of R ¹ and R ² is an organic group and the other is a hydrogen atom). hydrogen atom) or a phosphoric acid triester structure (both R ¹ and R ² are organic groups). The phosphoric acid ester structure is preferably a phosphoric acid monoester structure or a phosphoric diester structure in that the effects of the present invention can be more fully expressed.

As the radical reactive group, any appropriate polymer may be used as long as it is a group generally known as a radical reactive group and does not impair the effects of the present invention. In terms of being able to more effectively exhibit the effects of the present invention, such radical reactive groups are preferably groups having a carbon-carbon unsaturated double bond, and specific examples include vinyl groups, acrylic groups, methacrylic groups, acrylamide groups, and allyl groups.

The radical-reactive group preferably has a structure represented by formula (4) in that it can more effectively exhibit the effects of the present invention.

In formula (4), R ⁴ represents a methyl group or a hydrogen atom.

The compound (B) having such a phosphate ester structure and a radical-reactive group is preferably a compound represented by formula (5), since it can more effectively exhibit the effects of the present invention.

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

In formula (5), 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. An alkylene group having a chain, more 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. or a branched alkylene group, most preferably a linear or branched alkylene group having 1 to 4 carbon atoms.

In formula (5), 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. An alkylene group having a chain, more 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. or a branched alkylene group, most preferably a linear or branched alkylene group having 1 to 4 carbon atoms.

In formula (5), m is preferably 1 to 100, more preferably 1 to 50, still more preferably 1 to 40, particularly preferably 1 to 30.

In formula (5), b is preferably 0 to 100, more preferably 0 to 50, even more preferably 0 to 10, particularly preferably 0 to 5, and most preferably 0 or 1. It is.

As the compound (B), those available as commercial products may be employed. As such a compound (B), for example, from the viewpoint of compatibility, the trade name "KAYAMER (registered trademark) PM-21" (manufactured by Nippon Kayaku Co., Ltd.) may be mentioned.

When the total amount of monomer (A) and monomer (M) is taken as 100 parts by weight, the amount of compound (B) relative to the total amount is preferably 0.0001 to 0.0190 parts by weight, more preferably 0.0005 to 0.0190 parts by weight, even more preferably 0.0010 to 0.0170 parts by weight, and particularly preferably 0.0015 to 0.0150 parts by weight. If the amount of compound (B) is too small outside the above range, the average particle size may become small and the dispersion stability of the oil droplets may become insufficient, and the formation of polymerized lumps or coarse particles may occur frequently. If the content ratio of compound (B) is too large outside the above range, it may be difficult to form a shell portion and a hollow portion surrounded by the shell portion.

Polymer (P) may preferably be formed by reaction of monomer (A) and monomer (M).

The reaction between monomer (A) and monomer (M) can be carried out by any appropriate reaction within a range that does not impair the effects of the present invention. Such a reaction is preferably a suspension polymerization reaction.

When performing a suspension polymerization reaction, typically, an oil phase is added to an aqueous phase and suspended, and the polymerization reaction is performed. The aqueous phase and oil phase may contain any suitable solvent as long as the effects of the present invention are not impaired. Examples of such a solvent include an aqueous medium and a non-reactive solvent as described below. The number of solvents may be one, or two or more.

When reacting monomer (A) with monomer (M), any suitable additive (C) that does not fall under either monomer (A) or monomer (M) may be used within a range that does not impair the effects of the present invention. The additive (C) may be of only one type or of two or more types. The additive (C) does not include solvents such as aqueous media and non-reactive solvents, as described below, and dispersion stabilizers.

The content of additive (C) is preferably 0% to 40% by weight, more preferably 0% to 30% by weight, even more preferably 0% to 20% by weight, and particularly preferably 0% to 10% by weight, based on the total amount of monomer (A) and monomer (M).

As the additive (C), any suitable additive that does not fall under either the monomer (A) or the monomer (M) may be used as long as it does not impair the effects of the present invention. Examples of such additives (C) include non-crosslinkable polymers and polymerization initiators.

By including a non-crosslinkable polymer as the additive (C), phase separation between the polymer (P) generated as the reaction progresses and the solvent can be promoted, and shell formation can be promoted.

Examples of the non-crosslinkable polymer include at least one selected from the group consisting of polyolefins, styrene polymers, (meth)acrylic acid polymers, and styrene-(meth)acrylic acid polymers.

Examples of polyolefins include polyethylene, polypropylene, and poly-α-olefins. From the viewpoint of solubility in the monomer composition, it is preferable to use side-chain crystalline polyolefins using long-chain α-olefins as raw materials, and low-molecular-weight polyolefins and olefin oligomers produced with metallocene catalysts.

Examples of the styrene polymer include polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, and the like.

Examples of the (meth)acrylic acid polymer include polymethyl (meth)acrylate, polyethyl (meth)acrylate, polybutyl (meth)acrylate, and polypropyl (meth)acrylate.

Examples of styrene-(meth)acrylic acid polymers include styrene-methyl (meth)acrylate copolymers, styrene-ethyl (meth)acrylate copolymers, styrene-butyl (meth)acrylate copolymers, and styrene-propyl (meth)acrylate copolymers.

When reacting monomer (A) and monomer (M), any appropriate dispersion stabilizer (not applicable to either monomer (A) or monomer (M)) may be used within the range that does not impair the effects of the present invention. D) may also be used. The number of dispersion stabilizers (D) may be one, or two or more.

The dispersion stabilizer (D) is preferably used in an amount of 0.5 to 10 parts by weight per 100 parts by weight of the aqueous medium. The dispersion stabilizer (D) may be used in a single type or in a combination of two or more types.

Examples of the dispersion stabilizer (D) include inorganic water-soluble polymer compounds such as polyvinyl alcohol, polycarboxylic acids, celluloses (hydroxyethyl cellulose, carboxymethyl cellulose, etc.), polyvinylpyrrolidone, sodium tripolyphosphate, and the like. Further, as the dispersion stabilizer (D), phosphates such as calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate; pyrophosphates such as calcium pyrophosphate, magnesium pyrophosphate, aluminum pyrophosphate, zinc pyrophosphate; Also included are poorly water-soluble inorganic compounds such as calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, and colloidal silica. Among these, magnesium pyrophosphate is preferred because it is relatively easy to remove from the hollow resin particles and is unlikely to remain on the surface of the hollow resin particles.

1-3. Uses of hollow resin particles
The hollow resin particles according to the embodiment of the present invention can be used in various applications. In that the effects of the present invention can be more effectively utilized, the hollow resin particles according to the embodiment of the present invention are suitable for semiconductor members, and can be typically used in resin compositions for semiconductor members. In addition, the hollow resin particles according to the embodiment of the present invention can be used in applications such as paint compositions, cosmetics, paper coating compositions, heat insulating compositions, light diffusing compositions, and light diffusing films, in addition to the above-mentioned applications for resin compositions for semiconductor members.

<Resin composition for semiconductor members>
The hollow resin particles according to the embodiment of the present invention can achieve a low dielectric constant and a low dielectric loss tangent and exhibit excellent heat resistance, and therefore can be suitably used in a resin composition for a semiconductor member.

A resin composition for a semiconductor member according to an embodiment of the present invention includes hollow resin particles according to an embodiment of the present invention.

Semiconductor components refer to components that constitute semiconductors, such as semiconductor packages and semiconductor modules. In this specification, a resin composition for semiconductor components refers to a resin composition used for semiconductor components.

A semiconductor package is constructed using an IC chip as an essential component and at least one material selected from mold resin, underfill material, mold underfill material, die bond material, prepreg for semiconductor package substrates, metal-clad laminate for semiconductor package substrates, and build-up material for printed circuit boards for semiconductor packages.

A semiconductor module is constructed using a semiconductor package as an essential component and at least one member selected from prepregs for printed circuit boards, metal-clad laminates for printed circuit boards, build-up materials for printed circuit boards, solder resist materials, coverlay films, electromagnetic shielding films, and adhesive sheets for printed circuit boards.

<Coating composition>
The hollow resin particles according to the embodiments of the present invention can impart an excellent appearance to a coating film containing the particles, and therefore can be suitably used in a coating composition.

A coating composition according to an embodiment of the invention includes hollow resin particles according to an embodiment of the invention.

The coating composition according to the embodiment of the present invention preferably contains at least one selected from a binder resin and a UV curable resin. Only one type of binder resin may be used, or two or more types may be used. Only one type of UV curable resin may be used, or two or more types may be used.

As the binder resin, any suitable binder resin may be used as long as the effects of the present invention are not impaired. Examples of such binder resins include resins that are soluble in organic solvents or water, and emulsion-type aqueous resins that can be dispersed in water. Specific examples of the binder resin include acrylic resin, alkyd resin, polyester resin, polyurethane resin, chlorinated polyolefin resin, and amorphous polyolefin resin.

As the UV curable resin, any suitable UV curable resin may be used as long as the effects of the present invention are not impaired. Examples of such UV-curable resins include polyfunctional (meth)acrylate resins and polyfunctional urethane acrylate resins, and polyfunctional (meth)acrylate resins are preferred, with three or more (meth)acrylate resins in one molecule. More preferred is a polyfunctional (meth)acrylate resin having an acryloyl group. Specifically, the polyfunctional (meth)acrylate resin having three or more (meth)acryloyl groups in one molecule includes, for example, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, 1,2,4-cyclohexane tetra(meth)acrylate, pentaglycerol triacrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetra (meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol triacrylate, and tripentaerythritol hexaacrylate.

When the coating composition according to an embodiment of the present invention contains at least one selected from a binder resin and a UV-curable resin, the content ratio may be any appropriate content ratio depending on the purpose. Typically, the hollow resin particles according to an embodiment of the present invention are preferably 5% by weight to 50% by weight, more preferably 10% by weight to 50% by weight, and even more preferably 20% by weight to 40% by weight relative to the total amount of the binder resin (in terms of solids in the case of an emulsion-type aqueous resin) and at least one selected from a UV-curable resin and the hollow resin particles according to an embodiment of the present invention.

When a UV-curable resin is used, a photopolymerization initiator is preferably used in combination. Any appropriate photopolymerization initiator may be used as long as it does not impair the effects of the present invention. Examples of such photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, α-hydroxyalkylphenones, α-aminoalkylphenones, anthraquinones, thioxanthones, azo compounds, peroxides (described in JP-A-2001-139663, etc.), 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfonium compounds, onium salts, borate salts, active halogen compounds, and α-acyloxime esters.

The coating composition according to the embodiment of the present invention may contain a solvent. The solvent may be one type only, or may be two or more types. When the coating composition according to the embodiment of the present invention contains a solvent, the content ratio of the solvent may be any appropriate content ratio depending on the purpose.

As the solvent, any suitable solvent may be used as long as it does not impair the effects of the present invention. Such a solvent is preferably one that can dissolve or disperse the binder resin or UV-curable resin. For oil-based paints, such solvents include, for example, hydrocarbon solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; and ether solvents such as dioxane, ethylene glycol diethyl ether, and ethylene glycol monobutyl ether. For water-based paints, such solvents include, for example, water and alcohols.

The coating composition according to the embodiment of the present invention may be diluted to adjust the viscosity as necessary. Any appropriate diluent may be used depending on the purpose. Examples of such diluents include the above-mentioned solvents. The diluent may be one type or two or more types.

The coating composition according to the embodiment of the present invention may contain other components as necessary, such as a coating surface conditioner, a fluidity conditioner, an ultraviolet absorber, a light stabilizer, a curing catalyst, an extender pigment, a coloring pigment, a metal. Pigments, mica powder pigments, and dyes may also be included.

When forming a coating film using the coating composition according to an embodiment of the present invention, any appropriate coating method may be used depending on the purpose. Examples of such coating methods include spray coating, roll coating, brush coating, coating reverse roll coating, gravure coating, die coating, comma coating, and spray coating.

When forming a coating film using the coating composition according to an embodiment of the present invention, any suitable formation method may be adopted depending on the purpose. For example, such a formation method includes a method in which a coating film is formed by applying the coating composition to any coating surface of a substrate, drying the coating film, and then curing the coating film as necessary to form a coating film. Examples of substrates include metal, wood, glass, and plastics (PET (polyethylene terephthalate), PC (polycarbonate), acrylic resin, TAC (triacetyl cellulose), etc.).

<<2. Method for producing hollow resin particles>>
A method for producing hollow resin particles according to an embodiment of the present invention is a method for producing hollow resin particles having a shell portion and a hollow portion surrounded by the shell portion, which comprises reacting 30 to 70 parts by weight of monomer (A), which is a polycyclic aromatic hydrocarbon having a polymerization reactive group, with 70 to 30 parts by weight of monomer (M) that reacts with monomer (A) (the total amount of monomer (A) and monomer (M) being 100 parts by weight), in an aqueous medium in the presence of a non-reactive solvent, and wherein monomer (M) contains compound (B) having a phosphate ester structure and a radical reactive group.

The above manufacturing method makes it possible to easily manufacture hollow resin particles according to an embodiment of the present invention.

By reacting monomer (A) and monomer (M) in an aqueous medium in the presence of a non-reactive solvent, hollow resin particles having a shell portion and a hollow portion surrounded by the shell portion can be obtained, which can achieve a low dielectric constant and a low dielectric loss tangent and can exhibit excellent heat resistance.

In the method for producing hollow resin particles according to the embodiment of the present invention, monomer (A) and monomer (M) are preferably subjected to a suspension polymerization reaction.

Suspension polymerization is typically performed using an aqueous phase containing an aqueous medium and an oil phase containing monomer (A), monomer (M) and a non-reactive solvent. Preferably, the oil phase containing monomer (A), monomer (M) and a non-reactive solvent is added to the aqueous phase containing an aqueous medium, dispersed, and heated to perform suspension polymerization.

For dispersion, any suitable dispersion method may be employed as long as the oil phase can be present in the form of droplets in the aqueous phase, as long as the effects of the present invention are not impaired. Such a dispersion method typically uses a homomixer or a homogenizer, such as a Polytron homogenizer, an ultrasonic homogenizer, or a high-pressure homogenizer.

As the polymerization temperature, any appropriate polymerization temperature may be adopted as long as it is a temperature suitable for suspension polymerization, as long as it does not impair the effects of the present invention. The polymerization temperature is preferably 30°C to 80°C.

As the polymerization time, any appropriate polymerization time may be adopted as long as it is a time suitable for suspension polymerization and does not impair the effects of the present invention. The polymerization time is preferably 1 hour to 48 hours.

Post-heating, which is preferably carried out after polymerization, is a suitable treatment for obtaining hollow resin particles with a high degree of perfection.

The temperature of the post-heating preferably performed after polymerization may be any appropriate temperature within a range that does not impair the effects of the present invention. The temperature of such post-heating is preferably 70°C to 120°C.

As the time period for post-heating preferably carried out after polymerization, any appropriate time period can be adopted within a range that does not impair the effects of the present invention. The time for such post-heating is preferably 1 hour to 24 hours.

The content ratios of monomer (A), monomer (M), and various components are as follows: <<<1. Hollow resin particles≫≫≪1-2. The explanation in the item “Shell Portion” can be used as is.

Examples of aqueous media include water and mixtures of water and lower alcohols (methanol, ethanol, etc.).

The amount of the aqueous medium to be used may be any appropriate amount within a range that does not impair the effects of the present invention. The amount of such aqueous medium to be used is typically such that the suspension polymerization reaction, which is carried out by adding and suspending an oil phase to an aqueous phase, allows the reaction to proceed appropriately. The amount is preferably from 100 parts by weight to 5,000 parts by weight, more preferably from 150 parts by weight to 2,000 parts by weight, based on 100 parts by weight of the total amount of (M) and the non-reactive solvent.

The non-reactive solvent is a solvent that does not chemically react with either the monomer (A) or the monomer (M), and is preferably an organic solvent. The non-reactive solvent typically acts as a hollowing agent that gives the particles air space. Examples of non-reactive solvents include heptane, hexane, toluene, cyclohexane, methyl acetate, ethyl acetate, methyl ethyl ketone, chloroform, and carbon tetrachloride. In terms of ease of removal from the hollow resin particles, it is preferable that the boiling point of the non-reactive solvent is less than 100°C.

The non-reactive solvent used as the hollowing agent may be a single solvent or a mixed solvent.

The amount of non-reactive solvent added is preferably 20 to 250 parts by weight per 100 parts by weight of the total amount of monomer (A) and monomer (M).

When reacting monomer (A) with monomer (M), any suitable additive (C) that does not fall under either monomer (A) or monomer (M) may be used within a range that does not impair the effects of the present invention. The additive (C) may be of only one type, or of two or more types. The additive (C) does not include solvents such as aqueous media and non-reactive solvents, and dispersion stabilizers.

The content of additive (C) is preferably 0% to 40% by weight, more preferably 0% to 30% by weight, even more preferably 0% to 20% by weight, and particularly preferably 0% to 10% by weight, based on the total amount of monomer (A) and monomer (M).

As the additive (C), any suitable additive that does not fall under either the monomer (A) or the monomer (M) may be used as long as it does not impair the effects of the present invention. Examples of such additives (C) include non-crosslinkable polymers and polymerization initiators.

For non-crosslinkable polymers, see ≪≪1. Hollow resin particles≫≫≪1-2. The explanation in the item “Shell Portion” can be used as is.

As the polymerization initiator, any suitable polymerization initiator may be employed as long as the effects of the present invention are not impaired. Examples of such polymerization initiators include lauroyl peroxide, benzoyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, and t-butylperoxy-2- Organic peroxides such as ethylhexanoate and di-t-butyl peroxide; 2,2'-azobisisobutyronitrile, 1,1'-azobiscyclohexane carbonitrile, 2,2'-azobis(2 , 4-dimethylvaleronitrile); and the like. The number of polymerization initiators may be one, or two or more.

The content of the polymerization initiator is preferably in the range of 0.1% to 5% by weight based on the total amount of monomer (A) and monomer (M).

When reacting monomer (A) and monomer (M), any appropriate dispersion stabilizer (not applicable to either monomer (A) or monomer (M)) may be used within the range that does not impair the effects of the present invention. D) may also be used. The number of dispersion stabilizers (D) may be one, or two or more.

The dispersion stabilizer (D) is preferably used in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the aqueous medium. The number of dispersion stabilizers (D) may be one, or two or more.

Specific examples of the dispersion stabilizer (D) include <<<1. Hollow resin particles≫≫≪1-2. The explanation in the item “Shell Portion” can be used as is.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples. In addition, unless otherwise specified, "parts" means "parts by weight" and "%" means "% by weight."

≪Measurement of volume average particle diameter and coefficient of variation≫
The volume average particle diameter of the particles was measured by the Coulter method as follows.
The volume average particle diameter of the particles was measured using Coulter Multisizer (registered trademark) 3 (measurement device manufactured by Beckman Coulter, Inc.). Measurements were performed using an aperture calibrated according to the Multisizer® 3 User's Manual published by Beckman Coulter, Inc. In addition, for the aperture used in the measurement, if the assumed volume average particle diameter of the particles to be measured is 1 μm or more and 10 μm or less, select an aperture with a size of 50 μm, and if the assumed volume average particle diameter of the particles to be measured is larger than 10 μm. If the expected volume average particle size of the particles is 30 μm or less, select an aperture with a size of 100 μm; if the assumed volume average particle size of the particles is greater than 30 μm and 90 μm or less, select an aperture with a size of 280 μm; The aperture size was appropriately selected depending on the size of the particles to be measured, such as selecting an aperture having a size of 400 μm when the particle size was larger than 90 μm and less than 150 μm. If the volume average particle diameter after measurement was different from the expected volume average particle diameter, the aperture was changed to an appropriate size and the measurement was performed again. Current (aperture current) and Gain (gain) were appropriately set depending on the selected aperture size. For example, if you select an aperture with a size of 50 μm, Current (aperture current) is set to -800 and Gain (gain) is set to 4, and if you select an aperture with a size of 100 μm, Current (aperture current) is set to -800. 1600, Gain was set to 2, and when apertures having sizes of 280 μm and 400 μm were selected, Current (aperture current) was set to −3200, and Gain was set to 1.
As a sample for measurement, 0.1 g of particles was placed in 10 ml of a 0.1% by weight nonionic surfactant aqueous solution using a touch mixer (Yamato Scientific Co., Ltd., "TOUCHMIXER MT-31") and an ultrasonic cleaner (Vell Co., Ltd.). A dispersion liquid was prepared by dispersing the liquid using "ULTRASONIC CLEANER VS-150" (manufactured by Vokulea). During the measurement, the inside of the beaker was gently stirred to prevent air bubbles from entering, and the measurement was terminated when 100,000 particles were measured. The volume average particle diameter of the particles was the arithmetic mean of the volume-based particle size distribution of 100,000 particles.
The coefficient of variation (CV value) of the particle diameter of the particles was calculated using the following formula.
Coefficient of variation (%) of particle diameter of particles = (standard deviation of particle size distribution based on volume of particles ÷ volume average particle diameter of particles) x 100 (%)

≪Cross-sectional observation≫
The dried particles were mixed with a photocurable resin "D-800" (manufactured by JEOL Ltd.) and irradiated with ultraviolet light to obtain a cured product. Thereafter, the cured product was cut with nippers, the cross section was smoothed using a cutter, and the sample was coated using an "Auto Fine Coater JFC-1300" sputtering device manufactured by JEOL Ltd. Next, a cross section of the sample was photographed using a secondary electron detector of a "SU1510" scanning electron microscope manufactured by Hitachi High-Technologies Corporation.

≪Measurement of 5% weight loss temperature when heating at 10°C/min in nitrogen atmosphere≫
The 5% weight loss temperature was measured using a differential thermogravimetry simultaneous measuring device "TG/DTA6200, AST-2" manufactured by SII Nano Technology Co., Ltd. The sampling method and temperature conditions were as follows.
10.5±0.5 mg of the sample was filled in the bottom of a platinum measurement container without any gaps to prepare a sample for measurement. The 5% weight loss temperature was measured using alumina as a reference material under a nitrogen gas flow rate of 230 mL/min. The TG/DTA curve was obtained by heating the sample from 30°C to 500°C at a heating rate of 10°C/min. From this obtained curve, the temperature at 5% weight loss was calculated using analysis software attached to the apparatus, and was defined as the 5% weight loss temperature.

Example 1
An oil phase was prepared by mixing 3.30 g of a polycyclic aromatic hydrocarbon monomer having a polymerization reactive group (product name "Acenaphthylene", manufactured by JFE Chemical Corporation), 3.30 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Material Co., Ltd., 81% content, 19% is ethylvinylbenzene (EVB)), 3.30 g of cyclohexane, 0.13 g of 2,2'-azobis(isobutyronitrile) (AIBN, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) as a polymerization initiator, and 0.03 g of "KAYAMER (registered trademark) PM-21" (manufactured by Nippon Kayaku Co., Ltd.) as a radical polymerizable monomer having a phosphoric acid group.
The oil phase was added to 32 g of a 2 wt % aqueous dispersion of magnesium pyrophosphate as the aqueous phase, and dispersed at 7,000 rpm for 3 minutes using a Polytron homogenizer "PT10-35" (manufactured by Central Scientific Trading Co., Ltd.) to prepare a suspension. The resulting suspension was heated and stirred at 70°C for 24 hours to complete the polymerization reaction. Hydrochloric acid was added to the resulting slurry to decompose the magnesium pyrophosphate, and the solid content was separated by dehydration through filtration, purified by repeated washing with water, and then dried by heating to obtain particles (1).
When the obtained particles (1) were photographed with a scanning electron microscope (SEM), it was confirmed that the particle surface had no pores and was a smooth spherical particle.
A cross-sectional photograph of the obtained particle (1) is shown in Fig. 1. It was confirmed that the obtained particle (1) was a hollow resin particle having a porous structure surrounded by a shell.
The volume average particle size of the obtained particles (1) was 10.3 μm, and the variation coefficient was 39.2%.
The 5% weight loss temperature of the obtained particles (1) was 342.8°C when the temperature was increased at 10°C/min in a nitrogen atmosphere.
The blend amounts and various measurement results are shown in Table 1.

Example 2
Particles (2) were obtained in the same manner as in Example 1, except that 3.30 g of heptane was used instead of 3.30 g of cyclohexane, and 0.13 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (ADVM, trade name "V-65", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used instead of 0.13 g of 2,2'-azobis(isobutyronitrile).
When the obtained particles (2) were photographed with a scanning electron microscope (SEM), it was confirmed that the particle surface had no pores and was a smooth spherical particle.
A cross-sectional photograph of the obtained particle (2) is shown in Fig. 2. It was confirmed that the obtained particle (2) was a hollow resin particle having a porous structure surrounded by a shell.
The volume average particle size of the obtained particles (2) was 16.7 μm, and the coefficient of variation was 46.9%.
The 5% weight loss temperature of the obtained particles (2) was 383.9°C when the temperature was increased at 10°C/min in a nitrogen atmosphere.
The blend amounts and various measurement results are shown in Table 1.

Example 3
Particles (3) were obtained in the same manner as in Example 2, except that the amount of the polycyclic aromatic hydrocarbon monomer having a polymerization reactive group (product name "Acenaphthylene", manufactured by JFE Chemical Corporation) used was changed to 2.64 g, and the amount of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Material Corporation, 81% content, 19% is ethylvinylbenzene (EVB)) used was changed to 3.96 g.
When the obtained particles (3) were photographed with a scanning electron microscope (SEM), it was confirmed that the particle surface had no pores and was a smooth spherical particle.
A cross-sectional photograph of the obtained particle (3) is shown in Fig. 3. It was confirmed that the obtained particle (3) was a hollow resin particle having a porous structure surrounded by a shell.
The volume average particle size of the obtained particles (3) was 10.9 μm, and the variation coefficient was 42.3%.
The 5% weight loss temperature of the obtained particles (3) was 382.3°C when the temperature was increased at 10°C/min in a nitrogen atmosphere.
The blend amounts and various measurement results are shown in Table 1.

[Example 4]
The amount of polycyclic aromatic hydrocarbon monomer having a polymerization-reactive group (trade name "acenaphthylene", manufactured by JFE Chemical Corporation) was changed to 3.96 g, and the amount of divinylbenzene (DVB) 810 (Nippon Steel Chemical Co., Ltd.) was changed to 3.96 g. Particles (4) were obtained in the same manner as in Example 2, except that the amount of the product manufactured by & Materials Co., Ltd., containing 81% (19% ethylvinylbenzene (EVB)) was changed to 2.64 g.
When the obtained particle (4) was imaged using a scanning electron microscope (SEM), it was found that the particle surface had no pores and was a smooth spherical particle.
A cross-sectional photographic diagram of the obtained particles (4) is shown in FIG. It was confirmed that the obtained particles (4) were hollow resin particles consisting of one hollow area surrounded by a shell.
The volume average particle diameter of the obtained particles (4) was 10.9 μm, and the coefficient of variation was 36.7%.
The 5% weight loss temperature of the obtained particles (4) when heated at a rate of 10°C/min in a nitrogen atmosphere was 381.3°C.
Table 1 shows the blending amount and various measurement results.

Example 5
Particles (5) were obtained in the same manner as in Example 2, except that the amount of the polycyclic aromatic hydrocarbon monomer having a polymerization reactive group (product name "Acenaphthylene", manufactured by JFE Chemical Corporation) used was changed to 2.50 g, the amount of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Material Corporation, 81% content, 19% is ethylvinylbenzene (EVB)) used was changed to 2.50 g, the amount of heptane used was changed to 5.00 g, and the amount of 2,2'-azobis(2,4-dimethylvaleronitrile) used was changed to 0.10 g.
When the obtained particles (5) were photographed with a scanning electron microscope (SEM), it was confirmed that the particle surface had no pores and was a spherical particle having an uneven surface.
A cross-sectional photograph of the obtained particle (5) is shown in Fig. 5. It was confirmed that the obtained particle (5) was a hollow resin particle having one hollow region surrounded by a shell.
The volume average particle size of the obtained particles (5) was 12.8 μm, and the coefficient of variation was 34.0%.
The 5% weight loss temperature of the obtained particles (5) was 389.4°C when the temperature was increased at 10°C/min in a nitrogen atmosphere.
The blend amounts and various measurement results are shown in Table 1.

[Example 6]
Except that an ultrasonic homogenizer (BRANSON, SONIFIER 450, conditions: Duty Cycle = 50%, Output Control = 5, processing time 3 minutes) was used in place of the Polytron homogenizer "PT10-35" when preparing the suspension. Particles (6) were obtained in the same manner as in Example 2.
When the obtained particles (6) were imaged using a scanning electron microscope (SEM), it was found that there were no pores on the particle surface and that the particles were smooth spherical particles.
A cross-sectional photographic diagram of the obtained particles (6) is shown in FIG. It was confirmed that the obtained particles (6) were hollow resin particles in which a hollow surrounded by a shell had a porous structure.
The volume average particle diameter of the obtained particles (6) was 3.4 μm, and the coefficient of variation was 44.8%.
The 5% weight loss temperature of the obtained particles (6) when heated at a rate of 10°C/min in a nitrogen atmosphere was 385.4°C.
Table 1 shows the blending amount and various measurement results.

Example 7
Particles (7) were obtained in the same manner as in Example 6, except that the amount of the polycyclic aromatic hydrocarbon monomer having a polymerization reactive group (product name "Acenaphthylene", manufactured by JFE Chemical Corporation) used was changed to 2.00 g, the amount of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Material Corporation, 81% content, 19% is ethylvinylbenzene (EVB)) used was changed to 3.00 g, the amount of heptane used was changed to 5.00 g, and the amount of 2,2'-azobis(2,4-dimethylvaleronitrile) used was changed to 0.10 g.
When the obtained particles (7) were photographed with a scanning electron microscope (SEM), it was confirmed that the particle surface had no pores and was a smooth spherical particle.
A cross-sectional photograph of the obtained particle (7) is shown in Fig. 7. It was confirmed that the obtained particle (7) was a hollow resin particle having one hollow region surrounded by a shell.
The volume average particle size of the obtained particles (7) was 4.3 μm, and the variation coefficient was 30.7%.
The 5% weight loss temperature of the obtained particles (7) was 380.2°C when the temperature was increased at 10°C/min in a nitrogen atmosphere.
The blend amounts and various measurement results are shown in Table 1.

[Example 8]
Particles (8) were obtained in the same manner as in Example 7, except that 2.50 g of cyclohexane and 2.50 g of ethyl acetate were used instead of 5.00 g of heptane.
When the obtained particle (8) was imaged with a scanning electron microscope (SEM), it was found that the particle surface had no pores and was a smooth spherical particle.
A cross-sectional photographic diagram of the obtained particles (8) is shown in FIG. It was confirmed that the obtained particles (8) were hollow resin particles in which a hollow surrounded by a shell had a porous structure.
The volume average particle diameter of the obtained particles (8) was 3.3 μm, and the coefficient of variation was 38.0%.
The 5% weight loss temperature of the obtained particles (8) when heated at a rate of 10°C/min in a nitrogen atmosphere was 384.5°C.
Table 1 shows the blending amount and various measurement results.

Example 9
Particles (9) were obtained in the same manner as in Example 7, except that 3.75 g of cyclohexane and 1.25 g of ethyl acetate were used instead of 5.00 g of heptane.
When the obtained particles (9) were photographed with a scanning electron microscope (SEM), it was confirmed that the particle surface had no pores and was a smooth spherical particle.
A cross-sectional photograph of the obtained particle (9) is shown in Fig. 9. It was confirmed that the obtained particle (9) was a hollow resin particle having one hollow region surrounded by a shell.
The volume average particle size of the obtained particles (9) was 3.8 μm, and the variation coefficient was 42.1%.
The 5% weight loss temperature of the obtained particles (9) was 378.7°C when the temperature was increased at 10°C/min in a nitrogen atmosphere.
The blend amounts and various measurement results are shown in Table 1.

[Comparative example 1]
2.0 g of methyl methacrylate, 2.0 g of ethylene glycol dimethacrylate, 4.0 g of cyclohexane, 40 g of ethyl acetate, 2,2'-azobis(2,4-dimethylvaleronitrile) (trade name "V-") as a polymerization initiator. 65'' (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) 0.067 g, and 0.024 g of "KAYAMER (registered trademark) PM-21" (manufactured by Nippon Kayaku Co., Ltd.) as a radically polymerizable monomer having a phosphoric acid group were mixed. Then, an oil phase was prepared.
The oil phase was added to 32 g of a 2% by weight aqueous dispersion of magnesium pyrophosphate as the aqueous phase, and dispersed for 5 minutes at 7000 rpm using a Polytron homogenizer "PT10-35" (manufactured by Central Kagaku Boeki Co., Ltd.) to suspend the water. A liquid was prepared. The resulting suspension was heated and stirred at 55° C. for 24 hours to complete the polymerization reaction. Hydrochloric acid was added to the resulting slurry to decompose magnesium pyrophosphate, the solid content was separated by dehydration by filtration, purified by repeated washing with water, and then heated and dried to obtain particles (C1). Ta.
When the obtained particles (C1) were imaged with a scanning electron microscope (SEM), it was found that there were no pores on the particle surface and that the particles were smooth spherical particles.
A cross-sectional photographic diagram of the obtained particles (C1) is shown in FIG. It was confirmed that the obtained particles (10) were hollow resin particles in which a hollow surrounded by a shell had a porous structure.
The volume average particle diameter of the obtained particles (C1) was 7.6 μm, and the coefficient of variation was 26.8%.
The obtained particles (C1) had a 5% weight loss temperature of 240.0°C when heated at a rate of 10°C/min in a nitrogen atmosphere.
Table 1 shows the blending amount and various measurement results.

≪Performance evaluation: Relative permittivity and dielectric loss tangent evaluation≫
0.425 g of particles obtained in Examples and Comparative Examples, 8.3 g of ethyl acetate, and 1.7 g of solvent-soluble polyimide KPI-MX300F (manufactured by Kawamura Sangyo Co., Ltd.) were placed in a planetary stirring deaerator (KURABO). A mixture for evaluation was prepared by defoaming and stirring using a Mazerstar KK-250 (manufactured by Co., Ltd.).
After applying the evaluation mixture to a glass plate with a thickness of 5 mm using an applicator set to a wet thickness of 250 μm, the mixture was applied 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. After removing ethyl acetate by heating for minutes, a film sample containing each particle was obtained by cooling to room temperature. The dielectric constant and dielectric loss tangent of the obtained film were evaluated using the cavity resonance method (measurement frequency: 5.8 GHz). The measurement results were expressed as relative proportions (%) with the measured value of the film containing no particles taken as 100%. The results are shown in Table 2.

The results in Table 2 confirm that the hollow resin particles provided by the present invention have the effect of lowering the relative dielectric constant and dielectric loss tangent of the substrate, and are therefore effective in reducing the dielectric constant and dielectric loss tangent of semiconductor materials.

≪Cross-sectional observation of film≫
A cross-sectional sample of the film containing each particle used in the dielectric constant and dielectric loss tangent evaluation was prepared using the cross-section polisher method using a cross-section preparation device "IB-19500CP" (manufactured by JEOL Ltd.), and was manufactured by Hitachi High-Technologies Corporation. A cross-sectional photograph was taken using a scanning electron microscope "S-3400N" manufactured by Kabushiki Kaisha, Ltd., and the cross-section was observed.
In the cross-sectional photograph, the white part means polyimide, and the spherical substance that can be observed within the white part means hollow resin particles. Further, the black portion inside the hollow resin particle indicates an air layer.
FIG. 11 is a cross-sectional photographic diagram of a film produced using particles (8) obtained in Example 8. If the inside of the hollow resin particle is observed to be black as shown in Figure 11, it means that the voids of the hollow resin particle are maintained within the polyimide film, that is, the resin (polyimide) has not penetrated into the inside of the hollow resin particle. It means not.

The hollow resin particles according to the embodiments of the present invention and the hollow resin particles obtained by the manufacturing method according to the embodiments of the present invention can be used for semiconductor materials and the like. The hollow resin particles according to the embodiments of the present invention and the hollow resin particles obtained by the manufacturing method according to the embodiments of the present invention can be applied, for example, to resin compositions for semiconductor members.

Claims (13)

A hollow resin particle having a shell part and a hollow part surrounded by the shell part,
The shell portion contains a polymer (P) having a polycyclic aromatic hydrocarbon structural unit,
Hollow resin particles. The hollow resin particle according to claim 1, wherein the polycyclic aromatic hydrocarbon structural unit is a structural unit represented by formula (1).
A claim in which the polymer (P) is a polymer obtained by a reaction between a monomer (A) that is a polycyclic aromatic hydrocarbon having a polymerization-reactive group and a monomer (M) that reacts with the monomer (A). 1. The hollow resin particles according to 1. The ratio of the monomer (A) and the monomer (M) is based on the weight part ratio (monomer (A):monomer (M)) when the total amount of the monomer (A) and the monomer (M) is 100 parts by weight. ) and (30 parts by weight to 70 parts by weight): (70 parts by weight to 30 parts by weight), the hollow resin particles according to claim 3. The hollow resin particles according to claim 3, wherein the monomer (A) is acenaphthylene. The hollow resin particle according to claim 3, wherein the monomer (M) contains a compound (B) having a phosphate ester structure and a radically reactive group. The hollow resin particles according to claim 1, having a volume average particle diameter of 0.1 μm to 100 μm. The hollow resin particles according to claim 7, wherein the volume average particle diameter is 0.1 μm to 10 μm. The hollow resin particle according to claim 1, wherein the hollow portion consists of one hollow region. The hollow resin particle according to claim 1, wherein the hollow portion consists of a plurality of hollow regions. The hollow resin particles according to claim 1, wherein the 5% weight loss temperature when the hollow resin particles are heated at a rate of 10°C/min in a nitrogen atmosphere is 300°C or higher. The hollow resin particles according to claim 1, which are used in a resin composition for semiconductor members. A method for producing hollow resin particles having a shell portion and a hollow portion surrounded by the shell portion, the method comprising:
30 to 70 parts by weight of a monomer (A) that is a polycyclic aromatic hydrocarbon having a polymerization-reactive group and 70 to 30 parts by weight of a monomer (M) that reacts with the monomer (A) ) and monomer (M) (total amount of 100 parts by weight) are reacted in an aqueous medium in the presence of a non-reactive solvent,
The monomer (M) contains a compound (B) having a phosphate ester structure and a radically reactive group,
Method for manufacturing hollow resin particles.