Hollow resin particles, their manufacturing method, and their uses

Abstract

Provided are hollow resin particles having a shell part and a hollow portion surrounded by the shell part, said hollow resin particles being capable of achieving dielectric lowering and dielectric loss tangent lowering and exhibiting excellent heat resistance. Also provided is a method for producing the hollow resin particles. Further provided is use of the hollow resin particles.　Hollow resin particles according to one embodiment of the present invention have a shell part and a hollow portion surrounded by the shell part, wherein the shell part contains a polymer (P) that has an ether structure represented by formula (1) and a phosphoric acid ester structure.

Description

[Technical Field]

[0001] The present invention relates to hollow resin particles, a method for producing the same, and uses thereof. [Background technology]

[0002] In order to speed up 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 these efforts, studies have been made to introduce airspace into the resin layer by mixing hollow particles, each having a shell portion and a hollow portion surrounded by the shell portion, into a thermosetting resin, thereby reducing the dielectric constant and dielectric loss tangent.

[0003] Hollow resin particles used for 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 processing of a thermosetting resin containing the hollow resin particles or during use with solder.

[0004] Furthermore, when hollow resin particles are mixed with a thermosetting resin, with conventional hollow resin particles, the thermosetting resin may penetrate into the interior of the hollow resin particles during kneading, which can cause the problem of not being able to maintain the air space inside the hollow resin particles.

[0005] It has been reported that conventional hollow resin particles can be obtained by suspension polymerization of a monomer containing 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 dielectric constants and dielectric loss tangents, and insufficient heat resistance. For this reason, the acrylic hollow resin particles described in Patent Document 1 are unsuitable for achieving a low dielectric constant and dielectric loss tangent in a resin layer, or for imparting high heat resistance to a resin layer.

[0006] It has been reported that conventional hollow resin particles can be obtained by suspension polymerization of a monomer primarily 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 (Patent Document 2). However, acrylic resins have high dielectric constants and dielectric dissipation factors, 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 unsuitable for achieving a low dielectric constant and dielectric dissipation factor in the resin layer or for imparting high heat resistance to the resin layer. Furthermore, the porous hollow polymer particles have a thin shell surface, which allows thermosetting resins to easily penetrate into the interior of the porous hollow polymer particles.

[0007] Conventional hollow resin particles have been reported to be blended with resins to produce organic insulating materials with excellent insulating properties, low dielectric constants, and low dielectric dissipation factors. Specific examples of such hollow resin particles 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 monomer, which has a high dielectric constant and dielectric dissipation factor, resulting in insufficient low dielectric constant and low dielectric dissipation factor for the resin layer. Patent Document 3 also lists the 10% weight loss temperature measured by TG-DTA in a nitrogen atmosphere at a temperature increase rate of 10°C / min as a guideline for heat resistance, but the heat resistance is insufficient.

[0008] Conventional hollow resin particles have been reported in which the shell is composed of either a polymer or copolymer of a crosslinkable monomer or a copolymer of the crosslinkable monomer and a monofunctional monomer, and the shell has a single-phase structure. These particles are typically obtained by suspension polymerization of divinylbenzene with saturated hydrocarbons having 8 to 18 carbon atoms (more specifically, hexadecane). It has also been reported that resin compositions containing such hollow resin particles and a thermosetting resin are suitable for the production of multilayer printed circuit boards used in electronic devices (Patent Document 4). However, because the hollow resin particles described in Patent Document 4 use saturated hydrocarbons having 8 to 18 carbon atoms (more specifically, hexadecane) in their production, it is difficult to remove the solvent from the hollow portions by distillation or other methods. Consequently, saturated hydrocarbons having 8 to 18 carbon atoms remain in the resulting styrene-based hollow resin particles, making it difficult to obtain styrene-based hollow resin particles with the hollow portions completely replaced with air. Furthermore, the solvent removal required to obtain styrene-based hollow resin particles with the hollow portions completely replaced with air increases production costs. Furthermore, the styrene-based hollow resin particles described in Patent Document 4 have insufficient heat resistance.

[0009] Conventional hollow resin particles have been reported to be composed of a polymer containing vinyl monomer units and phosphate ester monomer units, and have a volume average particle diameter of 0.5 to 1000 μm (Patent Document 5). However, like the hollow resin particles described in Patent Document 3, the hollow resin particles described in Patent Document 5 use a styrene monomer in combination with an acrylic monomer with high dielectric constant and dielectric loss tangent, and therefore the resin layer does not have a sufficiently low dielectric constant and dielectric loss tangent, and the heat resistance is also insufficient.

[0010] Conventional hollow resin particles include hollow polymeric microparticles consisting of a shell and a hollow portion, the shell having a single-layer structure made of a copolymer of at least one crosslinkable monomer and at least one monofunctional monomer, and the copolymer being obtained by polymerizing a mixture containing 59.2 wt % or more of the crosslinkable monomer relative to the total amount of the monofunctional monomer and the crosslinkable monomer (Patent Document 6). However, the hollow resin particles described in Patent Document 6 are hollow resin particles of acrylic and styrene-based compositions. Acrylic compositions have high dielectric constants and dielectric loss tangents and insufficient heat resistance. Styrene-based compositions have insufficient heat resistance.

[0011] It has been reported that a curable resin composition containing as essential components a vinyl compound in which the terminals of a bifunctional polyphenylene ether oligomer are converted to vinyl groups and a high molecular weight component having a weight-average molecular weight of 10,000 or more gives a cured product with a low dielectric constant, low dielectric loss tangent, and excellent heat resistance (Patent Document 7). However, the resin composition described in Patent Document 7 is a resin composition containing vinyl groups and unsaturated double bonds. Heating of the vinyl groups and unsaturated double bonds during the manufacturing process causes an oxidation reaction, and heat generated by thermal decomposition can cause warping of the resin composition, or the thermal history of the resin composition can deteriorate the dielectric loss tangent.

[0012] It has been reported that a thermosetting resin composition containing a modified polyphenylene ether compound having a weight-average molecular weight of 1,000 or more and an intrinsic viscosity of 0.03 to 0.12 dL / g as measured in chloroform at 25°C, and terminally modified with a substituent having a terminal carbon-carbon unsaturated double bond, (B) a crosslinkable styrene-butadiene copolymer having a number-average molecular weight of less than 10,000 and a styrene content of 50 mass% or less and a butadiene content of 50 mass% or more in the molecule, (C) a styrene-based thermoplastic elastomer having a weight-average molecular weight of 10,000 or more, (D) a curing accelerator, (E) an inorganic filler, and (F) a flame retardant, in which the blending ratio of the component (A):[the component (B) + the component (C)] is 90:10 to 10:90, has excellent toughness and dielectric properties, and the resulting substrate can have reduced in-plane dielectric constant variation and can be prevented from warping (Patent Document 8). However, the resin composition described in Patent Document 8 requires a resin curing temperature of 100°C or higher, which is a temperature higher than the boiling point of the solvent. Therefore, it is difficult to produce hollow particles by suspension polymerization using this resin composition. [Prior art documents] [Patent documents]

[0013] [Patent Document 1] Patent No. 6513273 [Patent Document 2] Patent No. 4445495 [Patent Document 3] Japanese Patent Application Laid-Open No. 2000-313818 [Patent Document 4] Patent No. 4171489 [Patent Document 5] International Publication No. 2020 / 054816 Brochure [Patent Document 6] Patent No. 4448930 [Patent Document 7] Japanese Patent Application Laid-Open No. 2006-83364 [Patent Document 8] Japanese Patent Application Publication No. 2018-95815 Summary of the Invention [Problem to be solved by the invention]

[0014] The present invention has been made to solve the above-mentioned problems of the related art, and its main object is 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, a low dielectric loss tangent, and exhibit excellent heat resistance. It is also an object of the present invention to provide a method for producing such hollow resin particles. Furthermore, it is an object of the present invention to provide uses of such hollow resin particles. [Means for solving the problem]

[0015] [1] 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 an ether structure and a phosphate ester structure represented by formula (1). [ka] [2] In the hollow resin particles described in [1] above, the polymer (P) may be a polymer (AM) obtained by reacting a compound (A) having an ether structure and a radical-reactive group represented by the above formula (1) with a monomer (M) that reacts with the compound (A), and the monomer (M) may contain a compound (B) having a phosphate ester structure and a radical-reactive group. [3] In the hollow resin particles described in [2] above, the ratio of the compound (A) to the monomer (M) may be (20 to 80 parts by weight):(80 to 20 parts by weight) in terms of parts by weight (compound (A):monomer (M)), where the total amount of the compound (A) and the monomer (M) is taken as 100 parts by weight. [4] In the hollow resin particles according to the above [2] or [3], the total amount of the compound (A) and the monomer (M) is 1 When expressed in parts by weight, the amount of the compound (B) relative to the total amount may be 0.0001 to 0.0190 parts by weight. [5] In the hollow resin particles described in [1] above, the polymer (P) may contain elemental sulfur. [6] In the hollow resin particles described in [5] above, the residual vinyl group ratio of the hollow resin particles may be 15% or less. [7] In the hollow resin particles according to the above [5] or [6], the hollow resin particles may have an exothermic initiation temperature of 290°C or higher in the atmosphere. [8] In the hollow resin particles according to any one of the above items [5] to [7], the hollow resin particles may have a sulfur atom content of 0.1% by mass to 3.0% by mass. [9] In the hollow resin particles according to any one of [5] to [8] above, the polymer (P) may be a polymer obtained by reacting a polymer (AM) obtained by reacting a compound (A) having an ether structure and a radical reactive group represented by the above formula (1) with a monomer (M) that reacts with the compound (A), with a thiol.

[10] In the hollow resin particles described in [9] above, the ratio of the compound (A) to the monomer (M) may be (20 parts by weight to 80 parts by weight):(80 parts by weight to 20 parts by weight) in terms of parts by weight (compound (A):monomer (M)), where the total amount of the compound (A) and the monomer (M) is 100 parts by weight.

[11] In the hollow resin particles according to any one of the above items [1] to

[10] , the volume average particle diameter of the hollow resin particles may be 0.1 μm to 100 μm.

[12] In the hollow resin particles according to any one of the above items [1] to

[11] , the coefficient of variation (CV value) of the particle diameter of the hollow resin particles may be 10% to 50%.

[13] In the hollow resin particles according to any one of [1] to

[12] above, the hollow resin particles may have a 5% weight loss temperature of 290°C or higher when heated at a rate of 10°C / min in a nitrogen atmosphere.

[14] The hollow resin particles according to any one of the above items [1] to

[13] may be used in a resin composition for a semiconductor member.

[15] The hollow resin particles according to any one of the above items [1] to

[13] may be used in a coating composition.

[16] The hollow resin particles according to any one of the above items [1] to

[13] may be used in a heat insulating resin composition.

[17] The hollow resin particles according to any one of the above items [1] to

[13] may be used in a light-diffusing resin composition.

[18] The hollow resin particles according to any one of the above items [1] to

[13] may be used in a light diffusion film.

[19] A resin composition for a semiconductor member according to an embodiment of the present invention contains the hollow resin particles according to any one of [1] to

[13] above.

[20] A coating composition according to an embodiment of the present invention contains the hollow resin particles described in any one of [1] to

[13] above.

[21] A heat insulating resin composition according to an embodiment of the present invention contains the hollow resin particles according to any one of [1] to

[13] above.

[22] A light-diffusing resin composition according to an embodiment of the present invention contains the hollow resin particles described in any one of [1] to

[13] above.

[23] A light diffusion film according to an embodiment of the present invention contains the hollow resin particles according to any one of [1] to

[13] above.

[24] A method for producing hollow resin particles according to an embodiment of the present invention comprises reacting 20 to 80 parts by weight of a compound (A) having an ether structure and a radical-reactive group, represented by formula (1), with 80 to 20 parts by weight of a monomer (M) that reacts with the compound (A) (the total amount of the compound (A) and the monomer (M) being 100 parts by weight), in an aqueous medium in the presence of a non-reactive solvent, wherein the monomer (M) contains a compound (B) having a phosphate ester structure and a radical-reactive group. [ka]

[25] A method for producing hollow resin particles according to an embodiment of the present invention includes an oil phase preparation step (I) of mixing 20 to 80 parts by weight of a compound (A) having an ether structure and a radical-reactive group, represented by formula (1), and 80 to 20 parts by weight of a monomer (M) that reacts with the compound (A) (the total amount of the compound (A) and the monomer (M) being 100 parts by weight), with a non-reactive solvent to prepare an oil phase; a suspension polymerization step (II) of adding the oil phase to an aqueous phase containing an aqueous medium and stirring the mixture to prepare a suspension; and a thiol-ene reaction step (III) of adding a thiol to the suspension and reacting it to prepare a reaction product. [ka] [Effects of the Invention]

[0016] According to an embodiment of the present invention, hollow resin particles having a shell portion and a hollow portion surrounded by the shell portion can be provided, which can achieve a low dielectric constant and a low dielectric loss tangent and exhibit excellent heat resistance. Also, a method for producing such hollow resin particles can be provided. Furthermore, uses of such hollow resin particles can be provided. [Brief explanation of the drawings]

[0017] [Figure 1] FIG. 1 is a cross-sectional photograph of a particle (1) obtained in Example 1. [Figure 2] FIG. 2 is a cross-sectional photograph of the particle (2) obtained in Example 2. [Figure 3] FIG. 2 is a cross-sectional photograph of the particle (3) obtained in Example 3. [Figure 4] FIG. 1 is a cross-sectional photograph of particle (4) obtained in Example 4. [Figure 5] FIG. 1 is a cross-sectional photograph of particle (5) obtained in Example 5. [Figure 6] FIG. 1 is a cross-sectional photograph of particle (6) obtained in Example 6. [Figure 7] FIG. 1 is a cross-sectional photograph of particle (7) obtained in Example 7. [Figure 8]FIG. 2 is a cross-sectional photograph of the particles (C1) obtained in Comparative Example 1. [Figure 9] FIG. 2 is a cross-sectional photograph of particles (C3) obtained in Comparative Example 3. [Figure 10] FIG. 1 is a cross-sectional photograph of particle (8) obtained in Example 8. [Figure 11] FIG. 1 is a cross-sectional photograph of particle (9) obtained in Example 9. [Figure 12] FIG. 1 is a cross-sectional photograph of a particle (10) obtained in Example 10. [Figure 13] FIG. 1 is a cross-sectional photograph of a particle (11) obtained in Example 11. [Figure 14] FIG. 1 is a cross-sectional photograph of a particle (12) obtained in Example 12. [Figure 15] FIG. 1 is a cross-sectional photograph of a particle (13) obtained in Example 13. [Figure 16] FIG. 1 is a cross-sectional photograph of particle (14) obtained in Example 14. [Figure 17] FIG. 1 is a cross-sectional photograph of a particle (15) obtained in Example 15. [Figure 18] FIG. 1 is a cross-sectional photograph of a particle (16) obtained in Example 16. [Figure 19] FIG. 1 is a photograph of a cross section of a particle (17) obtained in Example 17. [Figure 20] FIG. 1 is a cross-sectional photograph of particles (C4) obtained in Comparative Example 4. [Figure 21] FIG. 1 is a cross-sectional photograph of particles (C5) obtained in Comparative Example 5. [Figure 22] FIG. 1 is a cross-sectional photograph of a film produced using particles (5) obtained in Example 5. [Figure 23] FIG. 1 is a cross-sectional photograph of a film produced using particles (C3) obtained in Comparative Example 3. [Figure 24] FIG. 1 shows the results of measurement of the coating composition (6-1) obtained in Example 21 using an ultraviolet-visible-near infrared spectrophotometer. [Figure 25] FIG. 1 shows the results of measurement of the coating composition (9-1) obtained in Example 24 using an ultraviolet-visible-near infrared spectrophotometer. DETAILED DESCRIPTION OF THE INVENTION

[0018] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these embodiments.

[0019] 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." Furthermore, 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.

[0020] ≪≪1. Hollow resin particles≫≫ 1-1. Structure and characteristics of hollow resin particles 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. Here, "hollow" means that the interior is filled with a substance other than resin, such as a gas or liquid, and preferably means that the interior is filled with a gas, in order to further exhibit the effects of the present invention.

[0021] The shell portion and the hollow portion surrounded by the shell portion may consist of one hollow region, or may consist of multiple hollow regions (porous structure).

[0022] The volume average particle diameter of the hollow resin particles according to an embodiment of the present invention is preferably 0.1 μm to 100 μm, more preferably 0.2 μm to 50.0 μm, even more preferably 0.3 μm to 30.0 μm, and particularly preferably 0.4 μm to 20.0 μm. When the volume average particle diameter of the hollow resin particles according to an embodiment of the present invention is within the above range, the effects of the present invention can be more effectively achieved. If the volume average particle diameter of the hollow resin particles according to an embodiment of the present invention is too small, outside the above range, the shell thickness becomes relatively thin, which may result in hollow resin particles that do not have sufficient strength. Furthermore, when the hollow resin particles are kneaded with a thermosetting resin, the thermosetting resin may penetrate into the hollow resin particles. If the volume average particle diameter of the hollow resin particles according to an embodiment of the present invention is too large, outside the above range, phase separation between the polymer and the solvent produced by polymerization of the monomer component during suspension polymerization may be difficult to occur, which may make it difficult to form the shell.

[0023] The coefficient of variation (CV value) of particle size of hollow resin particles according to an embodiment of the present invention is preferably 10% to 50%, more preferably 15% to 45%, even more preferably 18% to 42%, and particularly preferably 20% to 40%. When the coefficient of variation (CV value) of particle size of hollow resin particles according to an 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 particle size of hollow resin particles according to an embodiment of the present invention is too small and outside the above range, the hollow resin particles may be difficult to disperse in a thermosetting resin when kneaded with the thermosetting resin, and thickness variations may occur, for example, when a resin layer is formed from the resin composition. If the coefficient of variation (CV value) of particle size of hollow resin particles according to an embodiment of the present invention is too large and outside the above range, the amount of coarse particles may increase, making it difficult to form a thin film or causing thickness variations, for example, when a resin layer is formed from the resin composition.

[0024] The hollow resin particles according to an embodiment of the present invention preferably have a 5% weight loss temperature of 290°C or higher, more preferably 300°C or higher, even more preferably 320°C or higher, particularly preferably 340°C or higher, and most preferably 360°C or higher when heated at a rate of 10°C / min in a nitrogen atmosphere. The upper limit of the 5% weight loss temperature is preferably 500°C or lower. If the hollow resin particles according to an embodiment of the present invention have a 5% weight loss temperature within the above range when heated at a rate of 10°C / min in a nitrogen atmosphere, the hollow resin particles according to an embodiment of the present invention can exhibit excellent heat resistance. If the hollow resin particles according to an embodiment of the present invention have a 5% weight loss temperature outside the above range when heated at a rate of 10°C / min in a nitrogen atmosphere that is too low, the particles may deform upon heating. For example, when the hollow resin particles are mixed with a thermosetting resin, the hollow resin particles may deform upon heating for the curing reaction, resulting in the loss of the hollow portion and potentially reducing the effects of achieving a low dielectric constant and a low dielectric loss tangent.

[0025] The hollow resin particles according to an embodiment of the present invention preferably contain phosphorus in an amount of 1,000 μg / g or less, more preferably 750 μg / g or less, even more preferably 600 μg / g or less, and particularly preferably 500 μg / g or less. When the phosphorus content of the hollow resin particles according to an embodiment of the present invention is within the above range, the effects of the present invention can be more effectively exhibited. When the phosphorus content of the hollow resin particles according to an embodiment of the present invention is too high outside the above range, the resin layer formed from the resin composition containing the hollow resin particles may not be able to achieve a low dielectric constant and a low dielectric loss tangent.

[0026] The hollow resin particles according to an embodiment of the present invention preferably contain elemental magnesium of 200 μg / g or less, more preferably 150 μg / g or less, even more preferably 125 μg / g or less, and particularly preferably 100 μg / g or less. When the elemental magnesium contained in the hollow resin particles according to an embodiment of the present invention is within the above range, the effects of the present invention can be more effectively exhibited. When the elemental magnesium contained in the hollow resin particles according to an embodiment of the present invention is too large outside the above range, the resin layer formed from the resin composition containing the hollow resin particles may not be able to achieve a low dielectric constant and a low dielectric loss tangent.

[0027] ≪1-2. Shell part≫ The shell portion contains a polymer (P) having an ether structure and a phosphate ester structure represented by formula (1). When the shell portion contains a polymer (P) having such a structure, the effects of the present invention can be more effectively exhibited. [ka]

[0028] The polymer (P) may have only one type of ether structure represented by formula (1), or two or more types.

[0029] The polymer (P) may have only one type of phosphate ester structure, or two or more types.

[0030] The phosphate ester structure is preferably represented by formula (2) in that it can further exert the effects of the present invention. [ka]

[0031] In formula (2), R 1 , R 2 R in formula (2) each independently represents an organic group or a hydrogen atom. 1 , R 2The organic group that can be taken by is a group containing carbon atoms and may also contain inorganic atoms.

[0032] R in equation (2) 1 , R 2 The organic group that can be taken by is more preferably represented by formula (3) in that it can further exert the effects of the present invention. [ka]

[0033] In formula (3), R 1 , R 2 R in formula (3) each independently represents an organic group or a hydrogen atom. 1 , R 2 The organic group that can be taken by R is a group containing carbon atoms and may contain inorganic atoms. 3 represents a linear or branched alkylene group having 1 to 30 carbon atoms, and m represents 1 to 300.

[0034] 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.

[0035] 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.

[0036] The phosphate ester structure is a phosphate monoester structure (R 1 , R 2 where R 1 , R 2one of which is an organic group and the other is a hydrogen atom), or a phosphate triester structure (R 1 , R 2 In terms of being able to more effectively exhibit the effects of the present invention, the phosphate ester structure is preferably a phosphate monoester structure or a phosphate diester structure.

[0037] The polymer (P) may be of one type only, or of two or more types.

[0038] The content of polymer (P) in the shell portion 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.

[0039] The polymer (P) may contain a sulfur element, that is, the polymer (P) may contain an ether structure represented by formula (1), a phosphate ester structure, and a sulfur element.

[0040] The sulfur element that the polymer (P) may have is preferably a sulfur element contained in an alkylthio group (a group represented by RS—(R is an alkyl group)).

[0041] The alkyl group of the alkylthio group is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, more preferably a linear or branched alkyl group having 4 to 16 carbon atoms, even more preferably a linear or branched alkyl group having 6 to 12 carbon atoms, and particularly preferably a linear or branched alkyl group having 8 to 10 carbon atoms.

[0042] When the polymer (P) contains sulfur, the hollow resin particles according to an embodiment of the present invention preferably have a residual vinyl group ratio of 15% or less, more preferably 12% or less, even more preferably 10% or less, and particularly preferably 8% or less. If the residual vinyl group ratio of the hollow resin particles according to an embodiment of the present invention is within the above range, i.e., if the residual vinyl groups are very small, heat generation due to thermal decomposition (e.g., thermal decomposition at a manufacturing process temperature of about 200 to 300°C for semiconductor components) is suppressed, resulting in better heat resistance. Furthermore, in addition to contributing to improved heat resistance, if the residual vinyl group ratio of the hollow resin particles according to an embodiment of the present invention is within the above range, i.e., if the residual vinyl groups are very small, a lower dielectric constant and a lower dielectric loss tangent can be achieved. If the vinyl group residual ratio of the hollow resin particles according to the embodiment of the present invention is too large and deviates from the above range, an oxidation reaction may occur in the particles due to heating during the production process, resulting in decomposition and heat generation. For example, warping may occur in the thermosetting resin composition obtained by kneading the particles with a thermosetting resin, and further, a low dielectric constant and a low dielectric loss tangent may not be achieved.

[0043] When the polymer (P) contains sulfur, the hollow resin particles according to an embodiment of the present invention preferably have a sulfur atom content of 0.1 to 3.0% by mass, more preferably 0.5 to 2.5% by mass, even more preferably 0.8 to 2.0% by mass, and particularly preferably 1.0 to 1.5% by mass, as determined by X-ray fluorescence analysis. When the sulfur atom content of the hollow resin particles according to an embodiment of the present invention is within the above range, heat generation due to thermal decomposition (e.g., thermal decomposition at a manufacturing process temperature of approximately 200 to 300°C for semiconductor components) is suppressed. In addition to contributing to suppression of heat generation, when the sulfur atom content of the hollow resin particles according to an embodiment of the present invention is within the above range, the thiol-ene reaction with the particles proceeds sufficiently, thereby reducing the vinyl groups in the particles and further achieving a low dielectric constant and a low dielectric loss tangent. When the sulfur atom content of the hollow resin particles according to an embodiment of the present invention is too high, i.e., outside the above range, the hollow resin particles may have a strong odor, which may cause problems in practical use. If the sulfur atom content of the hollow resin particles according to the embodiment of the present invention is too small and deviates from the above range, the thiol-ene reaction of the particles will not proceed sufficiently, leaving many vinyl groups remaining in the particles, which may cause the particles to decompose and generate heat when heated during the production process. For example, warping may occur in the thermosetting resin composition obtained by kneading the particles with a thermosetting resin, and a low dielectric constant and a low dielectric loss tangent may not be achieved.

[0044] When the polymer (P) contains elemental sulfur, the hollow resin particles according to an embodiment of the present invention preferably have an exothermic heat generation onset temperature in the atmosphere of 290°C or higher, more preferably 300°C or higher, even more preferably 310°C or higher, and particularly preferably 315°C or higher. If the hollow resin particles according to an embodiment of the present invention have an exothermic heat generation onset temperature in the atmosphere within the above range, the hollow resin particles according to an embodiment of the present invention can exhibit even better heat resistance. If the hollow resin particles according to an embodiment of the present invention have an exothermic heat generation onset temperature in the atmosphere within the above range, the hollow resin particles according to an embodiment of the present invention can exhibit even better heat resistance. If the hollow resin particles according to an embodiment of the present invention have an exothermic heat generation onset temperature in the atmosphere that is too low, outside the above range, for example, the particles may undergo an oxidation reaction upon heating, causing the particles to decompose and generate heat, and for example, warping may occur in a thermosetting resin composition obtained by kneading the hollow resin particles with a thermosetting resin.

[0045] The shell portion may contain any other appropriate component within the range that does not impair the effects of the present invention.

[0046] As the polymer (P), any appropriate polymer can be used as long as it is a polymer having an ether structure and a phosphate ester structure represented by formula (1) and does not impair the effects of the present invention. In terms of being able to further exhibit the effects of the present invention, the following two embodiments of such a polymer (P) are preferred. (1) Embodiment 1 of polymer (P): A polymer having an ether structure and a phosphate ester structure represented by formula (1), preferably a polymer (AM) obtained by reacting a compound (A) having an ether structure represented by formula (1) and a radical-reactive group with a monomer (M) that reacts with the compound (A), wherein the monomer (M) contains a compound (B) having a phosphate ester structure and a radical-reactive group. (2) Embodiment 2 of polymer (P): A polymer having an ether structure represented by formula (1), a phosphate ester structure, and a sulfur element, preferably a polymer obtained by reacting a polymer (AM) obtained by reacting a compound (A) having an ether structure represented by formula (1) and a radical-reactive group with a monomer (M) that reacts with the compound (A), with a thiol, and the monomer (M) contains a compound (B) having a phosphate ester structure and a radical-reactive group.

[0047] <Embodiment 1 of Polymer (P)> One preferred embodiment 1 of polymer (P) is a polymer having an ether structure and a phosphate ester structure represented by formula (1), and is preferably polymer (AM) obtained by reacting compound (A) having the ether structure represented by formula (1) and a radical reactive group with monomer (M) that reacts with compound (A), and monomer (M) contains compound (B) having a phosphate ester structure and a radical reactive group. That is, one preferred embodiment 1 of polymer (P) is polymer (AM).

[0048] The compound (A) having an ether structure and a radical reactive group represented by formula (1) may be of one type only, or of two or more types.

[0049] The compound (B) having a phosphate ester structure and a radical reactive group may be of one type only, or of two or more types.

[0050] 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, 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, such a radical reactive group is preferably a group having a carbon-carbon unsaturated double bond, and specific examples thereof include a vinyl group, an acrylic group, a methacrylic group, an acrylamide group, and an allyl group.

[0051] The radical reactive group preferably has a structure represented by formula (4) in that the effects of the present invention can be more effectively exhibited. [ka]

[0052] In formula (4), R 4 represents a methyl group or a hydrogen atom.

[0053] The ratio of compound (A) to monomer (M), where the total amount of compound (A) and monomer (M) is 100 parts by weight, is preferably (20 parts by weight to 80 parts by weight):(80 parts by weight to 20 parts by weight), more preferably (20 parts by weight to 70 parts by weight):(80 parts by weight to 30 parts by weight), even more preferably (25 parts by weight to 60 parts by weight):(75 parts by weight to 40 parts by weight), and particularly preferably (30 parts by weight to 50 parts by weight):(70 parts by weight to 50 parts by weight). If the content of compound (A) is too low outside the above range, heat resistance may be insufficient. If the content of compound (A) is too high outside the above range, it may be difficult to form a shell portion and a hollow portion surrounded by the shell portion.

[0054] The total amount of compound (A) and monomer (M) 1 When expressed in 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, resulting in the frequent formation of polymerized lumps or coarse particles. If the content 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.

[0055] As the compound (A), any appropriate compound may be used as long as it has the ether structure represented by formula (1) and a radical reactive group, as long as the effects of the present invention are not impaired. In terms of being able to further demonstrate the effects of the present invention, polyphenylene ether is a preferred example of such compound (A). Commercially available polyphenylene ether products include, for example, the NORYL (registered trademark) series (NORYL (registered trademark) SA9000, etc.) (manufactured by SABIC Corporation), the Iupiace (registered trademark) series (manufactured by Mitsubishi Chemical Corporation), the Zylon (registered trademark) series (manufactured by Asahi Kasei Corporation), and the OPE-2St series (manufactured by Mitsubishi Gas Chemical Company, Inc.).

[0056] In view of the ease with which hollow resin particles having excellent heat resistance can be produced, the polyphenylene ether is preferably an oligomer, and the number average molecular weight Mn thereof is preferably 500 to 3,500.

[0057] As the compound (B), any appropriate compound having a phosphate ester structure and a radical reactive group can be used within a range that does not impair the effects of the present invention. In terms of being able to further exhibit the effects of the present invention, such compound (B) is preferably a compound represented by formula (5). [ka]

[0058] In formula (5), R 3 , R 5 is a linear or branched alkylene group 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.

[0059] In formula (5), R 3is 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.

[0060] 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, 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.

[0061] In formula (5), m is preferably 1 to 100, more preferably 1 to 50, even more preferably 1 to 40, and particularly preferably 1 to 30.

[0062] 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.

[0063] A commercially available product may be used as the compound (B). For example, from the viewpoint of compatibility, an example of such a compound (B) is the product name "KAYAMER (registered trademark) PM-21" (manufactured by Nippon Kayaku Co., Ltd.).

[0064] Examples of the monomer (M) other than the compound (B) include a crosslinkable monomer and a monofunctional monomer. In terms of being able to more effectively exhibit the effects of the present invention, a monomer that reacts with the terminal group of the compound (A) and / or the compound (B) is preferred.

[0065] 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; polyfunctional acrylamide derivatives such as N,N'-methylenebis(meth)acrylamide and N,N'-ethylenebis(meth)acrylamide; polyfunctional allyl derivatives such as diallylamine and tetraallyloxyethane; and aromatic crosslinkable monomers such as divinylbenzene, divinylnaphthalene, and diallyl phthalate. In terms of enhancing the effects of the present invention, aromatic crosslinkable monomers are preferred, and divinylbenzene is more preferred. The crosslinkable monomer may be one type or two or more types.

[0066] 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; aromatic monofunctional monomers, such as styrene, α-methylstyrene, ethylvinylbenzene, vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, vinylbiphenyl, and vinylnaphthalene; dicarboxylic acid ester monomers, such as dimethyl maleate, diethyl fumarate, dimethyl fumarate, and diethyl fumarate; maleic anhydride; N-vinylcarbazole; and (meth)acrylonitrile. In terms of enhancing the effects of the present invention, aromatic monofunctional monomers are preferred, and styrene and ethylvinylbenzene are more preferred. The monofunctional monomers may be one type or two or more types.

[0067] The reaction of the compound (A) with the monomer (M) can be carried out by any appropriate reaction method as long as the effects of the present invention are not impaired, and a preferred example of such a reaction is a suspension polymerization reaction.

[0068] When carrying out a suspension polymerization reaction, typically, an oil phase is added to an aqueous phase and suspended to carry out the polymerization reaction. The aqueous phase or oil phase may contain any appropriate solvent as long as it does not impair the effects of the present invention. Examples of such solvents include aqueous media and non-reactive solvents as described below. The solvent may be one type only, or two or more types.

[0069] When reacting the compound (A) with the monomer (M), any suitable additive (C) that does not correspond to either the compound (A) or the monomer (M) may be used as long as it does not impair the effects of the present invention. The additive (C) may be one type or two or more types. The additive (C) does not include solvents such as aqueous media and non-reactive solvents, and dispersion stabilizers, as described below.

[0070] The content of the 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, relative to the total amount of the compound (A) and the monomer (M).

[0071] As the additive (C), any suitable additive that does not fall under either the compound (A) or the monomer (M) can be used as long as it does not impair the effects of the present invention. Examples of such additive (C) include a non-crosslinkable polymer, a polymerization initiator, and a surfactant.

[0072] By including a non-crosslinkable polymer as the additive (C), phase separation between the polymer (P) produced as the reaction proceeds and the solvent is promoted, and shell formation can be accelerated.

[0073] Examples of the non-crosslinkable polymer include at least one selected from the group consisting of polyolefins, styrene-based polymers, (meth)acrylic acid-based polymers, and styrene-(meth)acrylic acid-based polymers.

[0074] Examples of polyolefins include polyethylene, polypropylene, polyα-olefins, etc. From the viewpoint of solubility in the monomer composition, it is preferable to use a side-chain crystalline polyolefin using a long-chain α-olefin as a raw material, or a low-molecular-weight polyolefin or olefin oligomer produced using a metallocene catalyst.

[0075] Examples of styrene-based polymers include polystyrene, styrene-acrylonitrile copolymers, and acrylonitrile-butadiene-styrene copolymers.

[0076] Examples of the (meth)acrylic acid polymer include polymethyl(meth)acrylate, polyethyl(meth)acrylate, polybutyl(meth)acrylate, and polypropyl(meth)acrylate.

[0077] Examples of styrene-(meth)acrylic acid polymers include styrene-methyl(meth)acrylate copolymer, styrene-ethyl(meth)acrylate copolymer, styrene-butyl(meth)acrylate copolymer, and styrene-propyl(meth)acrylate copolymer.

[0078] In the suspension polymerization reaction, a surfactant may be used as additive (C) from the viewpoint of more stable production of the desired hollow resin particles. As the surfactant, at least one selected from amphoteric surfactants and anionic surfactants is preferred, and it is more preferred to select at least an amphoteric surfactant, in order to further demonstrate the effects of the present invention. Specifically, it is preferred to add at least one selected from amphoteric surfactants and anionic surfactants to the aqueous phase containing the aqueous medium, and it is more preferred to add at least an amphoteric surfactant to the aqueous phase containing the aqueous medium (adding only an amphoteric surfactant, or adding both an amphoteric surfactant and an anionic surfactant).

[0079] As the amphoteric surfactant, any appropriate amphoteric surfactant may be used as long as it does not impair the effects of the present invention. As such an amphoteric surfactant, a known amphoteric surfactant that can be used in the production of resin particles may be used. Examples of amphoteric surfactants include lauryl dimethylamine oxide, lauryl dimethylaminoacetic acid betaine, phosphate surfactants, and phosphite surfactants. Only one type of amphoteric surfactant may be used, or two or more types may be used.

[0080] Any suitable anionic surfactant may be used as the anionic surfactant as long as it does not impair the effects of the present invention. Examples of such anionic surfactants include fatty acid salts, polysulfonates, polycarboxylates, alkyl sulfate ester salts, alkylaryl sulfonates, alkylnaphthalenesulfonates, dialkylsulfonates, dialkylsulfosuccinates, alkyl phosphates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylaryl ether sulfates, naphthalenesulfonate-formalin condensates, polyoxyethylene alkyl phosphate sulfonates, glycerol borate fatty acid esters, and polyoxyethylene glycerol fatty acid esters. Specific examples include sodium dodecylbenzenesulfonate, sodium lauryl sulfate, polyoxyethylene lauryl ether sodium sulfate, polyoxyethylene lauryl ether ammonium sulfate, polyoxyethylene nonylphenyl ether sulfate ester salts, and the sodium salt of β-naphthalenesulfonate-formalin condensates. The anionic surfactant may be used alone or in combination of two or more types.

[0081] The amount of the surfactant used is preferably within a range of 0.01 to 0.3 parts by weight, and more preferably within a range of 0.02 to 0.2 parts by weight, relative to 100 parts by weight of the aqueous medium.

[0082] When reacting the compound (A) with the monomer (M), any suitable dispersion stabilizer (D) that does not fall under either the compound (A) or the monomer (M) may be used within a range that does not impair the effects of the present invention. The dispersion stabilizer (D) may be one type or two or more types.

[0083] The dispersion stabilizer (D) is preferably used in an amount of 0.5 to 10 parts by weight relative to 100 parts by weight of the aqueous medium. The dispersion stabilizer (D) may be used alone or in combination of two or more kinds.

[0084] Examples of the dispersion stabilizer (D) include inorganic water-soluble polymer compounds such as polyvinyl alcohol, polycarboxylic acid, celluloses (e.g., hydroxyethyl cellulose, carboxymethyl cellulose), polyvinylpyrrolidone, and sodium tripolyphosphate. Other examples of the dispersion stabilizer include phosphates such as calcium phosphate, magnesium phosphate, aluminum phosphate, and zinc phosphate; pyrophosphates such as calcium pyrophosphate, magnesium pyrophosphate, aluminum pyrophosphate, and zinc pyrophosphate; and 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 less likely to remain on the surface of the hollow resin particles.

[0085] <Embodiment 2 of Polymer (P)> Another preferred embodiment 2 of polymer (P) is a polymer having an ether structure, a phosphate ester structure, and a sulfur element represented by formula (1), and is preferably a polymer obtained by reacting a thiol with polymer (AM) obtained by reacting a compound (A) having an ether structure and a radical-reactive group represented by formula (1) with a monomer (M) that reacts with compound (A), wherein the monomer (M) contains a compound (B) having a phosphate ester structure and a radical-reactive group. That is, another preferred embodiment 2 of polymer (P) is a polymer obtained by reacting polymer (AM) with a thiol.

[0086] For the polymer (AM), the explanation in <Embodiment 1 of the polymer (P)> can be cited.

[0087] The reaction of the polymer (AM) with the thiol can be carried out by any suitable method that is generally used in a reaction known as a thiol-ene reaction, as long as it does not impair the effects of the present invention. Typically, the reaction is obtained by mixing the polymer (AM), the thiol, and an initiator radical species, heating, and stirring. In this case, the polymer (AM) to be reacted with the thiol may be reacted with the thiol in the form of a reaction mixture (typically a suspension) of the compound (A) and the monomer (M).

[0088] As the thiol, any appropriate thiol can be used as long as it is a thiol represented by R-SH (R is an alkyl group) and does not impair the effects of the present invention. Typically, the alkyl group is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, more preferably a linear or branched alkyl group having 4 to 16 carbon atoms, even more preferably a linear or branched alkyl group having 6 to 12 carbon atoms, and particularly preferably a linear or branched alkyl group having 8 to 10 carbon atoms. Only one type of thiol may be used, or two or more types may be used.

[0089] By reacting the polymer (AM) with a thiol, a thiol-ene reaction occurs between the vinyl groups of the polymer (AM) and the thiol, converting at least a portion of the vinyl groups to alkylthio groups. This reduces the amount of residual vinyl groups in the hollow resin particles, suppressing heat generation due to thermal decomposition (for example, thermal decomposition at the manufacturing process temperature of a semiconductor member, about 200 to 300°C), and enabling the development of superior heat resistance. Furthermore, the reduction in the amount of residual vinyl groups in the hollow resin particles not only contributes to improved heat resistance, but also allows for a lower dielectric constant and a lower dielectric loss tangent.

[0090] ≪1-3. Uses of hollow resin particles≫ The hollow resin particles according to the embodiments of the present invention can be employed in various applications. Because the effects of the present invention can be more effectively utilized, the hollow resin particles according to the embodiments of the present invention are suitable for semiconductor components, and can be typically used in resin compositions for semiconductor components. In addition to the applications in the resin compositions for semiconductor components described above, the hollow resin particles according to the embodiments of the present invention can also be used in applications such as paint compositions, cosmetics, paper coating compositions, heat insulating compositions (e.g., heat insulating resin compositions), light diffusing compositions (e.g., light diffusing resin compositions), and light diffusing films.

[0091] <Resin composition for semiconductor members> The hollow resin particles according to an 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 resin compositions for semiconductor members.

[0092] The resin composition for a semiconductor member according to an embodiment of the present invention contains hollow resin particles according to an embodiment of the present invention.

[0093] The term "semiconductor member" refers to a member that constitutes a semiconductor, such as a semiconductor package or a semiconductor module. In this specification, the term "resin composition for a semiconductor member" refers to a resin composition used for a semiconductor member.

[0094] A semiconductor package is constructed using an IC chip as an essential component and at least one member selected from mold resin, underfill material, mold underfill material, die bond material, prepreg for semiconductor package substrate, metal-clad laminate for semiconductor package substrate, and build-up material for printed circuit board for semiconductor package.

[0095] A semiconductor module is constructed using a semiconductor package as an essential component and at least one member selected from the group consisting of 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 wave shielding films, and adhesive sheets for printed circuit boards.

[0096] <Paint composition> The hollow resin particles according to an embodiment of the present invention can impart an excellent appearance to a coating film containing the hollow resin particles, and therefore can be suitably used in a coating composition.

[0097] A coating composition according to an embodiment of the present invention includes hollow resin particles according to an embodiment of the present invention.

[0098] The coating composition according to an embodiment of the present invention preferably contains at least one selected from a binder resin and a UV-curable resin. The binder resin may be of only one type or may contain two or more types. The UV-curable resin may be of only one type or may contain two or more types.

[0099] Any suitable binder resin can be used as long as it does not impair the effects of the present invention. Examples of such binder resins include resins soluble in organic solvents or water, and emulsion-type aqueous resins that can be dispersed in water. Specific examples of binder resins include acrylic resins, alkyd resins, polyester resins, polyurethane resins, chlorinated polyolefin resins, and amorphous polyolefin resins.

[0100] Any suitable UV-curable resin can be used as the UV-curable resin as long as it does not impair the effects of the present invention. Examples of such UV-curable resins include polyfunctional (meth)acrylate resins and polyfunctional urethane acrylate resins. Polyfunctional (meth)acrylate resins are preferred, and polyfunctional (meth)acrylate resins having three or more (meth)acryloyl groups in one molecule are more preferred. Specific examples of polyfunctional (meth)acrylate resins having three or more (meth)acryloyl groups in one molecule include 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.

[0101] 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, any appropriate content ratio can be adopted 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 of the total amount of the binder resin (in solids content in the case of an emulsion-type aqueous resin), the at least one selected from the UV-curable resin, and the hollow resin particles according to an embodiment of the present invention.

[0102] When a UV-curable resin is used, a photopolymerization initiator is preferably used in combination. Any appropriate photopolymerization initiator can 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 2001-139663 A, etc.), 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfonium compounds, onium salts, borate salts, active halogen compounds, and α-acyloxime esters.

[0103] The coating composition according to the embodiment of the present invention may contain a solvent. The solvent may be one type only, or two or more types. When the coating composition according to the embodiment of the present invention contains a solvent, any appropriate content ratio may be adopted depending on the purpose.

[0104] As the solvent, any suitable solvent can be used as long as it does not impair the effects of the present invention. Such a solvent is preferably a solvent that can dissolve or disperse a binder resin or a UV-curable resin. Examples of such solvents include, for oil-based paints, 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, examples of such solvents include water and alcohols.

[0105] The coating composition according to the embodiment of the present invention may be diluted to adjust the viscosity as needed. Any appropriate diluent may be used depending on the purpose. Examples of such diluents include the solvents mentioned above. The diluent may be one type or two or more types.

[0106] The coating composition according to an embodiment of the present invention may contain other components, such as a coating surface conditioner, a flowability conditioner, an ultraviolet absorber, a light stabilizer, a curing catalyst, an extender pigment, a color pigment, a metal pigment, a mica powder pigment, or a dye, as needed.

[0107] When forming a coating film using the coating composition according to an embodiment of the present invention, any appropriate coating method can be adopted depending on the purpose, such as spray coating, roll coating, brush coating, coating reverse roll coating, gravure coating, die coating, comma coating, and spray coating.

[0108] When forming a coating film using the coating composition according to an embodiment of the present invention, any suitable method can be used depending on the purpose. For example, a coating film can be formed by applying the composition to any surface of a substrate, drying the coating film, and then curing the coating film as needed. Examples of substrates include metal, wood, glass, and plastics (PET (polyethylene terephthalate), PC (polycarbonate), acrylic resin, TAC (triacetyl cellulose), etc.).

[0109] <Thermal insulating resin composition> The hollow resin particles according to an embodiment of the present invention can impart excellent heat insulating properties to a coating film containing the hollow resin particles, and therefore can be suitably used in a heat insulating resin composition. A coating film containing the hollow resin particles according to an embodiment of the present invention can exhibit excellent reflectance in the wavelength range from ultraviolet light to near-infrared light.

[0110] The heat insulating resin composition according to an embodiment of the present invention includes hollow resin particles according to an embodiment of the present invention.

[0111] The heat insulating resin composition according to an embodiment of the present invention preferably contains at least one selected from a binder resin and a UV-curable resin. The above-mentioned explanations regarding the coating composition can be applied to the binder resin and the UV-curable resin.

[0112] The heat insulating resin composition according to the embodiment of the present invention may contain a solvent. Regarding the solvent, the above explanation regarding the coating composition may be cited.

[0113] The heat insulating resin composition according to the embodiment of the present invention may be diluted to adjust the viscosity as needed. The above description of the coating composition can be used as the diluent.

[0114] The heat insulating resin composition according to an embodiment of the present invention may contain other components, such as a coating surface conditioner, a flowability conditioner, an ultraviolet absorber, a light stabilizer, a curing catalyst, an extender pigment, a color pigment, a metal pigment, a mica powder pigment, or a dye, as needed.

[0115] When a coating film is formed using the heat insulating resin composition according to an embodiment of the present invention, the coating method and formation method can be applied as described above for the coating composition.

[0116] <Light-diffusing resin composition> The hollow resin particles according to the embodiment of the present invention can impart excellent light diffusibility to a coating film containing the hollow resin particles, and therefore can be suitably used in a light diffusing resin composition.

[0117] The light-diffusing resin composition according to an embodiment of the present invention includes hollow resin particles according to an embodiment of the present invention.

[0118] The light-diffusing resin composition according to the embodiment of the present invention preferably contains at least one selected from a binder resin and a UV-curable resin. The above-mentioned explanations regarding the coating composition can be applied to the binder resin and the UV-curable resin.

[0119] The light-diffusing resin composition according to the embodiment of the present invention may contain a solvent. Regarding the solvent, the above explanation regarding the coating composition may be cited.

[0120] The light-diffusing resin composition according to the embodiment of the present invention may be diluted to adjust the viscosity as needed. The above-mentioned description of the coating composition may be applied to the diluent.

[0121] The light-diffusing resin composition according to an embodiment of the present invention may contain other components, such as a coating surface conditioner, a flowability conditioner, an ultraviolet absorber, a light stabilizer, a curing catalyst, an extender pigment, a color pigment, a metal pigment, a mica powder pigment, or a dye, as needed.

[0122] When forming a coating film using the light-diffusing resin composition according to an embodiment of the present invention, the coating method and formation method can be applied as described above for the coating composition.

[0123] <Light diffusion film> The hollow resin particles according to the embodiment of the present invention can impart excellent light diffusibility to a film having a coating film containing the hollow resin particles, and therefore can be suitably used in light diffusion films.

[0124] The light diffusion film according to an embodiment of the present invention includes hollow resin particles according to an embodiment of the present invention.

[0125] The light diffusion film according to an embodiment of the present invention includes a light diffusion layer formed from the light-diffusing resin composition according to an embodiment of the present invention and a substrate. The light diffusion layer may or may not be the outermost layer of the light diffusion film. The light diffusion film according to an embodiment of the present invention may include any appropriate other layer depending on the purpose. Examples of such other layers include a protective layer, a hard coat layer, a planarizing layer, a high refractive index layer, an insulating layer, a conductive resin layer, a conductive metal fine particle layer, a conductive metal oxide fine particle layer, and a primer layer.

[0126] Examples of substrates include metal, wood, glass, plastic film, plastic sheet, plastic lens, plastic panel, cathode ray tube, fluorescent display tube, and liquid crystal display panel. Examples of plastics that make up the plastic film, plastic sheet, plastic lens, and plastic panel include PET (polyethylene terephthalate), PC (polycarbonate), acrylic resin, and TAC (triacetyl cellulose).

[0127] 2. Method for producing hollow resin particles As the method for producing hollow resin particles according to the embodiment of the present invention, the following two embodiments can be mentioned as preferred. (1) Embodiment 1 of the production method: 20 to 80 parts by weight of a compound (A) having an ether structure and a radical-reactive group, represented by formula (1), and 80 to 20 parts by weight of a monomer (M) that reacts with the compound (A) (the total amount of the compound (A) and the monomer (M) being 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 radical-reactive group. [ka] (2) Embodiment 2 of the production method: This method comprises an oil phase preparation step (I) of mixing 20 to 80 parts by weight of a compound (A) having an ether structure represented by formula (1) and a radical-reactive group and 80 to 20 parts by weight of a monomer (M) that reacts with the compound (A) (the total amount of the compound (A) and the monomer (M) is 100 parts by weight) with a non-reactive solvent to prepare an oil phase; a suspension polymerization step (II) of adding the oil phase to an aqueous phase containing an aqueous medium and stirring to prepare a suspension; and a thiol-ene reaction step (III) of adding a thiol to the suspension and reacting it to prepare a reaction product. [ka]

[0128] According to the above-described manufacturing method, the hollow resin particles according to the embodiment of the present invention can be preferably manufactured easily.

[0129] <First embodiment of manufacturing method> In one preferred embodiment 1 of the method for producing hollow resin particles of the present invention, 20 to 80 parts by weight of a compound (A) having an ether structure and a radical-reactive group represented by formula (1) are reacted with 80 to 20 parts by weight of a monomer (M) that reacts with the compound (A) (the total amount of the compound (A) and the monomer (M) being 100 parts by weight), in the presence of a non-reactive solvent, and the monomer (M) contains a compound (B) having a phosphate ester structure and a radical-reactive group. [ka]

[0130] According to the above-mentioned production method 1, hollow resin particles are typically obtained which have a shell portion and a hollow portion surrounded by the shell portion, and the shell portion contains a polymer (P) having an ether structure and a phosphate ester structure represented by formula (1). Preferably, the polymer (P) is a polymer (AM) obtained by reacting a compound (A) having the ether structure represented by formula (1) and a radical-reactive group with a monomer (M) which reacts with the compound (A), and the monomer (M) contains a compound (B) having a phosphate ester structure and a radical-reactive group.

[0131] The hollow resin particles according to the embodiment of the present invention can be obtained by reacting the compound (A) with the monomer (M) in an aqueous medium in the presence of a non-reactive solvent. Typically, the hollow resin particles according to the embodiment of the present invention can be produced by subjecting the compound (A) and the monomer (M) to a suspension polymerization reaction.

[0132] The suspension polymerization is typically performed using an aqueous phase containing an aqueous medium and an oil phase containing the compound (A), the monomer (M), and a non-reactive solvent. Preferably, the oil phase containing the compound (A), the monomer (M), and a non-reactive solvent is added to the aqueous phase containing an aqueous medium, dispersed, and heated to perform the suspension polymerization.

[0133] Any suitable dispersion method can be used for the dispersion, as long as it allows the oil phase to exist in the form of droplets in the aqueous phase, without impairing the effects of the present invention. Typical examples of such dispersion methods include dispersion methods using a homomixer or a homogenizer, such as a Polytron homogenizer, an ultrasonic homogenizer, or a high-pressure homogenizer.

[0134] The polymerization temperature may be any suitable temperature suitable for suspension polymerization within a range that does not impair the effects of the present invention, and is preferably 30°C to 80°C.

[0135] The polymerization time may be any appropriate time suitable for suspension polymerization, as long as it does not impair the effects of the present invention. Such a polymerization time is preferably 1 hour to 48 hours.

[0136] Post-heating, which is preferably carried out after polymerization, is a treatment suitable for obtaining hollow resin particles with a high degree of perfection.

[0137] The temperature for post-heating preferably carried out after polymerization can be any appropriate temperature within a range that does not impair the effects of the present invention, and is preferably 70°C to 120°C.

[0138] The post-heating time preferably carried out after polymerization can be any appropriate time within the range that does not impair the effects of the present invention, and is preferably 1 hour to 24 hours.

[0139] For the compound (A) and the monomer (M), the explanation in the section <<1-2. Shell Portion>> of <<1. Hollow Resin Particles>> can be directly applied.

[0140] Examples of aqueous media include water and mixed media of water and lower alcohols (methanol, ethanol, etc.).

[0141] The amount of the aqueous medium used may be any appropriate amount within the range that does not impair the effects of the present invention. The amount of such an aqueous medium used is typically an amount that allows the reaction to proceed appropriately in a suspension polymerization reaction carried out by adding an oil phase to an aqueous phase and suspending the oil phase, and is preferably 100 to 5,000 parts by weight, more preferably 150 to 2,000 parts by weight, relative to 100 parts by weight of the total amount of compound (A), monomer (M), and non-reactive solvent.

[0142] The non-reactive solvent is a solvent that does not undergo a chemical reaction with either the compound (A) or the monomer (M), and is preferably an organic solvent. The non-reactive solvent typically acts as a hollowing agent that provides air spaces to the particles. Examples of non-reactive solvents include heptane, hexane, toluene, cyclohexane, methyl acetate, ethyl acetate, methyl ethyl ketone, chloroform, and carbon tetrachloride. The boiling point of the non-reactive solvent is preferably less than 100°C, as this facilitates removal from the hollow resin particles.

[0143] The non-reactive solvent used as the hollowing agent may be a single solvent or a mixed solvent.

[0144] The amount of the non-reactive solvent added is preferably 20 to 250 parts by weight relative to 100 parts by weight of the total amount of the compound (A) and the monomer (M).

[0145] When reacting the compound (A) with the monomer (M), any suitable additive (C) that does not correspond to either the compound (A) or the monomer (M) may be used as long as it does not impair the effects of the present invention. The additive (C) may be one type or two or more types. The additive (C) does not include solvents such as aqueous media and non-reactive solvents, and dispersion stabilizers.

[0146] The content of the 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, relative to the total amount of the compound (A) and the monomer (M).

[0147] As the additive (C), any suitable additive that does not fall under either the compound (A) or the monomer (M) can be used as long as it does not impair the effects of the present invention. Examples of such additive (C) include a non-crosslinkable polymer and a polymerization initiator.

[0148] For the non-crosslinked polymer, the explanation in the section <<1-2. Shell Portion>> of <<1. Hollow Resin Particles>> can be directly applied.

[0149] As the polymerization initiator, any suitable polymerization initiator can be used as long as it does not impair the effects of the present invention. Examples of such polymerization initiators include organic peroxides such as lauroyl peroxide, benzoyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, t-butylperoxy-2-ethylhexanoate, and di-t-butyl peroxide; and azo compounds such as 2,2'-azobisisobutyronitrile, 1,1'-azobiscyclohexanecarbonitrile, and 2,2'-azobis(2,4-dimethylvaleronitrile).

[0150] The content of the polymerization initiator is preferably in the range of 0.1% by weight to 5% by weight based on the total amount of the compound (A) and the monomer (M). The polymerization initiator may be of one kind or two or more kinds.

[0151] When reacting the compound (A) with the monomer (M), any suitable dispersion stabilizer (D) that does not fall under either the compound (A) or the monomer (M) may be used within a range that does not impair the effects of the present invention. The dispersion stabilizer (D) may be one type or two or more types.

[0152] The dispersion stabilizer (D) is preferably used in an amount of 0.5 to 10 parts by weight relative to 100 parts by weight of the aqueous medium. The dispersion stabilizer (D) may be used alone or in combination of two or more kinds.

[0153] As specific examples of the dispersion stabilizer (D), the explanation in the section <<1-2. Shell Portion>> of <<1. Hollow Resin Particles>> can be directly cited.

[0154] <Second embodiment of manufacturing method> Another preferred embodiment 2 of the method for producing hollow resin particles of the present invention includes an oil phase preparation step (I) of mixing 20 to 80 parts by weight of a compound (A) having an ether structure and a radical-reactive group, represented by formula (1), and 80 to 20 parts by weight of a monomer (M) that reacts with the compound (A) (the total amount of the compound (A) and the monomer (M) being 100 parts by weight), with a non-reactive solvent to prepare an oil phase; a suspension polymerization step (II) of adding the oil phase to an aqueous phase containing an aqueous medium and stirring to prepare a suspension; and a thiol-ene reaction step (III) of adding a thiol to the suspension and reacting it to prepare a reaction product. [ka]

[0155] According to the above-mentioned production method 2, hollow resin particles are typically obtained which have a shell portion and a hollow portion surrounded by the shell portion, and the shell portion contains a polymer (P) having an ether structure represented by formula (1), a phosphate ester structure, and a sulfur element. Preferably, the polymer (P) is a polymer obtained by reacting a thiol with a polymer (AM) obtained by reacting a compound (A) having the ether structure represented by formula (1) and a radical-reactive group with a monomer (M) that reacts with the compound (A), and the monomer (M) contains a compound (B) having a phosphate ester structure and a radical-reactive group.

[0156] In the oil phase preparation step (I), 20 to 80 parts by weight of compound (A) and 80 to 20 parts by weight of monomer (M) (the total amount of compound (A) and monomer (M) is 100 parts by weight) are mixed with a non-reactive solvent to prepare an oil phase.

[0157] The ratio of compound (A) to monomer (M), where the total amount of compound (A) and monomer (M) is 100 parts by weight, is preferably (20 parts by weight to 80 parts by weight):(80 parts by weight to 20 parts by weight), more preferably (20 parts by weight to 70 parts by weight):(80 parts by weight to 30 parts by weight), even more preferably (25 parts by weight to 60 parts by weight):(75 parts by weight to 40 parts by weight), and particularly preferably (30 parts by weight to 50 parts by weight):(70 parts by weight to 50 parts by weight). If the content of compound (A) is too low outside the above range, heat resistance may be insufficient. If the content of compound (A) is too high outside the above range, it may be difficult to form a shell portion and a hollow portion surrounded by the shell portion.

[0158] For the compound (A) and the monomer (M), the explanation in the section <<1-2. Shell Portion>> of <<1. Hollow Resin Particles>> can be directly applied.

[0159] The non-reactive solvent is a solvent that does not undergo a chemical reaction with either the compound (A) or the monomer (M), and is preferably an organic solvent. The non-reactive solvent typically acts as a hollowing agent that provides air spaces to the particles. Examples of non-reactive solvents include heptane, hexane, toluene, cyclohexane, methyl acetate, ethyl acetate, methyl ethyl ketone, chloroform, and carbon tetrachloride. The boiling point of the non-reactive solvent is preferably less than 100°C, as this facilitates removal from the hollow resin particles.

[0160] The non-reactive solvent used as the hollowing agent may be a single solvent or a mixed solvent.

[0161] The amount of the non-reactive solvent added is preferably 20 to 250 parts by weight relative to 100 parts by weight of the total amount of the compound (A) and the monomer (M).

[0162] When reacting the compound (A) with the monomer (M), any suitable additive (C) that does not correspond to either the compound (A) or the monomer (M) may be used as long as it does not impair the effects of the present invention. The additive (C) may be one type or two or more types. The additive (C) does not include solvents such as aqueous media and non-reactive solvents, and dispersion stabilizers.

[0163] The content of the 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, relative to the total amount of the compound (A) and the monomer (M).

[0164] As the additive (C), any suitable additive that does not fall under either the compound (A) or the monomer (M) can be used as long as it does not impair the effects of the present invention. Examples of such additive (C) include a non-crosslinkable polymer and a polymerization initiator.

[0165] For the non-crosslinked polymer, the explanation in the section <<1-2. Shell Portion>> of <<1. Hollow Resin Particles>> can be directly applied.

[0166] As the polymerization initiator, any suitable polymerization initiator can be used as long as it does not impair the effects of the present invention. Examples of such polymerization initiators include organic peroxides such as lauroyl peroxide, benzoyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, t-butylperoxy-2-ethylhexanoate, and di-t-butyl peroxide; and azo compounds such as 2,2'-azobisisobutyronitrile, 1,1'-azobiscyclohexanecarbonitrile, and 2,2'-azobis(2,4-dimethylvaleronitrile).

[0167] The content of the polymerization initiator is preferably in the range of 0.1% by weight to 5% by weight based on the total amount of the compound (A) and the monomer (M). The polymerization initiator may be of one kind or two or more kinds.

[0168] In the suspension polymerization step (II), the oil phase obtained in the oil phase preparation step (I) is added to an aqueous phase containing an aqueous medium, and the mixture is stirred to prepare a suspension.

[0169] Examples of aqueous media include water and mixed media of water and lower alcohols (methanol, ethanol, etc.).

[0170] The amount of the aqueous medium used may be any appropriate amount within the range that does not impair the effects of the present invention. The amount of such an aqueous medium used is typically an amount that allows the reaction to proceed appropriately in a suspension polymerization reaction carried out by adding an oil phase to an aqueous phase and suspending the oil phase, and is preferably 100 to 5,000 parts by weight, more preferably 150 to 2,000 parts by weight, relative to 100 parts by weight of the total amount of the compound (A), the monomer (M), and the non-reactive solvent.

[0171] In the suspension polymerization step (II), the aqueous phase containing the aqueous medium may contain any appropriate dispersion stabilizer (D) that does not fall under either the compound (A) or the monomer (M), as long as the effect of the present invention is not impaired. The dispersion stabilizer (D) may be one type or two or more types.

[0172] The dispersion stabilizer (D) is preferably used in an amount of 0.5 to 10 parts by weight relative to 100 parts by weight of the aqueous medium.

[0173] As specific examples of the dispersion stabilizer (D), the explanation in the section <<1-2. Shell Portion>> of <<1. Hollow Resin Particles>> can be directly cited.

[0174] Any suitable dispersion method can be used for the dispersion, as long as it allows the oil phase to exist in the form of droplets in the aqueous phase, without impairing the effects of the present invention. Typical examples of such dispersion methods include dispersion methods using a homomixer or a homogenizer, such as a Polytron homogenizer, an ultrasonic homogenizer, or a high-pressure homogenizer.

[0175] The polymerization temperature may be any suitable temperature suitable for suspension polymerization within a range that does not impair the effects of the present invention, and is preferably 30°C to 80°C.

[0176] The polymerization time may be any appropriate time suitable for suspension polymerization, as long as it does not impair the effects of the present invention. Such a polymerization time is preferably 1 hour to 48 hours.

[0177] After polymerization, post-heating may be performed. By performing post-heating after polymerization, hollow resin particles with a higher degree of completion can be obtained. Any appropriate temperature can be used as the post-heating temperature as long as it does not impair the effects of the present invention. The post-heating temperature is preferably 70°C to 120°C.

[0178] The post-heating time can be any appropriate time as long as it does not impair the effects of the present invention, and is preferably 1 hour to 24 hours.

[0179] Post-heating may be carried out in the subsequent thiol-ene reaction step (III).

[0180] In the suspension polymerization step (II) described above, the resulting suspension contains a polymer (AM) obtained by the reaction of the compound (A) with the monomer (M).

[0181] In the thiol-ene reaction step (III), a thiol is added to the suspension obtained in the suspension polymerization step (II) and reacted to prepare a reaction product.

[0182] In the thiol-ene reaction step (III), a thiol-ene reaction occurs between the polymer (AM) contained in the suspension obtained in the suspension polymerization step (II) and a thiol. The thiol-ene reaction between the polymer (AM) and a thiol can be carried out by any appropriate method that is generally used in reactions known as thiol-ene reactions, as long as it does not impair the effects of the present invention. Typically, the reaction is obtained by mixing the polymer (AM), a thiol, and an initiator radical species, heating, and stirring.

[0183] As the conditions for the thiol-ene reaction step (III), any appropriate conditions can be adopted as long as they do not impair the effects of the present invention.

[0184] In the thiol-ene reaction step (III), a polymerization initiator may be used to promote the reaction. Specific examples of the polymerization initiator include azo-based polymerization initiators such as 2,2'-azobis-2,4-dimethylvaleronitrile and 2,2'-azobisisobutyronitrile; and peroxide-based polymerization initiators such as benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, methyl ethyl ketone peroxide, propyl peroxydicarbonate, cumene hydroperoxide, and t-butyl hydroperoxide. These polymerization initiators may be used alone or in combination of two or more.

[0185] The heating temperature in the thiol-ene reaction step (III) may be any appropriate temperature within a range that does not impair the effects of the present invention. The heating temperature is preferably a temperature at which 99% or more of the polymerization initiator used is decomposed.

[0186] The heating time in the thiol-ene reaction step (III) can be any appropriate time as long as it does not impair the effects of the present invention. Such a heating time is preferably a time for which 99% or more of the polymerization initiator used is decomposed.

[0187] For the thiol, the explanation in the section <<1-2. Shell Portion>> of <<1. Hollow Resin Particles>> can be directly applied.

[0188] By reacting the polymer (AM) with a thiol, a thiol-ene reaction occurs between the vinyl groups of the polymer (AM) and the thiol, converting at least a portion of the vinyl groups to alkylthio groups. This reduces the amount of residual vinyl groups in the hollow resin particles, suppressing heat generation due to thermal decomposition (for example, thermal decomposition at the manufacturing process temperature of a semiconductor member, about 200 to 300°C), and enabling the development of superior heat resistance. Furthermore, the reduction in the amount of residual vinyl groups in the hollow resin particles not only contributes to improved heat resistance, but also allows for a lower dielectric constant and a lower dielectric loss tangent.

[0189] The method for producing hollow resin particles according to an embodiment of the present invention may include any other appropriate steps, such as a washing step, as long as the steps include the oil phase preparation step (I), the suspension polymerization step (II), and the thiol-ene reaction step (III), without impairing the effects of the present invention. [Example]

[0190] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means "parts by weight" and "%" means "% by weight."

[0191] <<Measurement of volume average particle size and coefficient of variation>> The volume average particle size of the particles was measured by the Coulter method as follows. The volume average particle diameter of particles was measured using a Coulter Multisizer® 3 (a measuring 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. The aperture used for measurement was appropriately selected depending on the size of the particles to be measured. For example, a 50 μm aperture was selected when the assumed volume average particle diameter of the particles to be measured was 1 μm to 10 μm; a 100 μm aperture was selected when the assumed volume average particle diameter of the particles to be measured was 10 μm to 30 μm; a 280 μm aperture was selected when the assumed volume average particle diameter of the particles to be measured was 30 μm to 90 μm; and a 400 μm aperture was selected when the assumed volume average particle diameter of the particles to be measured was 90 μm to 150 μm. If the volume average particle diameter after measurement differed from the expected volume average particle diameter, the aperture was changed to one with an appropriate size and the measurement was performed again. The current (aperture current) and gain were set appropriately depending on the selected aperture size. For example, when an aperture with a size of 50 μm was selected, the current (aperture current) was set to -800 and the gain was set to 4. When an aperture with a size of 100 μm was selected, the current (aperture current) was set to -1600 and the gain was set to 2. When apertures with sizes of 280 μm and 400 μm were selected, the current (aperture current) was set to -3200 and the gain was set to 1. The measurement sample was 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 (Velvoclear Co., Ltd., "ULTRASONIC CLEANER VS-150") to prepare a dispersion. During the measurement, the beaker was gently stirred to prevent air bubbles from being introduced, and the measurement was stopped when 100,000 particles had been measured. The volume-average particle diameter of the particles was taken as the arithmetic mean of the particle size distribution based on the volume of 100,000 particles. The coefficient of variation (CV value) of particle diameter of the particles was calculated by the following formula. Coefficient of variation of particle size (%) = (standard deviation of particle volume-based particle size distribution ÷ volume-average particle size) × 100 (%)

[0192] <Cross-section 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. The cured product was then cut with nippers, and the cross section was smoothed using a cutter. The sample was then coated using a JEOL Ltd. "Auto Fine Coater JFC-1300" sputtering device. The cross section of the sample was then photographed using the secondary electron detector of a Hitachi High-Technologies Corporation "SU1510" scanning electron microscope.

[0193] <<Measurement of 5% Weight Loss Temperature When Heating at 10°C / min in a Nitrogen Atmosphere (Examples 1 to 7, Comparative Examples 1 to 3)>> The 5% weight loss temperature was measured using a "TG / DTA6200, AST-2" differential thermal and thermogravimetric simultaneous measurement device manufactured by SII NanoTechnology Inc. The sampling method and temperature conditions were as follows. The sample for measurement was prepared by packing 10.5±0.5 mg of sample into the bottom of a platinum measurement container without leaving any gaps. The 5% weight loss temperature was measured using alumina as the reference substance 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. The temperature at which 5% weight loss occurred was calculated from the curve using the analysis software provided with the instrument, and this was taken as the 5% weight loss temperature.

[0194] <<Measurement of 5% Weight Loss Temperature and Exotherm Onset Temperature when Heating at 10°C / min in a Nitrogen Atmosphere (Examples 8 to 17, Comparative Examples 4 to 5)>> The 5% weight loss temperature and heat release temperature were measured using a Hitachi High-Tech Science Corporation "NEXTA STA200RV" differential thermal and thermogravimetric simultaneous analyzer. The sampling method and temperature conditions were as follows. 10.5 ± 0.5 mg of sample was packed tightly into the bottom of a platinum measurement vessel. TG-DSC curves were obtained by heating the sample from 30°C to 800°C at a heating rate of 10°C / min. Alumina was used as the reference material. The 5% weight loss temperature was determined from the TG curve obtained using the analysis software provided with the instrument under a nitrogen gas flow rate of 300 mL / min. Specifically, the temperature at which the sample weight dropped by 5% compared to the initial weight was defined as the 5% weight loss temperature. The heat release temperature was determined from the DSC curve obtained using the analysis software provided with the instrument under an air gas flow rate of 200 mL / min and nitrogen gas as a protective gas at a flow rate of 100 mL / min. Specifically, the intersection point between the low-temperature baseline and the tangent to the point where the slope of the exothermic peak rises to its maximum on the DSC curve was determined. The temperature at this intersection was defined as the exothermic onset temperature. However, if there were multiple exothermic peaks, the lowest-temperature peak was used.

[0195] <Measurement of phosphorus and magnesium element content> The amounts of phosphorus and magnesium were measured using a multi-type ICP optical emission spectrometer (Shimadzu Corporation, "ICPE-9000"). Approximately 1.0 g of particles were precisely weighed and ashed by heating the weighed particles at 450°C for 3 hours in an electric furnace (Isuzu Corporation, muffle furnace "STR-15K"). The ashed particles were dissolved in 2 ml of concentrated hydrochloric acid and diluted to 50 ml with distilled water to prepare a measurement sample. The measurement sample was then measured using the multi-type ICP optical emission spectrometer under the following measurement conditions to obtain the peak intensities of the wavelengths of each element (Mg, P). The concentrations (μg / ml) of each element (Mg, P) in the measurement sample were then calculated from the peak intensities of the wavelengths of each element (Mg, P) based on the quantitative calibration curves prepared using the calibration curve preparation method described below. The calculated concentration Tc (μg / ml) of each element (Mg, P) and the weight W (g) of the precisely weighed particles were then substituted into the following formula to calculate the amount of each element in the particles. Element amount (μg / g)=(Tc(μg / ml) / W(g))×50(ml) <Measurement conditions> Measurement wavelength: Mg (285.213nm), P (177.499nm) Observation direction: Axial direction High frequency output: 1.20kW Carrier flow rate: 0.7 L / min Plasma flow rate: 10.0 L / min Auxiliary flow rate: 0.6L / min Exposure time: 30 seconds <How to create a calibration curve> Standard solutions for the calibration curve ("XSTC-13 (general-purpose mixed standard solution)" manufactured by SPEX, USA, elemental mixture (base 5% HNO3) - approximately 10 mg / L each) were serially diluted with distilled water to prepare standard solutions with concentrations of 0 ppm (blank), 0.2 ppm, 1 ppm, 2.5 ppm, and 5 ppm. Measurements were performed on the standard solutions of each concentration using the multi-type ICP optical emission spectrometer under the above measurement conditions, and the peak intensity of each element (Mg, P) was obtained. The concentration and peak intensity of each element (Mg, P) were plotted, and an approximate line (linear or quadratic curve) was determined using the least squares method. The approximate line obtained was used as the calibration curve for quantification.

[0196] <Sulfur atom content in particles measured by fluorescent X-rays> The sulfur atom content in the particles was determined by the order analysis method of X-ray fluorescence analysis. Specifically, sulfur intensity was measured under the following conditions using a Rigaku Corporation "ZSX PrimusIV" X-ray fluorescence analyzer, and the sulfur atom content in the particles was determined by the order analysis method. The sample was prepared by weighing approximately 20 mg of sample into a trace powder container (Rigaku, 3399O051), covering it with PP film (Rigaku, 3399G003), and placing it in a 10 mm diameter sample case included with the instrument. <Equipment conditions> ·Device:ZSX PrimusIV X-ray tube target: Rh Measuring diameter: 10mm Spin: No Atmosphere: Vacuum Sample type: Metal Balanced component: C8H8O Sample film: PP film Sample weight and thickness: Set <Qualitative elemental conditions> S-Kα ·Tube:Rh(30kV-100mA) Primary filter: OUT Attenuator: 1 / 1 Slit: S4 Analyzing crystal: GeH 2θ: 110.830° (measurement range: 107°~114°) Detector: PC PHA:150 Step: 0.05deg ·Time: 0.15sec

[0197] <Measurement of residual vinyl group rate> The residual rate of vinyl groups in the particles was measured in accordance with JIS K 0070-1992. A 200 ml Erlenmeyer flask was charged with 1.8 g of the particles produced in the Examples and Comparative Examples, 100 g of cyclohexane, and 25 g of Wiess's reagent (0.1 mol / L iodine chloride-acetic acid solution), and the mixture was thoroughly shaken to mix. The mixture was then left for 45 minutes to allow the ethylenically unsaturated groups contained in the particles to react with the iodine chloride. Next, 20 g of a 10 wt. % potassium iodide solution, 100 g of water, and 0.5 g of a 1 wt. % starch solution were added to the mixture and thoroughly shaken to produce a blue-colored mixture. The mixture was titrated with a 0.1 mol / L sodium thiosulfate solution until the blue color disappeared. The amount of iodine chloride remaining in the mixture (mol) was calculated from the titration amount. The amount of remaining vinyl groups (mol) in the particles (A) was then calculated from the amount of remaining iodine chloride (mol). The amount of vinyl groups when all of the polymers constituting 1.8 parts by weight of the particles produced in the Examples and Comparative Examples were monomers was taken as the (B) theoretical total amount of vinyl groups (mol) of the particles. The residual vinyl group rate (%) was calculated based on the following formula. Vinyl group residual rate (%) = [(A) amount of remaining vinyl groups / (B) theoretical total amount of vinyl groups] x 100

[0198] Productivity After the polymerization was completed, the entire amount of the obtained slurry was passed through JIS test sieves (mesh size: 150 μm and 75 μm) (JIS standard number: Z 8801-1:2019) while being manually shaken. The particles remaining on the sieve (particles that did not pass through the sieve) were dried and weighed. The relative ratio to the total amount of polymer was calculated and used as a measure of productivity.

[0199] Example 1 An oil phase was prepared by mixing 100 g of a reactive low-molecular-weight polyphenylene ether (product name "Noryl® SA9000-111 Resin" manufactured by SABIC Corporation) as a compound having an ether structure, 100 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Material Co., Ltd., 81% content, 19% ethylvinylbenzene (EVB)), 200 g of heptane, 2.34 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (product name "V-65" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator, and 1.20 g of "KAYAMER® PM-21" (manufactured by Nippon Kayaku Co., Ltd.) as a radically polymerizable monomer having a phosphate group. The oil phase was added to 1,281 g of a 2 wt % aqueous dispersion of magnesium pyrophosphate as the aqueous phase, and the mixture was dispersed at 7,000 rpm for 5 minutes using a Polytron homogenizer "PT10-35" (Central Scientific Trading Co., Ltd.) to prepare a suspension. The resulting suspension was heated at 55°C for 5 hours, after which the internal temperature of the polymerization vessel was increased to 80°C (secondary heating), and the suspension was stirred at 80°C for 2 hours to complete the polymerization reaction. Hydrochloric acid was added to the resulting slurry to decompose the magnesium pyrophosphate, and the solids were separated by dehydration through filtration, purified by repeated washing with water, and then dried at 80°C for 24 hours to obtain particles (1). A cross-sectional photograph of the obtained particle (1) is shown in FIG. It was confirmed that the obtained particles (1) were a mixture of hollow resin particles (1a) in which the hollow space surrounded by a shell consisted of a single hollow region, and hollow resin particles (1b) in which the hollow space surrounded by a shell consisted of a porous structure. The volume average particle size of the obtained particles (1) was 11.3 μm, and the coefficient of variation was 33.3%. The 5% weight loss temperature of the obtained particles (1) was 389°C when the temperature was increased at a rate of 10°C / min in a nitrogen atmosphere. The blend amounts and various measurement results are shown in Table 1.

[0200] Example 2 Particles (2) were obtained in the same manner as in Example 1, except that the amount of "KAYAMER (registered trademark) PM-21" (manufactured by Nippon Kayaku Co., Ltd.) used as the radical polymerizable monomer having a phosphoric acid group was changed to 2.00 g. A cross-sectional photograph of the obtained particle (2) is shown in FIG. The obtained particles (2) were confirmed to be hollow resin particles having a porous structure, with the hollow space surrounded by a shell and consisting of multiple hollow regions. The volume average particle size of the obtained particles (2) was 12.7 μm, and the coefficient of variation was 35.2%. The 5% weight loss temperature of the obtained particles (2) was 385°C when the temperature was increased at a rate of 10°C / min in a nitrogen atmosphere. The blend amounts and various measurement results are shown in Table 1.

[0201] Example 3 Particles (3) were obtained in the same manner as in Example 1, except that the amount of reactive low-molecular-weight polyphenylene ether (trade name "Noryl (registered trademark) SA9000-111 resin", manufactured by SABIC Corporation) used as the compound having an ether structure was changed to 80 g, and the amount of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Material Co., Ltd., 81% content, 19% being ethylvinylbenzene (EVB)) used was changed to 120 g. A cross-sectional photograph of the obtained particle (3) is shown in FIG. The obtained particles (3) were confirmed to be hollow resin particles having a porous structure, with the hollow space surrounded by a shell and consisting of multiple hollow regions. The volume average particle size of the obtained particles (3) was 11.3 μm, and the coefficient of variation was 34.9%. The temperature at which the obtained particles (3) lost 5% weight was 414°C when the temperature was increased at a rate of 10°C / min in a nitrogen atmosphere. The blend amounts and various measurement results are shown in Table 1.

[0202] Example 4 Particles (4) were obtained in the same manner as in Example 3, except that 80 g of a bifunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Co., Inc.) was used as a compound having an ether structure instead of 80 g of a reactive low-molecular-weight polyphenylene ether (trade name "Noryl (registered trademark) SA9000-111 resin", manufactured by SABIC Corporation) as a compound having an ether structure. A cross-sectional photograph of the obtained particle (4) is shown in FIG. The obtained particles (4) were confirmed to be hollow resin particles having a porous structure, with the hollow space surrounded by a shell and consisting of multiple hollow regions. The volume average particle size of the obtained particles (4) was 9.8 μm, and the coefficient of variation was 42.9%. The 5% weight loss temperature of the obtained particles (4) was 362°C when the temperature was increased at a rate of 10°C / min in a nitrogen atmosphere. The blend amounts and various measurement results are shown in Table 1.

[0203] Example 5 Particles (5) were obtained in the same manner as in Example 3, except that instead of adding the oil phase to 1,281 g of a 2 wt % aqueous dispersion of magnesium pyrophosphate as the aqueous phase and dispersing the mixture at 7,000 rpm for 5 minutes using a Polytron homogenizer "PT10-35" (manufactured by Central Scientific Trading Co., Ltd.) to prepare a suspension, the oil phase was added to 1,381 g of a 2.5 wt % aqueous dispersion of magnesium pyrophosphate as the aqueous phase and dispersing the mixture at 7,000 rpm for 5 minutes using a Polytron homogenizer "PT10-35" (manufactured by Central Scientific Trading Co., Ltd.), and then emulsifying the mixture at a processing pressure of 20 MPa using a high-pressure emulsifier NVL-AS200 (manufactured by Yoshida Kikai Kogyo Co., Ltd.) to prepare a suspension. A cross-sectional photograph of the obtained particle (5) is shown in FIG. The obtained particles (5) were confirmed to be hollow resin particles having a porous structure, with the hollow space surrounded by a shell and consisting of multiple hollow regions. The volume average particle size of the obtained particles (5) was 4.2 μm, and the coefficient of variation was 35.3%. The 5% weight loss temperature of the obtained particles (5) was 399°C when the temperature was increased at a rate of 10°C / min in a nitrogen atmosphere. The blend amounts and various measurement results are shown in Table 1.

[0204] Example 6 Particles (6) were obtained in the same manner as in Example 5, except that instead of adding the oil phase to 1,381 g of a 2.5 wt % aqueous dispersion of magnesium pyrophosphate as the aqueous phase, the oil phase was added to a mixture of 1,381 g of a 2.5 wt % aqueous dispersion of magnesium pyrophosphate as the aqueous phase and 0.51 g of lauryldimethylaminoacetic acid betaine (purity content 35%). A cross-sectional photograph of the obtained particle (6) is shown in FIG. The obtained particles (6) were confirmed to be hollow resin particles having a porous structure, with the hollow space surrounded by a shell and consisting of multiple hollow regions. The volume average particle size of the obtained particles (6) was 4.5 μm, and the coefficient of variation was 31.1%. The 5% weight loss temperature of the obtained particles (6) was 392°C when the temperature was increased at a rate of 10°C / min in a nitrogen atmosphere. The blend amounts and various measurement results are shown in Table 1.

[0205] Example 7 Particles (7) were obtained in the same manner as in Example 6, except that the amount of reactive low-molecular-weight polyphenylene ether (trade name "Noryl (registered trademark) SA9000-111 resin", manufactured by SABIC Corporation) used as the compound having an ether structure was changed to 60 g, and the amount of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Material Co., Ltd., 81% content, 19% being ethylvinylbenzene (EVB)) used was changed to 140 g. A cross-sectional photograph of the obtained particle (7) is shown in FIG. The obtained particles (7) were confirmed to be hollow resin particles having a porous structure, with the hollow space surrounded by a shell and consisting of multiple hollow regions. The volume average particle size of the obtained particles (7) was 3.8 μm, and the coefficient of variation was 29.4%. The 5% weight loss temperature of the obtained particles (7) was 394°C when the temperature was increased at a rate of 10°C / min in a nitrogen atmosphere. The blend amounts and various measurement results are shown in Table 1.

[0206] Comparative Example 1 An oil phase was prepared by mixing 80 g of methyl methacrylate, 80 g of ethylene glycol dimethacrylate, 120 g of cyclohexane, 40 g of ethyl acetate, 1.60 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (trade name "V-65", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator, 0.32 g of "KAYAMER (registered trademark) PM-21" (manufactured by Nippon Kayaku Co., Ltd.) as a radical polymerizable monomer having a phosphate group, and 140 g of lauryl phosphate. The oil phase was added to 1,281 g of a 2 wt % aqueous dispersion of magnesium pyrophosphate as the aqueous phase, and the mixture was dispersed at 7,000 rpm for 5 minutes using a Polytron homogenizer "PT10-35" (Central Scientific Trading Co., Ltd.) to prepare a suspension. The resulting suspension was heated at 55°C for 5 hours, after which the internal temperature of the polymerization vessel was increased to 80°C (secondary heating), and the suspension was stirred at 80°C for 2 hours to complete the polymerization reaction. Hydrochloric acid was added to the resulting slurry to decompose the magnesium pyrophosphate, and the solids were separated by dehydration through filtration, purified by repeated washing with water, and then dried at 80°C for 24 hours to obtain particles (C1). A cross-sectional photograph of the obtained particles (C1) is shown in FIG. It was confirmed that the obtained particles (C1) were a mixture of hollow resin particles (C1a) in which the hollow surrounded by a shell consists of a single hollow region, and hollow resin particles (C1b) in which the hollow surrounded by a shell consists of a porous structure. The resulting particles (C1) had a volume average particle size of 7.4 μm and a coefficient of variation of 26.6%. The 5% weight loss temperature of the obtained particles (C1) was 239°C when the temperature was increased at a rate of 10°C / min in a nitrogen atmosphere.

[0207] Comparative Example 2 The same procedure as in Example 1 was carried out, except that the amount of "KAYAMER (registered trademark) PM-21" (manufactured by Nippon Kayaku Co., Ltd.) used as the radical polymerizable monomer having a phosphoric acid group was changed to 4.00 g. As a result, the particles were crushed and hollow resin particles could not be obtained. The blend amounts and various measurement results are shown in Table 1.

[0208] Comparative Example 3 Particles (C3) were obtained in the same manner as in Example 1, except that 1.20 g of lauryl phosphate was used instead of 1.20 g of "KAYAMER (registered trademark) PM-21" (manufactured by Nippon Kayaku Co., Ltd.) as a radical polymerizable monomer having a phosphate group. A cross-sectional photograph of the obtained particle (C3) is shown in FIG. The obtained particles (C3) were confirmed to be hollow resin particles having a porous structure, with the hollow space surrounded by a shell and consisting of multiple hollow regions. The volume average particle size of the obtained particles (C3) was 12.3 μm, and the coefficient of variation was 34.5%. The 5% weight loss temperature of the obtained particles (C3) was 392°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.

[0209] Example 8 An oil phase was prepared by mixing 56 g of a reactive low-molecular-weight polyphenylene ether (product name "Noryl® SA9000-111 Resin" manufactured by SABIC Corporation) as a compound having an ether structure, 84 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Material Co., Ltd., 81% content, 19% ethylvinylbenzene (EVB)), 140 g of heptane, 2.34 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (product name "V-65" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator, and 0.84 g of "KAYAMER® PM-21" (manufactured by Nippon Kayaku Co., Ltd.) as a radically polymerizable monomer having a phosphate group. The oil phase was added to 1214 g of a 2.5 wt% aqueous dispersion of magnesium pyrophosphate as the aqueous phase, and the mixture was dispersed at 7000 rpm for 2 minutes using a Polytron homogenizer "PT10-35" (Central Scientific Trading Co., Ltd.). The mixture was then emulsified at a processing pressure of 20 MPa using a high-pressure emulsifier NVL-AS200 (Yoshida Kikai Kogyo Co., Ltd.) to produce a suspension. The resulting suspension was heated at 55°C for 5 hours, after which 0.7 g of 1-octanethiol (Tokyo Chemical Industry Co., Ltd.) was added as a thiol to the polymerization vessel. The internal temperature of the polymerization vessel was raised to 80°C (secondary heating), and the suspension was stirred at 80°C for 2 hours to complete the polymerization reaction. Hydrochloric acid was added to the obtained slurry to decompose the magnesium pyrophosphate, and then the solid content was separated by dehydration through filtration, purified by repeated washing with water, and then dried at 80°C for 24 hours to obtain particles (8). A cross-sectional photograph of the obtained particle (8) is shown in FIG. The obtained particles (8) were confirmed to be hollow resin particles with a porous structure surrounded by a shell. The volume average particle size of the obtained particles (8) was 3.8 μm, and the coefficient of variation was 28.4%. The 5% weight loss temperature of the obtained particles (8) was 403.3°C when the temperature was increased at a rate of 10°C / min in a nitrogen atmosphere. The blending amounts and various measurement results are shown in Table 2.

[0210] Example 9 Particles (9) were obtained in the same manner as in Example 8, except that the amount of 1-octanethiol used as the thiol was 7.0 g. A cross-sectional photograph of the obtained particle (9) is shown in FIG. The obtained particles (9) were confirmed to be hollow resin particles having a porous structure surrounded by a shell. The volume average particle size of the obtained particles (9) was 3.4 μm, and the coefficient of variation was 22.7%. The 5% weight loss temperature of the obtained particles (9) was 390.9°C when the temperature was increased at a rate of 10°C / min in a nitrogen atmosphere. The blending amounts and various measurement results are shown in Table 2.

[0211] Example 10 Particles (10) were obtained in the same manner as in Example 9, except that instead of adding the oil phase to 1214 g of a 2.5 wt % aqueous dispersion of magnesium pyrophosphate as the aqueous phase, the oil phase was added to a mixture of 1214 g of a 2.5 wt % aqueous dispersion of magnesium pyrophosphate as the aqueous phase and 0.51 g of lauryldimethylaminoacetic acid betaine (purity content 35%). A cross-sectional photograph of the obtained particle (10) is shown in FIG. The obtained particles (10) were confirmed to be hollow resin particles having a porous structure with the hollow space surrounded by a shell. The volume average particle size of the obtained particles (10) was 3.8 μm, and the coefficient of variation was 28.1%. The 5% weight loss temperature of the obtained particles (10) was 388.5°C when the temperature was increased at 10°C / min in a nitrogen atmosphere. The amount of phosphorus element in the obtained particles (10) was 230 μg / g, and the amount of magnesium element was 89 μg / g. The blending amounts and various measurement results are shown in Table 2.

[0212] Example 11 Particles (11) were obtained in the same manner as in Example 8, except that the amount of 1-octanethiol used as the thiol was 14.0 g. A cross-sectional photograph of the obtained particle (11) is shown in FIG. The obtained particles (11) were confirmed to be hollow resin particles having a porous structure with the hollow space surrounded by a shell. The volume average particle size of the obtained particles (11) was 3.6 μm, and the coefficient of variation was 24.8%. The 5% weight loss temperature of the obtained particles (11) was 299.4°C when the temperature was increased at a rate of 10°C / min in a nitrogen atmosphere. The blending amounts and various measurement results are shown in Table 2.

[0213] Example 12 Particles (12) were obtained in the same manner as in Example 8, except that 7.0 g of 1-hexanethiol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the thiol. A cross-sectional photograph of the obtained particle (12) is shown in FIG. The obtained particles (12) were confirmed to be hollow resin particles having a porous structure with the hollow space surrounded by a shell. The volume average particle size of the obtained particles (12) was 3.5 μm, and the coefficient of variation was 24.9%. The 5% weight loss temperature of the obtained particles (12) was 382.7°C when the temperature was increased at a rate of 10°C / min in a nitrogen atmosphere. The blending amounts and various measurement results are shown in Table 2.

[0214] Example 13 Particles (13) were obtained in the same manner as in Example 8, except that 7.0 g of 1-dodecanethiol (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the thiol. A cross-sectional photograph of the obtained particle (13) is shown in FIG. The obtained particles (13) were confirmed to be hollow resin particles having a porous structure with the hollow space surrounded by a shell. The volume average particle size of the obtained particles (13) was 3.3 μm, and the coefficient of variation was 24.5%. The 5% weight loss temperature of the obtained particles (13) was 375.9°C when the temperature was increased at a rate of 10°C / min in a nitrogen atmosphere. The blending amounts and various measurement results are shown in Table 2.

[0215] Example 14 The mixture was dispersed at 7000 rpm for 2 minutes using a Polytron homogenizer "PT10-35" (manufactured by Central Scientific Trading Co., Ltd.), and the resulting suspension was heated at 55°C for 5 hours. 7.0 g of 1-octanethiol as a thiol was then added to the polymerization vessel, the internal temperature of the polymerization vessel was raised to 80°C (secondary heating), and the suspension was stirred at 80°C for 2 hours to complete the polymerization reaction. The procedure was carried out in the same manner as in Example 8, except for this, to obtain particles (14). A cross-sectional photograph of the obtained particle (14) is shown in FIG. The obtained particles (14) were confirmed to be hollow resin particles having a porous structure with the hollow space surrounded by a shell. The average particle size of the obtained particles (14) was 10.3 μm, and the coefficient of variation was 38.9%. The 5% weight loss temperature of the obtained particles (14) was 361.8°C when the temperature was increased at a rate of 10°C / min in a nitrogen atmosphere. The blending amounts and various measurement results are shown in Table 2.

[0216] Example 15 Particles (15) were obtained in the same manner as in Example 8, except that 56 g of a bifunctional polyphenylene ether oligomer (trade name "OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Co., Inc.) was used as the compound having an ether structure, and the amount of 1-octanethiol used as the thiol was changed to 7.0 g. A cross-sectional photograph of the obtained particle (15) is shown in FIG. The obtained particles (15) were confirmed to be hollow resin particles having a porous structure surrounded by a shell. The volume average particle size of the obtained particles (15) was 3.7 μm, and the coefficient of variation was 25.8%. The 5% weight loss temperature of the obtained particles (15) was 339.0°C when the temperature was increased at a rate of 10°C / min in a nitrogen atmosphere. The blending amounts and various measurement results are shown in Table 2.

[0217] Example 16 Particles (16) were obtained in the same manner as in Example 8, except that 42 g of a reactive low-molecular-weight polyphenylene ether (trade name "Noryl (registered trademark) SA9000-111 resin", manufactured by SABIC Corporation) as a compound having an ether structure, 98 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Material Co., Ltd., 81% content, 19% is ethylvinylbenzene (EVB)), and 7 g of 1-octanethiol as a thiol were added to a polymerization vessel, the internal temperature of the polymerization vessel was raised to 80°C (secondary heating), and the suspension was stirred at 80°C for 2 hours to complete the polymerization reaction. A cross-sectional photograph of the obtained particle (16) is shown in FIG. The obtained particles (16) were confirmed to be hollow resin particles with a porous structure surrounded by a shell. The volume average particle size of the obtained particles (16) was 4.6 μm, and the coefficient of variation was 41.2%. The 5% thermal weight loss temperature of the obtained particles (16) was 392.3°C when the temperature was increased at a rate of 10°C / min in a nitrogen atmosphere. The blending amounts and various measurement results are shown in Table 2.

[0218] Example 17 Particles (17) were obtained in the same manner as in Example 8, except that 84 g of a reactive low-molecular-weight polyphenylene ether (trade name "Noryl (registered trademark) SA9000-111 resin", manufactured by SABIC Corporation) as a compound having an ether structure, 56 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Material Co., Ltd., 81% content, 19% being ethylvinylbenzene (EVB)), and 7 g of 1-octanethiol as a thiol were added to a polymerization vessel, the internal temperature of the polymerization vessel was raised to 80°C (secondary heating), and the suspension was stirred at 80°C for 2 hours to complete the polymerization reaction. A cross-sectional photograph of the obtained particle (17) is shown in FIG. The obtained particles (17) were confirmed to be hollow resin particles having a single structure with a hollow space surrounded by a shell. The average particle size of the obtained particles (17) was 6.4 μm. The 5% thermal weight loss temperature of the obtained particles (17) was 354.4°C when the temperature was increased at a rate of 10°C / min in a nitrogen atmosphere. The blending amounts and various measurement results are shown in Table 2.

[0219] Comparative Example 4 An oil phase was prepared by mixing 70 g of methyl methacrylate, 70 g of ethylene glycol dimethacrylate, 35 g of ethyl acetate, 105 g of cyclohexane, 1.4 g of 2,2′-azobis(2,4-dimethylvaleronitrile) (trade name “V-65” manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator, and 0.28 g of “KAYAMER (registered trademark) PM-21” (manufactured by Nippon Kayaku Co., Ltd.). The oil phase was added to 1214 g of a 2.5 wt % aqueous dispersion of magnesium pyrophosphate as the aqueous phase, and the mixture was dispersed at 7000 rpm for 2 minutes using a Polytron homogenizer "PT10-35" (manufactured by Central Scientific Trading Co., Ltd.) to prepare a suspension. The resulting suspension was heated at 55°C for 5 hours, after which the internal temperature of the polymerization vessel was raised to 80°C (secondary heating), and the suspension was stirred at 80°C for 2 hours to complete the polymerization reaction. Hydrochloric acid was added to the obtained slurry to decompose the magnesium pyrophosphate, and then the solid matter was separated by dehydration through filtration, purified by repeated washing with water, and then dried at 80°C for 24 hours to obtain particles (C4). A cross-sectional photograph of the obtained particles (C4) is shown in FIG. The obtained particles (C4) were confirmed to be hollow resin particles having a porous structure with the hollow space surrounded by a shell. The resulting particles (C4) had a volume average particle size of 7.4 μm and a coefficient of variation of 26.6%. The 5% thermal weight loss temperature of the obtained particles (C4) was 239.2°C when the temperature was increased at a rate of 10°C / min in a nitrogen atmosphere. The blending amounts and various measurement results are shown in Table 2.

[0220] Comparative Example 5 An oil phase was prepared by mixing 56 g of a bifunctional polyphenylene ether oligomer (trade name "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Inc.) as a compound having an ether structure, 84 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Material Co., Ltd., 81% content, 19% ethylvinylbenzene (EVB)), 140 g of heptane, 2.34 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (trade name "V-65" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator, and 0.84 g of "KAYAMER® PM-21" (manufactured by Nippon Kayaku Co., Ltd.) as a radically polymerizable monomer having a phosphate group. The oil phase was added to 1214 g of a 2.5 wt % aqueous dispersion of magnesium pyrophosphate as the aqueous phase, and the mixture was dispersed at 7000 rpm for 2 minutes using a Polytron homogenizer "PT10-35" (manufactured by Central Scientific Trading Co., Ltd.). The mixture was then emulsified at a processing pressure of 20 MPa using a high-pressure emulsifier NVL-AS200 (manufactured by Yoshida Kikai Kogyo Co., Ltd.) to produce a suspension. The resulting suspension was heated at 55°C for 5 hours, after which the internal temperature of the polymerization vessel was raised to 80°C (secondary heating), and the suspension was stirred at 80°C for 2 hours to complete the polymerization reaction. Hydrochloric acid was added to the obtained slurry to decompose the magnesium pyrophosphate, and then the solid matter was separated by dehydration through filtration, purified by repeated washing with water, and then dried at 80°C for 24 hours to obtain particles (C5). A cross-sectional photograph of the obtained particle (C5) is shown in FIG. The obtained particles (C5) were confirmed to be hollow resin particles having a porous structure with the hollow space surrounded by a shell. The volume average particle size of the obtained particles (C5) was 9.8 μm, and the coefficient of variation was 42.9%. The 5% thermal weight loss temperature of the obtained particles (C5) was 371.6°C when the temperature was increased at a rate of 10°C / min in a nitrogen atmosphere. The blending amounts and various measurement results are shown in Table 2.

[0221] [Table 1]

[0222] [Table 2]

[0223] Example 18 0.425 g of the hollow resin particles (particles (1)) obtained in Example 1, 8.3 g of ethyl acetate, and 1.7 g of solvent-soluble polyimide KPI-MX300F (manufactured by Kawamura Sangyo Co., Ltd.) were degassed and stirred using a planetary stirring degasser (manufactured by KURABO Corporation, "Mazerustar KK-250") to produce resin composition (1). Resin composition (1) was applied to a 5 mm thick glass plate using an applicator set to a wet thickness of 250 μm, and then heated at 60°C for 30 minutes, 90°C for 10 minutes, 150°C for 30 minutes, and 200°C for 30 minutes to remove ethyl acetate. After that, the film was cooled to room temperature to obtain film (1).

[0224] Example 19 The procedure of Example 18 was repeated, except that 0.425 g of the hollow resin particles (particles (1)) obtained in Example 1 was replaced with 0.425 g of the hollow resin particles (particles (5)) obtained in Example 5, to obtain a resin composition (5) and a film (5). A cross-sectional sample of film (5) was prepared by a cross-section polisher using a cross-section preparation device "IB-19500CP" (manufactured by JEOL Ltd.), and the cross-section was observed using a scanning electron microscope "S-3400N" manufactured by Hitachi High-Technologies Corporation. The obtained cross-sectional photograph is shown in FIG. In the cross-sectional photograph, the white areas represent polyimide, the spherical materials observed within the white areas represent hollow resin particles, and the black areas inside the hollow resin particles represent air spaces. When the inside of a hollow resin particle is observed to be black, as shown in Figure 22, it means that the voids of the hollow resin particle are maintained within the polyimide film, i.e., the resin (polyimide) has not penetrated into the inside of the hollow resin particle.

[0225] Comparative Example 6 The procedure of Example 18 was repeated, except that 0.425 g of the hollow resin particles (particles (C1)) obtained in Comparative Example 1 was used instead of 0.425 g of the hollow resin particles (particles (1)) obtained in Example 1, to obtain a resin composition (C1) and a film (C1).

[0226] Comparative Example 7 The procedure of Example 18 was repeated, except that 0.425 g of hollow resin particles (particles (C3)) obtained in Comparative Example 3 was used instead of 0.425 g of hollow resin particles (particles (1)) obtained in Example 1, to obtain a resin composition (C3) and a film (C3). A cross-sectional sample of film (C3) was prepared by the cross-section polisher method using a cross-section preparation device "IB-19500CP" (manufactured by JEOL Ltd.), and the cross-section was observed using a scanning electron microscope "S-3400N" (manufactured by Hitachi High-Technologies Corp.) The obtained cross-sectional photograph is shown in Figure 23. In the cross-sectional photograph, the white areas represent polyimide, the spherical materials observed within the white areas represent hollow resin particles, and the black areas inside the hollow resin particles represent air spaces. As shown in Figure 23, if part of the interior of a hollow resin particle is observed to be gray or white instead of black, this means that the resin (polyimide) has partially penetrated into the hollow resin particle, reducing the void space.

[0227] <Performance evaluation: relative permittivity and dielectric loss tangent evaluation> The dielectric constant and dielectric loss tangent of the films obtained in Examples 18 and 19 and Comparative Examples 6 and 7 were evaluated using a cavity resonance method (measurement frequency: 5.8 GHz). The measurement results were expressed as a relative percentage (%), with the measurement value for a film containing no particles taken as 100%. The results are shown in Table 3.

[0228] [Table 3]

[0229] From the results in Table 3, it can be confirmed 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 for the purpose of lowering the dielectric constant and dielectric loss tangent of semiconductor materials.

[0230] Example 20 0.425 g of the hollow resin particles (particles (9)) obtained in Example 9, 8.3 g of ethyl acetate, and 1.7 g of solvent-soluble polyimide KPI-MX300F (manufactured by Kawamura Sangyo Co., Ltd.) were degassed and stirred using a planetary stirring degasser (manufactured by KURABO Corporation, "Mazerustar KK-250") to produce resin composition (9). Resin composition (9) was applied to a 5 mm thick glass plate using an applicator set to a wet thickness of 250 μm, and then heated at 60°C for 30 minutes, 90°C for 10 minutes, 150°C for 30 minutes, and 200°C for 30 minutes to remove ethyl acetate. After that, the film was cooled to room temperature to obtain film (9).

[0231] Comparative Example 8 The procedure of Example 20 was repeated, except that 0.425 g of the hollow resin particles (particles (C4)) obtained in Comparative Example 4 was used instead of 0.425 g of the hollow resin particles (particles (9)) obtained in Example 9, to obtain a resin composition (C4) and a film (C4).

[0232] <Performance evaluation: relative permittivity and dielectric loss tangent evaluation> The dielectric constant and dielectric loss tangent of the films obtained in Example 20 and Comparative Example 8 were evaluated by a cavity resonance method (measurement frequency: 5.8 GHz). The measurement results were expressed as a relative percentage (%), with the measurement value for a film containing no particles being 100%. The results are shown in Table 4.

[0233] [Table 4]

[0234] From the results in Table 4, it can be confirmed 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 for the purpose of lowering the dielectric constant and dielectric loss tangent of semiconductor materials.

[0235] Example 21 To 10 g of a commercially available water-based paint (manufactured by Asahipen Co., Ltd., product name "Water-based Multi-Purpose Color Clear"), 2.5 g of the hollow resin particles (particles (6)) obtained in Example 6 was added, and the mixture was degassed and stirred using a planetary stirring defoamer (manufactured by KURABO Corporation, Mazerustar KK-250) to obtain a paint composition (6-1).

[0236] <Performance evaluation: Evaluation of ultraviolet, visible, and near-infrared light reflection characteristics> The coating composition (6-1) obtained in Example 21 was applied to the black side of the hiding power test paper using an applicator set to a wet thickness of 250 μm, and then thoroughly dried at room temperature to obtain a sample plate for evaluation. The reflectance of the sample plate to ultraviolet light, visible light, and near-infrared light was evaluated according to the following procedure. The reflectance was measured using a Shimadzu UV-Visible-Near-Infrared Spectrophotometer (Solid Spec3700) and the reflectance (%) of the coated surface of the sample plate for UV to near-infrared light (wavelengths 300 nm to 2500 nm). The measurements were performed using a 60 mm diameter integrating sphere and Spectralon as a standard white plate. The results obtained are shown in Figure 24. As shown in Figure 24, it can be seen that the film has a high reflectance of 40% or more for almost all wavelengths from ultraviolet light to near-infrared light. Furthermore, it is clear that the film has a near-infrared reflective effect, which imparts a heat insulating effect.

[0237] Example 22 Two parts by weight of the hollow resin particles (particles (6)) obtained in Example 6 and 20 parts by weight of a commercially available acrylic water-based gloss paint (Campe Papio, product name "Super Hit") were mixed for 3 minutes using a planetary agitator defoamer (KURABO, Mazerustar KK-250) and defoamed for 1 minute to obtain coating composition (6-2). The resulting coating composition (6-2) was applied to an ABS resin (acrylonitrile-butadiene-styrene resin) plate using a coating device equipped with a 75 μm clearance blade, and then dried to obtain coating film (6-2).

[0238] <Performance evaluation: Matte property evaluation> The coating composition (6-2) obtained in Example 22 was spray-coated onto a 3 mm thick acrylic plate to form a 50 μm thick matte coating film. The resulting coating film had no visible bumps (protrusions) and had good matte properties.

[0239] Example 23 7.5 parts by weight of the hollow resin particles (particles (6)) obtained in Example 6, 30 parts by weight of an acrylic resin (manufactured by DIC Corporation, product name "ACRYDIC A811"), 10 parts by weight of a crosslinker (manufactured by DIC Corporation, product name "VM-D"), and 50 parts by weight of butyl acetate as a solvent were mixed for 3 minutes using a planetary stirring defoamer (manufactured by KURABO Corporation, Mazerustar KK-250) and defoamed for 1 minute, to obtain a light-diffusing resin composition (6). The obtained light-diffusing resin composition (6) was applied onto a 125 μm thick PET film using a coating device equipped with a blade with a clearance of 50 μm, and then dried at 70°C for 10 minutes to obtain a light-diffusing film (6).

[0240] <Performance evaluation: Light diffusion evaluation> The total light transmittance and haze of the light diffusion film (6) obtained in Example 23 were measured according to JIS K 7361-1:1997 and JIS K 7136:2000, respectively, using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name "NDH 2000") The higher the diffusibility of light transmitted through the light diffusion film (transmitted light), the higher the haze value. As a result of the measurements, the haze was 42.1% and the total light transmittance was 83.6, and it was confirmed that the light diffusion film (6) obtained in Example 23 had excellent light diffusion properties.

[0241] Example 24 To 10 g of a commercially available water-based paint (manufactured by Asahipen Co., Ltd., product name "Water-based Multi-Purpose Color Clear"), 2.5 g of the hollow resin particles (particles (9)) obtained in Example 9 was added, and the mixture was degassed and stirred using a planetary stirring defoamer (manufactured by KURABO Corporation, Mazerustar KK-250) to obtain a paint composition (9-1).

[0242] <Performance evaluation: Evaluation of ultraviolet, visible, and near-infrared light reflection characteristics> The coating composition (9-1) obtained in Example 24 was applied to the black side of a hiding power test paper using an applicator set to a wet thickness of 250 μm, and then thoroughly dried at room temperature to obtain a sample plate for evaluation. The reflectance of the sample plate to ultraviolet light, visible light, and near-infrared light was evaluated according to the following procedure. The reflectance was measured using a Shimadzu UV-Visible-Near-Infrared Spectrophotometer (Solid Spec3700) and the reflectance (%) of the coated surface of the sample plate for UV to near-infrared light (wavelengths 300 nm to 2500 nm). The measurements were performed using a 60 mm diameter integrating sphere and Spectralon as a standard white plate. The results obtained are shown in Figure 25. As shown in Figure 25, it can be seen that the film has a high reflectance of 40% or more for almost all wavelengths from ultraviolet light to near-infrared light. Furthermore, it is clear that the film has a near-infrared reflective effect, which imparts a heat insulating effect.

[0243] Example 25 Two parts by weight of the hollow resin particles (particles (9)) obtained in Example 9 and 20 parts by weight of a commercially available acrylic water-based gloss paint (Campe Papio, product name "Super Hit") were mixed for 3 minutes using a planetary agitator defoamer (KURABO, Mazerustar KK-250) and defoamed for 1 minute to obtain coating composition (9-2). The resulting coating composition (9-2) was applied to an ABS resin (acrylonitrile-butadiene-styrene resin) plate using a coating device equipped with a 75 μm clearance blade, and then dried to obtain coating film (9-2).

[0244] <Performance evaluation: Matte property evaluation> The coating composition (9-2) obtained in Example 25 was spray-coated onto a 3 mm thick acrylic plate to form a 50 μm thick matte coating film. The resulting coating film had no visible bumps (protrusions) and had good matte properties.

[0245] Example 26 7.5 parts by weight of the hollow resin particles (particles (9)) obtained in Example 9, 30 parts by weight of an acrylic resin (manufactured by DIC Corporation, product name "ACRYDIC A811"), 10 parts by weight of a crosslinker (manufactured by DIC Corporation, product name "VM-D"), and 50 parts by weight of butyl acetate as a solvent were mixed for 3 minutes using a planetary stirring defoamer (manufactured by KURABO Corporation, Mazerustar KK-250) and defoamed for 1 minute, to obtain a light-diffusing resin composition (9). The obtained light-diffusing resin composition (9) was applied onto a 125 μm thick PET film using a coating device equipped with a blade with a clearance of 50 μm, and then dried at 70°C for 10 minutes to obtain a light-diffusing film (9).

[0246] <Performance evaluation: Light diffusion evaluation> The total light transmittance and haze of the light diffusion film (9) obtained in Example 26 were measured according to JIS K 7361-1:1997 and JIS K 7136:2000, respectively, using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name "NDH 2000") The higher the diffusibility of light transmitted through the light diffusion film (transmitted light), the higher the haze value. As a result of the measurements, the haze was 40.4% and the total light transmittance was 82.1, and it was confirmed that the light diffusion film (9) obtained in Example 26 had excellent light diffusion properties. [Industrial Applicability]

[0247] The hollow resin particles according to the embodiment of the present invention and the hollow resin particles obtained by the production method according to the embodiment of the present invention can be used as semiconductor materials, etc. The hollow resin particles according to the embodiment of the present invention and the hollow resin particles obtained by the production method according to the embodiment of the present invention can be used, for example, in resin compositions for semiconductor members.

Claims

1. A hollow resin particle having a shell portion and a hollow portion surrounded by the shell portion, the shell portion comprises a polymer (P) having an ether structure and a phosphate ester structure represented by formula (1), the polymer (P) is a polymer (AM) obtained by reacting a compound (A) having an ether structure and a radical-reactive group, which is represented by formula (1), with a monomer (M) that reacts with the compound (A), the monomer (M) containing a compound (B) having a phosphate ester structure and a radical-reactive group, The compound (A) is a reactive low-molecular-weight polyphenylene ether or a bifunctional polyphenylene ether oligomer; Hollow resin particles. 【Chemistry 1】

2. 2. The hollow resin particles according to claim 1, wherein a ratio of the compound (A) to the monomer (M) is (20 parts by weight to 80 parts by weight):(80 parts by weight to 20 parts by weight) in parts by weight ratio (compound (A):monomer (M)), where the total amount of the compound (A) and the monomer (M) is 100 parts by weight.

3. 2. The hollow resin particles according to claim 1, wherein the amount of the compound (B) relative to the total amount of the compound (A) and the monomer (M) is 0.0001 to 0.0190 parts by weight, when the total amount of the compound (A) and the monomer (M) is 1 part by weight.

4. A hollow resin particle having a shell portion and a hollow portion surrounded by the shell portion, the shell portion comprises a polymer (P) having an ether structure and a phosphate ester structure represented by formula (1), The polymer (P) contains a sulfur element, the polymer (P) is a polymer obtained by reacting a polymer (AM) obtained by reacting a compound (A) having an ether structure and a radical-reactive group, which is represented by formula (1), with a monomer (M) that reacts with the compound (A), with a thiol; the monomer (M) contains a compound (B) having a phosphate ester structure and a radical reactive group, The compound (A) is a reactive low-molecular-weight polyphenylene ether or a bifunctional polyphenylene ether oligomer; Hollow resin particles. 【Chemistry 2】

5. The hollow resin particles according to claim 4, wherein the residual vinyl group ratio is 15% or less.

6. The hollow resin particles according to claim 4, wherein the exothermic initiation temperature in the atmosphere is 290°C or higher.

7. 5. The hollow resin particles according to claim 4, wherein the sulfur atom content is 0.1% by mass to 3.0% by mass.

8. The hollow resin particles according to claim 4, wherein a ratio of the compound (A) to the monomer (M) is (20 parts by weight to 80 parts by weight):(80 parts by weight to 20 parts by weight) in parts by weight ratio (compound (A):monomer (M)), where the total amount of the compound (A) and the monomer (M) is 100 parts by weight.

9. 9. The hollow resin particles according to claim 1, wherein the volume average particle diameter is 0.1 μm to 100 μm.

10. 9. The hollow resin particles according to claim 1, wherein the coefficient of variation (CV value) of particle diameter is 10% to 50%.

11. 9. The hollow resin particles according to claim 1, wherein the hollow resin particles have a 5% weight loss temperature of 290°C or higher when heated at a rate of 10°C / min in a nitrogen atmosphere.

12. The hollow resin particles according to any one of claims 1 to 8, which are used in a resin composition for a semiconductor member.

13. The hollow resin particles according to any one of claims 1 to 8, which are used in a coating composition.

14. The hollow resin particles according to any one of claims 1 to 8, which are used in a heat insulating resin composition.

15. The hollow resin particle according to claim 1 , which is used in a light-diffusing resin composition.

16. The hollow resin particles according to any one of claims 1 to 8, which are used in a light diffusion film.

17. A resin composition for a semiconductor member, comprising the hollow resin particles according to any one of claims 1 to 8.

18. A coating composition comprising the hollow resin particles according to any one of claims 1 to 8.

19. A heat insulating resin composition comprising the hollow resin particles according to any one of claims 1 to 8.

20. A light-diffusing resin composition comprising the hollow resin particles according to any one of claims 1 to 8.

21. A light-diffusing film comprising the hollow resin particles according to any one of claims 1 to 8.

22. 20 to 80 parts by weight of a compound (A) having an ether structure and a radical reactive group represented by formula (1) and 80 to 20 parts by weight of a monomer (M) reactive with the compound (A) (the total amount of the compound (A) and the monomer (M) being 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 radical reactive group, The compound (A) is a reactive low-molecular-weight polyphenylene ether or a bifunctional polyphenylene ether oligomer; A method for producing hollow resin particles. 【Transformation 3】

23. an oil phase preparation step (I) of mixing 20 to 80 parts by weight of a compound (A) having an ether structure represented by formula (1) and a radical reactive group and 80 to 20 parts by weight of a monomer (M) that reacts with the compound (A) (the total amount of the compound (A) and the monomer (M) being 100 parts by weight) with a non-reactive solvent to prepare an oil phase; a suspension polymerization step (II) of adding the oil phase to an aqueous phase containing an aqueous medium and stirring the mixture to prepare a suspension; a thiol-ene reaction step (III) of adding a thiol to the suspension to react with the thiol to prepare a reaction product; Including, The compound (A) is a reactive low-molecular-weight polyphenylene ether or a bifunctional polyphenylene ether oligomer; A method for producing hollow resin particles. 【Chemistry 4】

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