WO2023157597A1 - 中空樹脂粒子、その製造方法、およびその用途 - Google Patents

中空樹脂粒子、その製造方法、およびその用途 Download PDF

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Publication number
WO2023157597A1
WO2023157597A1 PCT/JP2023/002380 JP2023002380W WO2023157597A1 WO 2023157597 A1 WO2023157597 A1 WO 2023157597A1 JP 2023002380 W JP2023002380 W JP 2023002380W WO 2023157597 A1 WO2023157597 A1 WO 2023157597A1
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Prior art keywords
resin particles
weight
hollow resin
parts
compound
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Ceased
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PCT/JP2023/002380
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English (en)
French (fr)
Japanese (ja)
Inventor
晋弥 松野
健太郎 田中
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Sekisui Kasei Co Ltd
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Sekisui Kasei Co Ltd
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Priority to CN202380022326.1A priority Critical patent/CN118715257A/zh
Priority to KR1020247027836A priority patent/KR102940057B1/ko
Priority to JP2024501056A priority patent/JP7811985B2/ja
Priority to EP23756125.3A priority patent/EP4480976A4/en
Publication of WO2023157597A1 publication Critical patent/WO2023157597A1/ja
Priority to US18/802,130 priority patent/US20240400796A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/08—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B01J13/16—Interfacial polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/18—Suspension polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/18—Suspension polymerisation
    • C08F2/20—Suspension polymerisation with the aid of macromolecular dispersing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
    • C08F212/36—Divinylbenzene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/53—Core-shell polymer

Definitions

  • the present invention relates to hollow resin particles, methods for producing the same, and uses thereof.
  • the hollow resin particles used for such applications for example, when the thermosetting resin in which the hollow resin particles are mixed are heated during molding or using solder, the hollow resin particles are substantially There is a demand for high heat resistance that does not cause significant changes.
  • thermosetting resin when the hollow resin particles are mixed with the thermosetting resin, the thermosetting resin may enter the inside of the hollow resin particles during kneading in the conventional hollow resin particles, and the air space inside the hollow resin particles becomes large. The problem of not being able to maintain can arise.
  • acrylic hollow resin particles are obtained by suspension polymerization of monomers mainly composed of acrylic polyfunctional monomers such as trimethylolpropane tri(meth)acrylate and dipentaerythritol hexaacrylate together with a hydrophobic solvent. It has been reported that resin particles can be obtained (Patent Document 1). However, acrylic resins have high values of dielectric constant and dielectric loss tangent, and are insufficient in heat resistance. For this reason, the acrylic hollow resin particles described in Patent Document 1 are not suitable for the purpose of lowering the dielectric constant and dielectric loss tangent of the resin layer, and for the purpose of imparting high heat resistance to the resin layer. .
  • porous hollow polymer particles As conventional hollow resin particles, monomers mainly composed of acrylic polyfunctional monomers such as trimethylolpropane tri(meth)acrylate and acrylic monofunctional monomers such as methyl methacrylate, and a dispersion stabilizer are used. It has been reported that porous hollow polymer particles can be obtained by suspension polymerization with a polar solvent (Patent Document 2). However, acrylic resins have high values of dielectric constant and dielectric loss tangent, and are insufficient in 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 used for the purpose of reducing the dielectric constant and dielectric loss tangent of the resin layer. It is unsuitable for the purpose of imparting high heat resistance. Furthermore, the porous hollow polymer particles have a thin shell surface layer, and the thermosetting resin easily penetrates into the inside of the porous hollow polymer particles.
  • hollow resin particles by blending hollow resin particles obtained by polymerizing a polyfunctional monomer and a monofunctional monomer into a resin, an organic insulating material with excellent insulating properties, a low dielectric constant and a low dielectric loss tangent can be obtained.
  • specific monomers used include styrene, methyl methacrylate, divinylbenzene, trimethylolpropane tri(meth)acrylate and the like (Patent Document 3).
  • Patent Document 3 since the hollow resin particles described in Patent Document 3 use both a styrene-based monomer and an acrylic monomer having high dielectric constant and dielectric loss tangent values, it is possible to reduce the dielectric constant and dielectric loss tangent of the resin layer.
  • Patent Document 3 as a guideline for heat resistance, a 10% weight loss temperature by TG-DTA measurement under a nitrogen atmosphere and a temperature increase condition of 10 ° C./min is shown, but the heat resistance is insufficient. is.
  • the shell is made of either a polymer or copolymer of a crosslinkable monomer, or a copolymer of the crosslinkable monomer and a monofunctional monomer, and has a single-phase structure.
  • styrene-based hollow resin particles obtained by suspension polymerization of divinylbenzene together with saturated hydrocarbons having 8 to 18 carbon atoms (more specifically, hexadecane). It has been reported that a resin composition containing a curable resin is suitable for manufacturing multilayer printed circuit boards used in electronic devices and the like (Patent Document 4).
  • the hollow resin particles described in Patent Document 4 use saturated hydrocarbons having 8 to 18 carbon atoms (more specifically, hexadecane) for their production, the solvent from the hollow part is removed by distillation or the like. Removal is difficult, and saturated hydrocarbons having 8 to 18 carbon atoms remain in the obtained styrene hollow resin particles, making it difficult to obtain styrene hollow resin particles in which the hollow portions are completely replaced with air.
  • the removal of the solvent as described above requires a high manufacturing cost.
  • the styrene-based hollow resin particles described in Patent Document 4 have insufficient heat resistance.
  • Patent Document 5 As a conventional hollow resin particle, a hollow resin particle made of a polymer containing a vinyl monomer unit and a phosphate ester monomer unit and having a volume average particle diameter of 0.5 to 1000 ⁇ m has been reported (Patent Document 5). .
  • the hollow resin particles described in Patent Document 5 use both a styrene-based monomer and an acrylic monomer having a high dielectric constant and dielectric loss tangent. The dielectric constant and dielectric loss tangent of the layer are insufficient, and the heat resistance is also insufficient.
  • a single layer structure is used, which is a hollow polymer fine particle comprising a shell and a hollow portion, wherein the shell comprises a copolymer of at least one crosslinkable monomer and at least one monofunctional monomer. and the copolymer is a hollow obtained by polymerizing a mixture containing 59.2% by weight or more of the crosslinkable monomer with respect to the total amount of the monofunctional monomer and the crosslinkable monomer Polymer microparticles have been reported (Patent Document 6).
  • the hollow resin particles described in Patent Document 6 are hollow resin particles having acrylic and styrene compositions. Acrylic compositions have high values of dielectric constant and dielectric loss tangent, and have insufficient heat resistance. Styrenic compositions have insufficient heat resistance.
  • a curable resin composition containing, as essential components, a vinyl compound obtained by converting a terminal of a bifunctional polyphenylene ether oligomer into a vinyl group and a high molecular weight substance having a weight average molecular weight of 10,000 or more has a low dielectric constant, a low dielectric loss tangent, and a high heat resistance. It has been reported that a cured product having excellent properties is obtained (Patent Document 7).
  • the resin composition described in Patent Document 7 is a resin composition having vinyl groups and unsaturated double bonds. Vinyl groups and unsaturated double bonds undergo an oxidation reaction when heated during the manufacturing process, and the heat generated by thermal decomposition causes warpage in the resin composition, and the heat history of the resin composition may cause the dielectric loss tangent to deteriorate. do.
  • thermosetting resin composition in which the blending ratio of [the (B) component + the (C) component] is 90: 10 to 10: 90 has toughness and excellent dielectric properties. It has been reported that in-plane variations in dielectric constant in a substrate can be suppressed and warping can be suppressed (Patent Document 8).
  • the resin composition described in Patent Document 8 has a resin curing temperature of 100° C. or higher, and requires a solvent or a temperature higher than the boiling point of the solvent. It is difficult to make hollow particles by
  • the present invention has been made to solve the above-described conventional problems, and a main object thereof is to provide a hollow resin particle having a shell portion and a hollow portion surrounded by the shell portion, which provides a low dielectric constant and a low dielectric constant.
  • An object of the present invention is to provide hollow resin particles capable of achieving a dielectric loss tangent and exhibiting excellent heat resistance.
  • Another object of the present invention is to provide a method for producing such hollow resin particles.
  • a further object is to provide uses for such hollow resin particles.
  • a hollow resin particle according to an embodiment of the present invention is a hollow resin particle having a shell portion and a hollow portion surrounded by the shell portion, wherein the shell portion has an ether structure represented by formula (1) and a polymer (P) having a phosphate ester structure.
  • the polymer (P) is a compound (A) having an ether structure and a radical reactive group represented by the above formula (1), and the compound (A).
  • a polymer (AM) obtained by reacting a monomer (M) that reacts with, wherein the monomer (M) may contain a compound (B) having a phosphate ester structure and a radical reactive group.
  • the ratio of the compound (A) and the monomer (M) is such that the total amount of the compound (A) and the monomer (M) is 100 parts by weight.
  • the weight ratio (compound (A):monomer (M)) may be (20 to 80 parts by weight):(80 to 20 parts by weight).
  • the compound (B ) when the total amount of the compound (A) and the monomer (M) is 100 parts by weight, the compound (B ) may be from 0.0001 to 0.0190 parts by weight.
  • the polymer (P) may contain elemental sulfur.
  • the vinyl group residual ratio of the hollow resin particles may be 15% or less.
  • the exothermic start temperature of the hollow resin particles in the atmosphere may be 290° C. or higher.
  • the hollow resin particles according to any one of [5] to [7] above may have a sulfur atom content of 0.1% by mass to 3.0% by mass.
  • the polymer (P) is a compound ( It may be a polymer obtained by reacting a polymer (AM) obtained by reacting A) with a monomer (M) that reacts with the compound (A) and a thiol.
  • the ratio of the compound (A) and the monomer (M) is such that the total amount of the compound (A) and the monomer (M) is 100 parts by weight. In this case, the weight ratio (compound (A):monomer (M)) may be (20 to 80 parts by weight):(80 to 20 parts by weight).
  • the hollow resin particles may have a volume average particle diameter of 0.1 ⁇ m to 100 ⁇ m.
  • the coefficient of variation (CV value) of the particle diameter of the hollow resin particles may be 10% to 50%.
  • the 5% weight loss temperature when the hollow resin particles are heated at 10°C/min in a nitrogen atmosphere is 290°C. or more.
  • the hollow resin particles according to any one of [1] to [13] above may be used in a resin composition for semiconductor members.
  • the hollow resin particles according to any one of [1] to [13] above may be used in a coating composition.
  • the hollow resin particles described in any one of [1] to [13] above may be used in a heat insulating resin composition.
  • the hollow resin particles may be used in a light-diffusing resin composition.
  • the hollow resin particles may be used in a light diffusion film.
  • a resin composition for a semiconductor member according to an embodiment of the present invention comprises the hollow resin particles according to any one of [1] to [13] above.
  • a coating composition according to an embodiment of the present invention comprises the hollow resin particles according to any one of [1] to [13] above.
  • a heat insulating resin composition according to an embodiment of the present invention comprises the hollow resin particles according to any one of [1] to [13] above.
  • a light-diffusing resin composition according to an embodiment of the present invention comprises the hollow resin particles according to any one of [1] to [13] above.
  • a light diffusion film according to an embodiment of the present invention comprises the hollow resin particles described in any one of [1] to [13] above.
  • a method for producing hollow resin particles according to an embodiment of the present invention comprises 20 to 80 parts by weight of a compound (A) having an ether structure represented by formula (1) and a radical reactive group, and ) reacts with 80 parts by weight to 20 parts by weight of the monomer (M) (the total amount of the compound (A) and the monomer (M) is 100 parts by weight) in the presence of a non-reactive solvent in an aqueous medium. and the monomer (M) contains a compound (B) having a phosphate ester structure and a radical reactive group.
  • a method for producing hollow resin particles according to an embodiment of the present invention comprises 20 to 80 parts by weight of a compound (A) having an ether structure represented by formula (1) and a radical reactive group, and ) and 80 to 20 parts by weight of the monomer (M) reacting with (the total amount of the compound (A) and the monomer (M) being 100 parts by weight) is mixed with a non-reactive solvent to prepare an oil phase.
  • an oil phase preparation step (I) a suspension polymerization step (II) in which a suspension is prepared by adding the oil phase to an aqueous phase containing an aqueous medium and stirring, and adding a thiol to the suspension and a thiolene reaction step (III) of adding and reacting to prepare a reactant.
  • a hollow resin particle having a shell portion and a hollow portion surrounded by the shell portion can achieve a low dielectric constant and a low dielectric loss tangent, and exhibit excellent heat resistance.
  • a method for producing such hollow resin particles can be provided. Further, applications of such hollow resin particles can be provided.
  • FIG. 1 is a cross-sectional photograph of particles (1) obtained in Example 1.
  • FIG. 2 is a cross-sectional photograph of particles (2) obtained in Example 2.
  • FIG. 2 is a cross-sectional photograph of particles (3) obtained in Example 3.
  • FIG. 4 is a cross-sectional photograph of particles (4) obtained in Example 4.
  • FIG. 2 is a cross-sectional photograph of particles (5) obtained in Example 5.
  • FIG. 10 is a cross-sectional photograph of particles (6) obtained in Example 6;
  • FIG. 10 is a cross-sectional photograph of particles (7) obtained in Example 7;
  • 1 is a cross-sectional photograph of particles (C1) obtained in Comparative Example 1.
  • FIG. 3 is a cross-sectional photograph of particles (C3) obtained in Comparative Example 3.
  • FIG. 10 is a cross-sectional photograph of particles (8) obtained in Example 8;
  • FIG. 10 is a cross-sectional photograph of particles (9) obtained in Example 9.
  • FIG. 10 is a cross-sectional photograph of particles (10) obtained in Example 10;
  • FIG. 11 is a cross-sectional photograph of particles (11) obtained in Example 11;
  • FIG. 10 is a cross-sectional photograph of particles (12) obtained in Example 12;
  • FIG. 10 is a cross-sectional photograph of particles (13) obtained in Example 13;
  • FIG. 10 is a cross-sectional photograph of particles (14) obtained in Example 14;
  • FIG. 10 is a cross-sectional photographic view of particles (15) obtained in Example 15;
  • FIG. 10 is a cross-sectional photograph of particles (16) obtained in Example 16;
  • FIG. 10 is a cross-sectional photograph of particles (17) obtained in Example 17; 4 is a cross-sectional photograph of particles (C4) obtained in Comparative Example 4.
  • FIG. 3 is a cross-sectional photograph of particles (C5) obtained in Comparative Example 5.
  • FIG. 1 is a cross-sectional photographic view of a film produced using particles (5) obtained in Example 5.
  • FIG. 2 is a cross-sectional photographic view of a film produced using particles (C3) obtained in Comparative Example 3.
  • FIG. FIG. 10 is a drawing showing the results of UV-visible-near-infrared spectrophotometer measurement of coating composition (6-1) obtained in Example 21.
  • FIG. 10 is a diagram showing the measurement results of the coating composition (9-1) obtained in Example 24 with an ultraviolet-visible-near-infrared spectrophotometer.
  • (meth) acrylic when used in this specification, it means “acrylic and/or methacrylic", and when the expression “(meth) acrylate” is used, “acrylate and/or methacrylate ", and the expression “(meth)allyl” means “allyl and/or methallyl”, and the expression “(meth)acrolein” means “acrolein and/or methacrolein”. means rain.
  • the expression “acid (salt)” in this specification 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.
  • a hollow resin particle according to an embodiment of the present invention is a hollow resin particle having a shell portion and a hollow portion surrounded by the shell portion.
  • the term "hollow” as used herein means a state in which the interior is filled with a substance other than resin, such as gas or liquid. means the state of being
  • the shell portion and the hollow portion surrounded by the shell portion may consist of one hollow region or may consist of a plurality of hollow regions (porous structure).
  • the volume average particle diameter of the hollow resin particles according to the embodiment of the present invention is preferably 0.1 ⁇ m to 100 ⁇ m, more preferably 0.2 ⁇ m to 50.0 ⁇ m, still more preferably 0.3 ⁇ m to 30.0 ⁇ m. It is preferably 0.4 ⁇ m to 20.0 ⁇ m. If the volume-average particle diameter of the hollow resin particles according to the embodiment of the invention is within the above range, the effects of the invention can be exhibited more effectively. If the volume-average particle diameter of the hollow resin particles according to the embodiment of the present invention is too small outside the above range, the thickness of the shell portion becomes relatively thin, and the hollow resin particles may not have sufficient strength.
  • thermosetting resin when the hollow resin particles are kneaded with the thermosetting resin, the thermosetting resin may enter the interior of the hollow resin particles. If the average particle diameter of the hollow resin particles according to the embodiment of the present invention is too large outside the above range, phase separation between the polymer and the solvent caused by polymerization of the monomer component during suspension polymerization may be difficult to occur. This may make it difficult to form the shell portion.
  • the coefficient of variation (CV value) of the particle diameter of the hollow resin particles according to the embodiment of the present invention is preferably 10% to 50%, more preferably 15% to 45%, and still more preferably 18% to 42%. and particularly preferably 20% to 40%. If the coefficient of variation (CV value) of the particle size of the hollow resin particles according to the embodiment of the present invention is within the above range, the effects of the present invention can be exhibited more effectively. When the coefficient of variation (CV value) of the particle size of the hollow resin particles according to the embodiment of the present invention is too small outside the above range, when the hollow resin particles are kneaded with the thermosetting resin, the hollow resin particles are not thermoset.
  • the thickness of the resin layer may vary. If the coefficient of variation (CV value) of the particle diameter of the hollow resin particles according to the embodiment of the present invention is too large outside the above range, an increase in the amount of coarse particles may cause, for example, a thin film when a resin layer is formed from a resin composition. There is a possibility that it may become difficult and the thickness may vary.
  • CV value coefficient of variation
  • the hollow resin particles according to the embodiment of the present invention have a 5% weight loss temperature of preferably 290° C. or higher, more preferably 300° C. or higher when heated at 10° C./min in a nitrogen atmosphere. It is preferably 320° C. or higher, particularly preferably 340° C. or higher, and most preferably 360° C. or higher. Realistically, the upper limit of the 5% weight loss temperature is preferably 500°C or less. If the 5% weight loss temperature of the hollow resin particles according to the embodiment of the present invention when heated at 10°C/min in a nitrogen atmosphere is within the above range, the hollow resin particles according to the embodiment of the present invention are excellent. Heat resistance can be expressed.
  • the 5% weight loss temperature of the hollow resin particles according to the embodiment of the present invention when heated at 10° C./min in a nitrogen atmosphere is too low outside the above range, the particles will be deformed by heating.
  • the hollow resin particles are kneaded with a thermosetting resin, the hollow resin particles are deformed by heating for the curing reaction, and the hollow part is lost, resulting in a low dielectric constant effect and a low dielectric loss tangent. There is a possibility that the effect will decrease.
  • the amount of elemental phosphorus contained in the hollow resin particles is preferably 1,000 ⁇ g/g or less, more preferably 750 ⁇ g/g or less, and still more preferably 600 ⁇ g/g. g or less, and particularly preferably 500 ⁇ g/g or less. If the amount of elemental phosphorus contained in the hollow resin particles according to the embodiment of the present invention is within the above range, the effects of the present invention can be exhibited more effectively. If the phosphorus element content in the hollow resin particles according to the embodiment of the present invention is too large outside the above range, the dielectric constant and dielectric loss tangent of the resin layer formed from the resin composition containing the hollow resin particles are reduced. may not be achieved.
  • the elemental magnesium content in the hollow resin particles is preferably 200 ⁇ g/g or less, more preferably 150 ⁇ g/g or less, and still more preferably 125 ⁇ g/g or less. and particularly preferably 100 ⁇ g/g or less. If the amount of elemental magnesium contained in the hollow resin particles according to the embodiment of the present invention is within the above range, the effects of the present invention can be further exhibited. If the amount of elemental magnesium contained in the hollow resin particles according to the embodiment of the present invention is too large outside the above range, the dielectric constant and dielectric loss tangent of the resin layer formed from the resin composition containing the hollow resin particles are reduced. may not be achieved.
  • the shell portion contains a polymer (P) having an ether structure and a phosphate ester structure represented by formula (1).
  • the polymer (P) may have only one ether structure represented by formula (1), or may have two or more ether structures.
  • the polymer (P) may have only one type of phosphate ester structure, or may have two or more types.
  • the phosphate structure is preferably represented by formula (2) in that the effect of the present invention can be exhibited more effectively.
  • R 1 and R 2 each independently represent an organic group or a hydrogen atom.
  • the organic group that can be taken by R 1 and R 2 in formula (2) is a group containing a carbon atom and may contain an inorganic atom.
  • the organic groups that can be taken by R 1 and R 2 in formula (2) are more preferably represented by formula (3) in that the effects of the present invention can be exhibited more.
  • R 1 and R 2 each independently represent an organic group or a hydrogen atom.
  • the organic group that can be taken by R 1 and R 2 in formula (3) is a group containing a carbon atom and may contain an inorganic atom.
  • R 3 is a linear or branched alkylene group having 1-30 carbon atoms, and m represents 1-300.
  • R 3 is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably a linear or branched chain having 1 to 10 carbon atoms.
  • An alkylene group having a chain more preferably a linear or branched alkylene group having 1 to 8 carbon atoms, particularly preferably a linear alkylene group having 1 to 6 carbon atoms or an alkylene group having a branched chain, most preferably a linear or branched alkylene group having 1 to 4 carbon atoms.
  • m is preferably 1-100, more preferably 1-50, even more preferably 1-40, and particularly preferably 1-30.
  • the phosphate ester structure may be a phosphate monoester structure (both of R 1 and R 2 are hydrogen atoms), or a phosphate diester structure (one of R 1 and R 2 is an organic group and the other is hydrogen atom) or a phosphate triester structure (both of R 1 and R 2 are organic groups).
  • the phosphate ester structure is preferably a phosphate monoester structure or a phosphate diester structure in that the effects of the present invention can be expressed more effectively.
  • the polymer (P) may be of only one type, or may be of two or more types.
  • the content of the polymer (P) in the shell portion is preferably 60% by weight to 100% by weight, more preferably 70% by weight to 100% by weight, from the viewpoint that the effects of the present invention can be more expressed, More preferably 80% to 100% by weight, particularly preferably 90% to 100% by weight.
  • the polymer (P) may have a sulfur element. That is, the polymer (P) may have an ether structure, a phosphate ester structure, and elemental sulfur represented by Formula (1).
  • 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)).
  • 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 chain having 4 to 16 carbon atoms. , more preferably a linear or branched alkyl group having 6 to 12 carbon atoms, particularly preferably a linear or branched alkyl group having 8 to 10 carbon atoms, or It is an alkyl group having a branched chain.
  • the vinyl group residual ratio is preferably 15% or less, more preferably 12% or less, and still more preferably 10%. or less, and particularly preferably 8% or less. If the vinyl group residual ratio of the hollow resin particles according to the embodiment of the present invention is within the above range, that is, if the residual vinyl group is very small, thermal decomposition (for example, the semiconductor member manufacturing process temperature of about 200 to 300 ° C. Heat generation due to thermal decomposition below the surface is suppressed, and superior heat resistance can be exhibited.
  • thermal decomposition for example, the semiconductor member manufacturing process temperature of about 200 to 300 ° C. Heat generation due to thermal decomposition below the surface is suppressed, and superior heat resistance can be exhibited.
  • the vinyl group residual ratio of the hollow resin particles according to the embodiment of the present invention is within the above range, that is, if the residual vinyl group is very small, low dielectric A higher efficiency 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 outside the above range, the particles may undergo an oxidation reaction due to heating in the production process, resulting in decomposition and heat generation. In addition, there is a possibility that the thermosetting resin composition obtained by kneading with the thermosetting resin may warp, and there is a possibility that a low dielectric constant and a low dielectric loss tangent cannot be achieved.
  • the sulfur atom content by fluorescent X-ray analysis is preferably 0.1% by mass to 3.0% by mass, and more It is preferably 0.5% by mass to 2.5% by mass, more preferably 0.8% by mass to 2.0% by mass, and particularly preferably 1.0% by mass to 1.5% by mass. If the sulfur atom content of the hollow resin particles according to the embodiment of the present invention is within the above range, heat generation due to thermal decomposition (for example, thermal decomposition under the semiconductor member manufacturing process temperature of about 200 to 300 ° C.) is suppressed. be.
  • thermal decomposition for example, thermal decomposition under the semiconductor member manufacturing process temperature of about 200 to 300 ° C.
  • the sulfur atom content of the hollow resin particles according to the embodiment of the present invention is within the above range, the thiolene reaction to the particles will proceed sufficiently, accompanied by By reducing the number of vinyl groups in the particles, a lower dielectric constant and a lower dielectric loss tangent can be achieved. If the sulfur atom content of the hollow resin particles according to the embodiment of the present invention is out of the above range and is too large, the odor will become strong, which may cause problems in actual use.
  • the sulfur atom content of the hollow resin particles according to the embodiment of the present invention is too small outside the above range, the thiolene reaction on the particles will not proceed sufficiently, and many vinyl groups will remain in the particles, resulting in There is a risk that the particles will decompose and heat will be generated by heating in, for example, the thermosetting resin composition obtained by kneading with the thermosetting resin may warp, and the low dielectric constant reduction and low dielectric loss tangent may not be achieved.
  • the hollow resin particles according to the embodiment of the present invention preferably have an exothermic start temperature of 290° C. or higher, more preferably 300° C. or higher, still more preferably It is 310° C. or higher, and particularly preferably 315° C. or higher. If the exothermic start temperature of the hollow resin particles according to the embodiment of the present invention in the atmosphere is within the above range, the hollow resin particles according to the embodiment of the present invention can exhibit more excellent heat resistance. Moreover, if the exothermic start temperature of the hollow resin particles according to the embodiment of the present invention in the atmosphere is within the above range, the hollow resin particles according to the embodiment of the present invention can exhibit more excellent heat resistance.
  • the particles may undergo an oxidation reaction due to heating, and the particles may decompose and generate heat.
  • the thermosetting resin composition obtained by kneading with the thermosetting resin may warp.
  • the shell portion may contain any appropriate other component within a range that does not impair the effects of the present invention.
  • any appropriate polymer can be adopted as long as it is a polymer having an ether structure and a phosphate ester structure represented by formula (1), as long as it does not impair the effects of the present invention.
  • the following two embodiments are preferred as such a polymer (P) in that the effects of the present invention can be more expressed.
  • Embodiment 1 of polymer (P) A polymer having an ether structure and a phosphate ester structure represented by formula (1), preferably radically reactive with the ether structure represented by formula (1)
  • a polymer (AM) obtained by reacting a compound (A) having a group and a monomer (M) that reacts with the compound (A), wherein the monomer (M) has a phosphate ester structure and a radical reactive group.
  • B A polymer having an ether structure and a phosphate ester structure represented by formula (1), preferably radically reactive with the ether structure represented by formula (1)
  • a polymer (AM) obtained by reacting a compound (A) having a group and a monomer (M) that reacts with the compound (A), wherein the monomer (M) has a phosphate ester structure and a radical reactive group.
  • Embodiment 2 of polymer (P) A polymer having an ether structure represented by formula (1), a phosphate ester structure, and a sulfur element, preferably an ether structure represented by formula (1)
  • a polymer obtained by reacting a compound (A) having a radically reactive group with a monomer (M) that reacts with the compound (A) and a polymer (AM) obtained by reacting a thiol with the monomer (M) contains a compound (B) having a phosphate ester structure and a radically reactive group.
  • One preferred embodiment 1 of the polymer (P) is a polymer having an ether structure and a phosphate ester structure represented by formula (1), preferably the ether structure represented by formula (1) and a radical reaction A polymer (AM) obtained by reacting a compound (A) having a reactive group and a monomer (M) that reacts with the compound (A), wherein the monomer (M) has a phosphate ester structure and a radical reactive group. Contains compound (B).
  • one preferred embodiment 1 of polymer (P) is polymer (AM).
  • the compound (A) having an ether structure and a radical-reactive group represented by formula (1) may be of only one type, or may be of two or more types.
  • the compound (B) having a phosphate ester structure and a radical reactive group may be of only one type, or may be of two or more types.
  • radical reactive group any suitable polymer can be adopted 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.
  • a radical reactive group preferably includes a group having a carbon-carbon unsaturated double bond, specifically, for example, a vinyl group, Acryl groups, methacryl groups, acrylamide groups, and allyl groups can be mentioned.
  • the radical-reactive group preferably has a structure represented by formula (4) in that the effects of the present invention can be exhibited more effectively.
  • R4 represents a methyl group or a hydrogen atom.
  • the ratio of the compound (A) and the monomer (M) is the weight part ratio (compound (A):monomer (M)) when the total amount of the compound (A) and the monomer (M) is 100 parts by weight. , preferably (20 to 80 parts by weight): (80 to 20 parts by weight), more preferably (20 to 70 parts by weight): (80 to 30 parts by weight), More preferably (25 to 60 parts by weight): (75 to 40 parts by weight), particularly preferably (30 to 50 parts by weight): (70 to 50 parts by weight). If the content of the compound (A) is too small outside the above range, the heat resistance may be insufficient. If the content of the compound (A) is too large outside the above range, it may be difficult to form the shell and the hollow portion surrounded by the shell.
  • the amount of compound (B) with respect to the total amount is preferably 0.0001 to 0.0190 parts by weight, and more It is preferably 0.0005 to 0.0190 parts by weight, 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 the compound (B) is too small outside the above range, the average particle size will be reduced and the dispersion stability of the oil droplets will be insufficient, resulting in frequent formation of polymer lumps and coarse particles. If the content of the compound (B) is too large outside the above range, it may be difficult to form the shell portion and the hollow portion surrounded by the shell portion.
  • any appropriate compound can be adopted as long as it does not impair the effects of the present invention.
  • Such a compound (A) is preferably polyphenylene ether in that the effects of the present invention can be expressed more effectively.
  • polyphenylene ethers include, for example, the trade name "NORYL (registered trademark)” series (NORYL (registered trademark) SA9000, etc.) (manufactured by SABIC Corporation), the trade name “Iupiace (registered trademark)” series (Mitsubishi Chemical Corporation company), trade name “Zylon (registered trademark)” series (manufactured by Asahi Kasei Corporation), and trade name “OPE-2St” series (manufactured by Mitsubishi Gas Chemical Co., Ltd.).
  • the polyphenylene ether is preferably an oligomer, and preferably has a number average molecular weight Mn of 500 to 3,500, from the viewpoint that hollow resin particles with excellent heat resistance can be produced more easily.
  • any appropriate compound can be employed as long as it has a phosphate ester structure and a radical reactive group, as long as it does not impair the effects of the present invention.
  • the compound (B) is preferably a compound represented by the formula (5) in that the effects of the present invention can be exhibited more effectively.
  • R 3 and R 5 are linear or branched alkylene groups having 1 to 30 carbon atoms, and R 4 represents a methyl group or a hydrogen atom.
  • m represents 1-300.
  • n represents 1-3.
  • a is 0 or 1
  • b is 0-300
  • c is 0 or 1.
  • R 3 is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably a linear or branched chain having 1 to 10 carbon atoms.
  • An alkylene group having a chain more preferably a linear or branched alkylene group having 1 to 8 carbon atoms, particularly preferably a linear alkylene group having 1 to 6 carbon atoms or an alkylene group having a branched chain, most preferably a linear or branched alkylene group having 1 to 4 carbon atoms.
  • R 5 is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably a linear or branched chain having 1 to 10 carbon atoms.
  • An alkylene group having a chain more preferably a linear or branched alkylene group having 1 to 8 carbon atoms, particularly preferably a linear alkylene group having 1 to 6 carbon atoms or an alkylene group having a branched chain, most preferably a linear or branched alkylene group having 1 to 4 carbon atoms.
  • m is preferably 1-100, more preferably 1-50, even more preferably 1-40, and particularly preferably 1-30.
  • b is preferably 0 to 100, more preferably 0 to 50, still more preferably 0 to 10, particularly preferably 0 to 5, most preferably 0 or 1 is.
  • a commercially available product may be used as the compound (B).
  • compound (B) for example, from the viewpoint of compatibility, trade name "KAYAMER (registered trademark) PM-21” (manufactured by Nippon Kayaku Co., Ltd.) can be mentioned.
  • Examples of monomers (M) other than compound (B) include crosslinkable monomers and monofunctional monomers.
  • a monomer that reacts with the terminal group of the compound (A) and/or the compound (B) is preferred in that the effects of the present invention can be more expressed.
  • crosslinkable monomers examples include polyfunctional (meth)acrylic acid esters such as ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and glycerin tri(meth)acrylate; N,N'-methylenebis(meth) polyfunctional acrylamide derivatives such as acrylamide and N,N'-ethylenebis(meth)acrylamide; polyfunctional allyl derivatives such as diallylamine and tetraallyloxyethane; aromatic crosslinkable monomers such as divinylbenzene, divinylnaphthalene and diallyl phthalate; is mentioned.
  • the crosslinkable monomer an aromatic crosslinkable monomer is preferable, and divinylbenzene is more preferable, in that the effects of the present invention can be more expressed.
  • the number of crosslinkable monomers may be one, or two or more.
  • monofunctional monomers examples include alkyl (meth)acrylate esters having 1 to 16 carbon atoms such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and cetyl (meth)acrylate; styrene, ⁇ -Aromatic monofunctional monomers such as methylstyrene, ethylvinylbenzene, vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, vinylbiphenyl, and vinylnaphthalene; dimethyl maleate, diethyl fumarate, dimethyl fuma dicarboxylic acid ester monomers such as diethyl fumarate; maleic anhydride; N-vinylcarbazole; (meth)acrylonitrile; As the monofunctional monomer, aromatic monofunctional monomers are preferred, and styrene and ethylvinyl
  • the reaction between the compound (A) and the monomer (M) can be carried out by any appropriate reaction within the range that does not impair the effects of the present invention.
  • a reaction is preferably a suspension polymerization reaction.
  • the oil phase is added to the water phase and suspended, and the polymerization reaction is carried out.
  • the water phase and oil phase may contain any appropriate solvent within a range that does not impair the effects of the present invention.
  • solvents include, for example, aqueous media and non-reactive solvents as described later. Only one kind of solvent may be used, or two or more kinds thereof may be used.
  • any suitable additive (C ) may be used.
  • Additives (C) may be used alone or in combination of two or more.
  • the additive (C) as used herein does not include a solvent such as an aqueous medium or a non-reactive solvent, and a dispersion stabilizer, which will be described later.
  • the content of additive (C) is preferably 0% to 40% by weight, more preferably 0% to 30% by weight, relative to the total amount of compound (A) and monomer (M). more preferably 0 wt % to 20 wt %, particularly preferably 0 wt % to 10 wt %.
  • additive (C) any suitable additive that does not correspond to either the compound (A) or the monomer (M) can be adopted as long as it does not impair the effects of the present invention.
  • additives (C) include non-crosslinkable polymers, polymerization initiators and surfactants.
  • phase separation between the polymer (P) generated as the reaction progresses and the solvent can be promoted, and shell formation can be promoted.
  • non-crosslinkable polymers 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.
  • Polyolefins include, for example, polyethylene, polypropylene, and poly ⁇ -olefins. From the viewpoint of solubility in the monomer composition, side-chain crystalline polyolefins using long-chain ⁇ -olefins as starting materials, low-molecular-weight polyolefins produced with metallocene catalysts, and olefin oligomers are preferably used.
  • styrene polymers include polystyrene, styrene-acrylonitrile copolymers, and acrylonitrile-butadiene-styrene copolymers.
  • (Meth)acrylic acid-based polymers include, for example, polymethyl (meth)acrylate, polyethyl (meth)acrylate, polybutyl (meth)acrylate, and polypropyl (meth)acrylate.
  • styrene-(meth)acrylic acid-based polymers examples include styrene-methyl (meth)acrylate copolymer, styrene-ethyl (meth)acrylate copolymer, styrene-butyl (meth)acrylate copolymer, styrene-propyl (Meth)acrylate copolymers and the like.
  • a surfactant may be used as the additive (C) from the viewpoint of producing the desired hollow resin particles more stably.
  • the surfactant at least one selected from amphoteric surfactants and anionic surfactants is preferable, and at least amphoteric surfactants are more preferably selected from the viewpoint that the effects of the present invention can be more expressed.
  • amphoteric surfactant can be employed as the amphoteric surfactant within the range that does not impair the effects of the present invention.
  • amphoteric surfactants known amphoteric surfactants that can be used in the production of resin particles can be used.
  • amphoteric surfactants include lauryldimethylamine oxide, betaine lauryldimethylaminoacetate, phosphate surfactants, and phosphite surfactants. Only one type of amphoteric surfactant may be used, or two or more types may be used.
  • anionic surfactant Any appropriate anionic surfactant can be employed as the anionic surfactant as long as it does not impair the effects of the present invention.
  • anionic surfactants include fatty acid salts, polysulfonates, polycarboxylates, alkyl sulfate ester salts, alkylarylsulfonates, alkylnaphthalenesulfonates, dialkylsulfonates, and dialkylsulfosuccinates.
  • alkyl phosphate alkyl phosphate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate sulfonate, glycerol borate fatty acid ester, polyoxyethylene glycerol
  • fatty acid esters include sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, ammonium polyoxyethylene lauryl ether sulfate, polyoxyethylene nonylphenyl ether sulfate, ⁇ - Sodium salts of naphthalenesulfonic acid formalin condensates may be mentioned. Only one kind of anionic surfactant may be used, or two or more kinds thereof may be used.
  • the amount of surfactant used is preferably in the range of 0.01 to 0.3 parts by weight, more preferably 0.02 to 0.2 parts by weight, per 100 parts by weight of the aqueous medium. is within the range of
  • any suitable dispersion stabilizer ( D) may be used.
  • the dispersion stabilizer (D) may be used alone or in combination of two or more.
  • the dispersion stabilizer (D) is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the aqueous medium.
  • the dispersion stabilizer (D) may be used alone or in combination of two or more.
  • dispersion stabilizer (D) examples include inorganic water-soluble polymer compounds such as polyvinyl alcohol, polycarboxylic acid, celluloses (hydroxyethylcellulose, carboxymethylcellulose, etc.), polyvinylpyrrolidone, and sodium tripolyphosphate.
  • inorganic water-soluble polymer compounds such as polyvinyl alcohol, polycarboxylic acid, celluloses (hydroxyethylcellulose, carboxymethylcellulose, etc.), polyvinylpyrrolidone, and sodium tripolyphosphate.
  • Dispersion stabilizers include phosphates such as calcium phosphate, magnesium phosphate, aluminum phosphate and zinc phosphate; pyrophosphates such as calcium pyrophosphate, magnesium pyrophosphate, aluminum pyrophosphate and zinc pyrophosphate; calcium carbonate; poorly water-soluble inorganic compounds such as magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, and colloidal silica; Among these, magnesium pyrophosphate is preferable because it is relatively easy to remove from the hollow resin particles and hardly remains on the surface of the hollow resin particles.
  • Another preferred embodiment 2 of the polymer (P) is a polymer having an ether structure, a phosphate ester structure, and a sulfur element represented by formula (1), preferably represented by formula (1)
  • another preferred embodiment 2 of polymer (P) is a polymer obtained by reacting polymer (AM) with a thiol.
  • the reaction between the polymer (AM) and thiol can be carried out by any appropriate method as long as it is a method generally employed in a reaction known as thiolene reaction, as long as it does not impair the effects of the present invention. It is typically obtained by mixing the polymer (AM), thiol and 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 compound (A) and monomer (M).
  • a reaction mixture typically a suspension
  • any appropriate thiol can be adopted as long as it is a thiol represented by R-SH (R is an alkyl group) as long as it does not impair the effects of the present invention.
  • 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.
  • An alkyl group having a chain more preferably a linear or branched alkyl group having 6 to 12 carbon atoms, particularly preferably a linear alkyl group having 8 to 10 carbon atoms or an alkyl group having a branched chain. Only one kind of thiol may be used, or two or more kinds thereof may be used.
  • a thiolene reaction occurs between the vinyl group of the polymer (AM) and the thiol, and at least part of the vinyl group is converted to an alkylthio group.
  • heat generation due to thermal decomposition for example, thermal decomposition under the manufacturing process temperature of a semiconductor member of about 200 to 300° C.
  • excellent heat resistance can be exhibited.
  • by reducing the residual vinyl groups in the hollow resin particles it is possible not only to contribute to the improvement of heat resistance, but also to achieve a lower dielectric constant and a lower dielectric loss tangent.
  • Hollow resin particles according to embodiments of the present invention can be employed in various applications.
  • the hollow resin particles according to the embodiments of the present invention are suitable for semiconductor members, and typically can be suitably used for resin compositions for semiconductor members, in that the effects of the present invention can be utilized more effectively.
  • the hollow resin particles according to the embodiment of the present invention can be used in coating compositions, cosmetics, paper coating compositions, heat insulating compositions (e.g., heat insulating (light-diffusing resin composition), light-diffusing composition (for example, light-diffusing resin composition), light-diffusing film, and the like.
  • the hollow resin particles according to the embodiment of the present invention can achieve a low dielectric constant and a low dielectric loss tangent, and can exhibit excellent heat resistance, so that they can be suitably used for a resin composition for semiconductor members.
  • a resin composition for semiconductor members according to an embodiment of the present invention contains hollow resin particles according to an embodiment of the present invention.
  • a semiconductor member means a member that constitutes a semiconductor, and includes, for example, a semiconductor package and a semiconductor module.
  • the resin composition for semiconductor members means a resin composition used for semiconductor members.
  • a semiconductor package includes an IC chip as an essential component, a mold resin, an underfill material, a mold underfill material, a die bonding material, a prepreg for semiconductor package substrates, a metal-clad laminate for semiconductor package substrates, and a printed circuit substrate for semiconductor packages. is constructed using at least one member selected from the build-up materials of
  • a semiconductor module is a semiconductor package as an essential component, and includes prepreg 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 printed It is constructed using at least one member selected from adhesive sheets for circuit boards.
  • the hollow resin particles according to the embodiment of the present invention can impart an excellent appearance to coating films containing the hollow resin particles, and thus can be suitably used in coating compositions.
  • a coating composition according to an embodiment of the present invention contains hollow resin particles according to an embodiment of the present invention.
  • the coating composition according to the embodiment of the present invention preferably contains at least one selected from binder resins and UV curable resins. Only one kind of binder resin may be used, or two or more kinds thereof may be used. Only one kind of UV curable resin may be used, or two or more kinds thereof may be used.
  • binder resin any appropriate binder resin can be adopted as the binder resin as long as it does not impair the effects of the present invention.
  • binder resins include, for example, organic solvent- or water-soluble resins, and emulsion-type water-based 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.
  • UV curable resins include, for example, polyfunctional (meth)acrylate resins and polyfunctional urethane acrylate resins. Polyfunctional (meth)acrylate resins are preferred, and 3 or more (meth) Polyfunctional (meth)acrylate resins having acryloyl groups are more preferred.
  • polyfunctional (meth)acrylate resins having 3 or more (meth)acryloyl groups in one molecule include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, 1,2,4-cyclohexanetetra(meth)acrylate, pentaglycerol triacrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetra (Meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol triacrylate, and tripentaerythritol hexaacrylate.
  • the coating composition according to the embodiment of the present invention contains at least one selected from binder resins and UV-curable resins
  • any appropriate content can be adopted as the content according to the purpose.
  • the hollow resin particles according to embodiments of the invention are preferably 5 wt% to 50 wt%, more preferably 10 wt% to 50 wt%, even more preferably 20 wt% to 40 wt%.
  • a photopolymerization initiator is preferably used together.
  • the photopolymerization initiator any appropriate photopolymerization initiator can be adopted as long as the effects of the present invention are not impaired.
  • photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, ⁇ -hydroxyalkylphenones, ⁇ -aminoalkylphenones, anthraquinones, thioxanthones, azo compounds, Peroxides (described in JP-A-2001-139663, etc.), 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, onium salts, borate salts, active halogen compounds, and ⁇ -acyl oxime esters.
  • a coating composition according to an embodiment of the present invention may contain a solvent. Only one kind of solvent may be used, or two or more kinds thereof may be used. When the coating composition according to the embodiment of the present invention contains a solvent, any appropriate content can be adopted as the content according to the purpose.
  • any appropriate solvent can be used as the solvent as long as it does not impair the effects of the present invention.
  • a solvent is preferably a solvent capable of dissolving or dispersing the binder resin or the UV-curable resin.
  • solvents for oil-based paints include hydrocarbon solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; Ether-based solvents such as ethylene glycol diethyl ether and ethylene glycol monobutyl ether; and water-based paints include, for example, water and alcohols.
  • the coating composition according to the embodiment of the present invention may be diluted in order to adjust the viscosity as necessary.
  • Any appropriate diluent can be employed as the diluent depending on the purpose. Examples of such diluents include the solvents described above. Only one type of diluent may be used, or two or more types may be used.
  • the coating composition according to the embodiment of the present invention may optionally contain other components such as coating surface modifiers, fluidity modifiers, UV absorbers, light stabilizers, curing catalysts, extender pigments, coloring pigments, metals, Pigments, mica powder pigments and dyes may be included.
  • coating surface modifiers such as coating surface modifiers, fluidity modifiers, UV absorbers, light stabilizers, curing catalysts, extender pigments, coloring pigments, metals, Pigments, mica powder pigments and dyes may be included.
  • any appropriate coating method can be adopted as the coating method depending on the purpose.
  • coating methods include spray coating, roll coating, brush coating, coating reverse roll coating, gravure coating, die coating, comma coating, and spray coating.
  • any suitable formation method can be adopted as the formation method depending on the purpose.
  • a forming method for example, a coating film is prepared by coating on any coating surface of the base material, the coating film is dried, and then the coating film is cured as necessary.
  • a method of forming a coating film is mentioned by.
  • base materials include metal, wood, glass, and plastics (PET (polyethylene terephthalate), PC (polycarbonate), acrylic resin, TAC (triacetylcellulose), etc.).
  • the hollow resin particles according to the embodiment of the present invention can impart excellent heat insulating properties to a coating film containing the hollow resin particles, they can be suitably used for a heat insulating resin composition.
  • a coating film containing hollow resin particles according to an embodiment of the present invention can exhibit excellent reflectance in a wavelength range from ultraviolet light to near-infrared light.
  • a heat insulating resin composition according to an embodiment of the present invention contains hollow resin particles according to an embodiment of the present invention.
  • the heat insulating resin composition according to the embodiment of the present invention preferably contains at least one selected from binder resins and UV curable resins.
  • binder resin and the UV-curable resin the above description of the coating composition can be used.
  • the heat insulating resin composition according to the embodiment of the present invention may contain a solvent.
  • the solvent the above description of the coating composition can be used.
  • the heat insulating resin composition according to the embodiment of the present invention may be diluted in order to adjust the viscosity as necessary.
  • the diluent the description of the coating composition described above can be used.
  • the heat-insulating resin composition according to the embodiment of the present invention may optionally contain other components such as coating surface conditioners, fluidity modifiers, ultraviolet absorbers, light stabilizers, curing catalysts, extender pigments, and color pigments. , metallic pigments, mica powder pigments, and dyes.
  • the above description of the coating composition can be used.
  • 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 thus can be suitably used in a light diffusing resin composition.
  • a light diffusing resin composition according to an embodiment of the present invention contains hollow resin particles according to an embodiment of the present invention.
  • the light diffusing resin composition according to the embodiment of the present invention preferably contains at least one selected from binder resins and UV curable resins.
  • binder resin and the UV-curable resin the above description of the coating composition can be used.
  • the light diffusing resin composition according to the embodiment of the present invention may contain a solvent.
  • the solvent the above description of the coating composition can be used.
  • the light diffusing resin composition according to the embodiment of the present invention may be diluted in order to adjust the viscosity as necessary.
  • the description of the coating composition described above can be used.
  • the light diffusing resin composition according to the embodiment of the present invention may optionally contain other components such as coating surface modifiers, fluidity modifiers, UV absorbers, light stabilizers, curing catalysts, extender pigments, and colorants. Pigments, metallic pigments, mica powder pigments and dyes may be included.
  • the above-described description of the coating composition can be used.
  • the hollow resin particles according to the embodiment of the present invention can impart excellent light diffusibility to a film provided with a coating film containing the hollow resin particles, they can also be suitably used for a light diffusion film.
  • a light diffusion film according to an embodiment of the present invention contains hollow resin particles according to an embodiment of the present invention.
  • a light diffusion film according to an embodiment of the present invention includes a light diffusion layer formed from a 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 diffusing film according to the embodiment of the present invention may contain other suitable layers depending on the purpose. Such other layers include, for example, 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, a primer layer.
  • base materials include metals, wood, glass, plastic films, plastic sheets, plastic lenses, plastic panels, cathode ray tubes, fluorescent display tubes, and liquid crystal display panels.
  • plastics constituting plastic films, plastic sheets, plastic lenses, and plastic panels include PET (polyethylene terephthalate), PC (polycarbonate), acrylic resins, and TAC (triacetylcellulose).
  • Embodiment 1 of production method 20 parts by weight to 80 parts by weight of compound (A) having an ether structure and a radical reactive group represented by formula (1) and a monomer (M ) 80 parts by weight to 20 parts by weight (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 to obtain the monomer (M) contains a compound (B) having a phosphate ester structure and a radically reactive group.
  • Embodiment 2 of production method 20 parts by weight to 80 parts by weight of compound (A) having an ether structure and a radical reactive group represented by formula (1) and a monomer (M )
  • An oil phase preparation step (I ) a suspension polymerization step (II) in which a suspension is prepared by adding the oil phase to an aqueous phase containing an aqueous medium and stirring, and a thiol is added to the suspension and reacted to react and a thiolene reaction step (III) to prepare the product.
  • the hollow resin particles according to the embodiment of the present invention can be easily manufactured.
  • One preferred embodiment 1 of the method for producing hollow resin particles of the present invention comprises 20 to 80 parts by weight of a compound (A) having an ether structure and a radical reactive group represented by formula (1) and the compound ( 80 parts by weight to 20 parts by weight of the monomer (M) that reacts with A) (the total amount of the compound (A) and the monomer (M) is 100 parts by weight) in the presence of a non-reactive solvent in an aqueous medium
  • the reacted monomer (M) contains a compound (B) having a phosphate ester structure and a radical reactive group.
  • the hollow resin particles have a shell portion and a hollow portion surrounded by the shell portion, wherein the shell portion has an ether structure represented by formula (1) and Hollow resin particles containing a polymer (P) having a phosphate ester structure are obtained, and preferably the polymer (P) is a compound (A ) and 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.
  • the hollow resin particles according to the embodiment of the present invention can be obtained by reacting the compound (A) and the monomer (M) in an aqueous medium in the presence of a non-reactive solvent.
  • hollow resin particles according to embodiments of the present invention can be produced by subjecting compound (A) and monomer (M) to a suspension polymerization reaction.
  • Suspension polymerization is typically suspension polymerization using an aqueous phase containing an aqueous medium and an oil phase containing the compound (A), the monomer (M) and a non-reactive solvent.
  • An oil phase containing the compound (A), the monomer (M) and a non-reactive solvent is added to an aqueous phase containing a medium, dispersed, and heated to carry out suspension polymerization.
  • any appropriate dispersion method can be adopted as long as it does not impair the effects of the present invention.
  • a dispersion method is typically a dispersion method using a homomixer or a homogenizer, such as a polytron homogenizer, an ultrasonic homogenizer, or a high-pressure homogenizer.
  • Any appropriate polymerization temperature can be adopted as long as the polymerization temperature is suitable for suspension polymerization, as long as it does not impair the effects of the present invention.
  • Such a polymerization temperature is preferably 30°C to 80°C.
  • any appropriate polymerization time can be adopted as long as it does not impair the effects of the present invention.
  • Such polymerization time is preferably 1 hour to 48 hours.
  • Post-heating which is preferably performed after polymerization, is a suitable treatment for obtaining hollow resin particles with a high degree of perfection.
  • any appropriate temperature can be adopted as the temperature of the post-heating that is preferably performed after polymerization within the range that does not impair the effects of the present invention.
  • the temperature for such post-heating is preferably 70°C to 120°C.
  • the post-heating time which is preferably performed after polymerization, within a range that does not impair the effects of the present invention.
  • the time for such post-heating is preferably 1 hour to 24 hours.
  • aqueous media examples include water and mixed media of water and lower alcohols (methanol, ethanol, etc.).
  • any appropriate amount can be adopted as the amount of the aqueous medium used as long as the effects of the present invention are not impaired.
  • the amount of such an aqueous medium to be 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 it. It is preferably 100 to 5,000 parts by weight, more preferably 150 to 2,000 parts by weight with respect to 100 parts by weight of the total amount of (M) and the non-reactive solvent.
  • the non-reactive solvent is a solvent that does not chemically react with both the compound (A) and the monomer (M), preferably an organic solvent.
  • a non-reactive solvent typically acts as a hollowing agent to provide voids in the particles.
  • Non-reactive solvents include, for example, heptane, hexane, toluene, cyclohexane, methyl acetate, ethyl acetate, methyl ethyl ketone, chloroform, carbon tetrachloride.
  • the boiling point of the non-reactive solvent is preferably less than 100° C. in terms of ease of removal from the hollow resin particles.
  • the non-reactive solvent as the hollowing agent may be a single solvent or a mixed solvent.
  • the amount of the non-reactive solvent added is preferably 20 to 250 parts by weight with respect to 100 parts by weight of the total amount of the compound (A) and the monomer (M).
  • any suitable additive (C ) may be used.
  • Additives (C) may be used alone or in combination of two or more.
  • the additive (C) as used herein does not include an aqueous medium, a solvent such as a non-reactive solvent, or a dispersion stabilizer.
  • the content of additive (C) is preferably 0% to 40% by weight, more preferably 0% to 30% by weight, relative to the total amount of compound (A) and monomer (M). more preferably 0 wt % to 20 wt %, particularly preferably 0 wt % to 10 wt %.
  • additive (C) any appropriate additive that does not correspond to either the compound (A) or the monomer (M) can be adopted as long as it does not impair the effects of the present invention.
  • additives (C) include non-crosslinkable polymers and polymerization initiators.
  • non-crosslinkable polymers ⁇ 1. ⁇ 1-2.
  • the description in the item of shell part>> can be used as it is.
  • any appropriate polymerization initiator can be used as the polymerization initiator as long as the effects of the present invention are not impaired.
  • examples of such polymerization initiators include lauroyl peroxide, benzoyl peroxide, orthochlorobenzoyl peroxide, orthomethoxy benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, t-butylperoxy-2- Organic peroxides such as ethylhexanoate and di-t-butyl peroxide; , 4-dimethylvaleronitrile) and other azo compounds;
  • the content of the polymerization initiator is preferably in the range of 0.1% by weight to 5% by weight with respect to the total amount of the compound (A) and the monomer (M). Only one polymerization initiator may be used, or two or more polymerization initiators may be used.
  • any suitable dispersion stabilizer ( D) may be used.
  • the dispersion stabilizer (D) may be used alone or in combination of two or more.
  • the dispersion stabilizer (D) is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the aqueous medium.
  • the dispersion stabilizer (D) may be used alone or in combination of two or more.
  • dispersion stabilizer (D) examples include ⁇ 1. ⁇ 1-2.
  • the description in the item of shell part>> can be used as it is.
  • Another preferred embodiment 2 of the method for producing hollow resin particles of the present invention comprises 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 parts by weight to 20 parts by weight of the monomer (M) that reacts with the compound (A) (the total amount of the compound (A) and the monomer (M) is 100 parts by weight) is mixed with a non-reactive solvent to obtain an oil.
  • An oil phase preparation step (I) for preparing a phase a suspension polymerization step (II) for preparing a suspension by adding the oil phase to an aqueous phase containing an aqueous medium and stirring, and the suspension and a thiolene reaction step (III) in which a thiol is added to and reacted to prepare a reactant.
  • hollow resin particles having a shell portion and a hollow portion surrounded by the shell portion, wherein the shell portion has an ether structure represented by formula (1) Hollow resin particles containing a phosphate ester structure and a polymer (P) having a sulfur element are obtained, preferably the polymer (P) has an ether structure represented by the formula (1) and a radical reactive group.
  • oil phase preparation step (I) 20 parts by weight to 80 parts by weight of the compound (A) and 80 parts by weight to 20 parts by weight of the monomer (M) (the total amount of the compound (A) and the monomer (M) is 100 parts by weight ) is mixed with a non-reactive solvent to prepare the oil phase.
  • the ratio of the compound (A) and the monomer (M) is the weight part ratio (compound (A):monomer (M)) when the total amount of the compound (A) and the monomer (M) is 100 parts by weight. , preferably (20 to 80 parts by weight): (80 to 20 parts by weight), more preferably (20 to 70 parts by weight): (80 to 30 parts by weight), More preferably (25 to 60 parts by weight): (75 to 40 parts by weight), particularly preferably (30 to 50 parts by weight): (70 to 50 parts by weight). If the content of the compound (A) is too small outside the above range, the heat resistance may be insufficient. If the content of the compound (A) is too large outside the above range, it may be difficult to form the shell and the hollow portion surrounded by the shell.
  • the non-reactive solvent is a solvent that does not chemically react with both the compound (A) and the monomer (M), preferably an organic solvent.
  • a non-reactive solvent typically acts as a hollowing agent to provide voids in the particles.
  • Non-reactive solvents include, for example, heptane, hexane, toluene, cyclohexane, methyl acetate, ethyl acetate, methyl ethyl ketone, chloroform, carbon tetrachloride.
  • the boiling point of the non-reactive solvent is preferably less than 100° C. in terms of ease of removal from the hollow resin particles.
  • the non-reactive solvent as the hollowing agent may be a single solvent or a mixed solvent.
  • the amount of the non-reactive solvent added is preferably 20 to 250 parts by weight with respect to 100 parts by weight of the total amount of the compound (A) and the monomer (M).
  • any suitable additive (C ) may be used.
  • Additives (C) may be used alone or in combination of two or more.
  • the additive (C) as used herein does not include an aqueous medium, a solvent such as a non-reactive solvent, or a dispersion stabilizer.
  • the content of additive (C) is preferably 0% to 40% by weight, more preferably 0% to 30% by weight, relative to the total amount of compound (A) and monomer (M). more preferably 0 wt % to 20 wt %, particularly preferably 0 wt % to 10 wt %.
  • additive (C) any appropriate additive that does not correspond to either the compound (A) or the monomer (M) can be adopted as long as it does not impair the effects of the present invention.
  • additives (C) include non-crosslinkable polymers and polymerization initiators.
  • non-crosslinkable polymers ⁇ 1. ⁇ 1-2.
  • the description in the item of shell part>> can be used as it is.
  • any appropriate polymerization initiator can be used as the polymerization initiator as long as the effects of the present invention are not impaired.
  • examples of such polymerization initiators include lauroyl peroxide, benzoyl peroxide, orthochlorobenzoyl peroxide, orthomethoxy benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, t-butylperoxy-2- Organic peroxides such as ethylhexanoate and di-t-butyl peroxide; , 4-dimethylvaleronitrile) and other azo compounds;
  • the content of the polymerization initiator is preferably in the range of 0.1% by weight to 5% by weight with respect to the total amount of the compound (A) and the monomer (M). Only one polymerization initiator may be used, or two or more polymerization initiators may be used.
  • a suspension is prepared by adding the oil phase obtained in the oil phase preparation step (I) to the aqueous phase containing the aqueous medium and stirring.
  • aqueous media examples include water and mixed media of water and lower alcohols (methanol, ethanol, etc.).
  • any appropriate amount can be adopted as the amount of the aqueous medium used as long as the effects of the present invention are not impaired.
  • the amount of such an aqueous medium to be 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 it. It is preferably 100 to 5,000 parts by weight, more preferably 150 to 2,000 parts by weight, based on 100 parts by weight of the total amount of the monomer (M) and the non-reactive solvent.
  • any suitable dispersion stabilizer that does not correspond to either the compound (A) or the monomer (M) is added to the aqueous phase containing the aqueous medium as long as the effects of the present invention are not impaired.
  • (D) may be included.
  • the dispersion stabilizer (D) may be used alone or in combination of two or more.
  • the dispersion stabilizer (D) is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the aqueous medium.
  • dispersion stabilizer (D) examples include ⁇ 1. ⁇ 1-2.
  • the description in the item of shell part>> can be used as it is.
  • any appropriate dispersion method can be adopted as long as it does not impair the effects of the present invention.
  • a dispersion method is typically a dispersion method using a homomixer or a homogenizer, such as a polytron homogenizer, an ultrasonic homogenizer, or a high-pressure homogenizer.
  • Any appropriate polymerization temperature can be adopted as long as the polymerization temperature is suitable for suspension polymerization, as long as it does not impair the effects of the present invention.
  • Such a polymerization temperature is preferably 30°C to 80°C.
  • any appropriate polymerization time can be adopted as long as it does not impair the effects of the present invention.
  • Such polymerization time is preferably 1 hour to 48 hours.
  • Post-heating may be performed after polymerization. Hollow resin particles with a higher degree of perfection can be obtained by post-heating after the polymerization. Any appropriate temperature can be adopted as the post-heating temperature within a range that does not impair the effects of the present invention.
  • the temperature for such post-heating is preferably 70°C to 120°C.
  • the time for such post-heating is preferably 1 hour to 24 hours.
  • Post-heating may be performed in the following thiolene reaction step (III).
  • the suspension obtained contains the polymer (AM) obtained by the reaction of the compound (A) and the monomer (M).
  • thiol is added to the suspension obtained in the suspension polymerization step (II) and reacted to prepare a reaction product.
  • 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 thiol.
  • the thiol-ene reaction between the polymer (AM) and thiol can be carried out by any appropriate method as long as it is a method generally employed in a reaction known as thiol-ene reaction, as long as the effects of the present invention are not impaired. . It is typically obtained by mixing the polymer (AM), thiol and initiator radical species, heating and stirring.
  • a polymerization initiator may be used in the thiolene reaction step (III) for the purpose of promoting the reaction.
  • polymerization initiators include azo polymerization initiators such as 2,2′-azobis-2,4-dimethylvaleronitrile and 2,2′-azobisisobutyronitrile; peroxide-based polymerization initiators such as lauroyl oxide, octanoyl peroxide, methyl ethyl ketone peroxide, propyl peroxydicarbonate, cumene hydroperoxide, t-butyl hydroperoxide; Only one kind of these polymerization initiators may be used, or two or more kinds thereof may be used.
  • the temperature for such heating is preferably a temperature at which 99% or more of the polymerization initiator used is decomposed.
  • heating time in the thiolene reaction step (III) is preferably a time during which the polymerization initiator used is decomposed by 99% or more.
  • a thiolene reaction occurs between the vinyl group of the polymer (AM) and the thiol, and at least part of the vinyl group is converted to an alkylthio group.
  • heat generation due to thermal decomposition for example, thermal decomposition under the manufacturing process temperature of a semiconductor member of about 200 to 300° C.
  • excellent heat resistance can be exhibited.
  • by reducing the residual vinyl groups in the hollow resin particles it is possible not only to contribute to the improvement of heat resistance, but also to achieve a lower dielectric constant and a lower dielectric loss tangent.
  • the method for producing hollow resin particles according to the embodiment of the present invention includes the oil phase preparation step (I), the suspension polymerization step (II), and the thiolene reaction step (III), the effects of the present invention are not impaired. and may include any other suitable steps. Such other steps include, for example, washing steps.
  • Parts means “parts by weight” and “%” means “% by weight” unless otherwise specified.
  • the volume average particle diameter of particles was measured by the Coulter method as follows.
  • the volume average particle diameter of the particles was measured by Coulter Multisizer (registered trademark) 3 (measurement device manufactured by Beckman Coulter, Inc.). Measurements were performed with an aperture calibrated according to the Multisizer® 3 User's Manual published by Beckman Coulter, Inc.
  • the aperture used for measurement when the assumed volume average particle diameter of the particles to be measured is 1 ⁇ m or more and 10 ⁇ m or less, an aperture having a size of 50 ⁇ m is selected, and the assumed volume average particle diameter of the particles to be measured is larger than 10 ⁇ m.
  • An aperture having a size of 400 ⁇ m is selected when the diameter is greater than 90 ⁇ m and 150 ⁇ m or less.
  • Variation coefficient of particle diameter of particles (%) (standard deviation of volume-based particle size distribution of particles / volume average particle diameter of particles) x 100 (%)
  • ⁇ Measurement of 5% weight loss temperature when temperature is increased at 10°C/min under 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 thermogravimetric simultaneous measurement device manufactured by SII Nanotechnology Co., Ltd.
  • the sampling method and temperature conditions were as follows. 10.5 ⁇ 0.5 mg of a sample was filled in the bottom of a platinum measuring container without leaving any gaps to obtain a sample for measurement. Under a nitrogen gas flow rate of 230 mL/min, the 5% weight loss temperature was measured using alumina as a reference material.
  • a TG/DTA curve was obtained by heating the sample from 30°C to 500°C at a heating rate of 10°C/min. From this obtained curve, the temperature at which the weight was reduced by 5% was calculated using analysis software attached to the apparatus, and the temperature was defined as the 5% weight reduction temperature.
  • the 5% weight loss temperature was obtained from the TG curve obtained at a nitrogen gas flow rate of 300 mL/min using analysis software attached to the apparatus. Specifically, the temperature at which the sample weight decreased by 5% relative to the sample weight at the start of measurement was taken as the 5% weight loss temperature.
  • the exothermic start temperature was obtained from the DSC curve obtained with an air gas flow rate of 200 mL/min and a nitrogen gas flow rate of 100 mL/min as a protective gas using analysis software attached to the apparatus. Specifically, the intersection point between the baseline on the low temperature side and the tangent line at the point where the slope at the rise of the exothermic peak in the DSC curve is maximum was determined. The temperature at this intersection point was taken as the exothermic start temperature. However, when there were multiple exothermic peaks, the peak on the lowest temperature side was used.
  • the elemental phosphorus content and the elemental magnesium content were measured using a multi-type ICP emission spectrometer (manufactured by Shimadzu Corporation, "ICPE-9000"). About 1.0 g of particles was accurately weighed, and the accurately weighed particles were incinerated by heating at 450° C. for 3 hours using an electric furnace (muffle furnace “STR-15K” manufactured by Isuzu Co., Ltd.). The incinerated particles were dissolved in 2 ml of concentrated hydrochloric acid and diluted to 50 ml with distilled water to obtain a measurement sample.
  • the measurement sample was measured by the multi-type ICP emission spectrometer under the following measurement conditions to obtain the peak intensity of each element (Mg, P) at the wavelength. Then, from the peak intensity of the wavelength of each element (Mg, P) obtained, based on the calibration curve for quantification created by the following calibration curve creation method, the concentration ( ⁇ g /ml) was calculated. Then, the calculated concentration Tc ( ⁇ g/ml) of each element (Mg, P) and the weight W (g) of the precisely weighed particles are substituted into the following formula to calculate the amount of each element in the particles. did.
  • Amount of element ( ⁇ g/g) (Tc ( ⁇ g/ml)/W (g)) ⁇ 50 (ml) ⁇ Measurement conditions> Measurement wavelength: Mg (285.213 nm), P (177.499 nm) Observation direction: axial direction High frequency output: 1.20 kW Carrier flow rate: 0.7 L/min Plasma flow rate: 10.0 L/min Auxiliary flow rate: 0.6 L/min Exposure time: 30 seconds ⁇ Calibration curve creation method> A standard solution for calibration curve ("XSTC-13 (general-purpose mixed standard solution)" manufactured by SPEX in the United States, element mixture (base 5% HNO 3 ) - about 10 mg/l each) was diluted stepwise with distilled water.
  • XSTC-13 general-purpose mixed standard solution
  • Example weight thickness set ⁇ qualitative element condition> ⁇ S-K ⁇ ⁇ Tube: Rh (30kV-100mA) ⁇ Primary filter: OUT ⁇ Attenuator: 1/1 ⁇ Slit: S4 ⁇ Analysis crystal: GeH ⁇ 2 ⁇ : 110.830 deg (measurement range: 107 deg to 114 deg) ⁇ Detector: PC ⁇ PHA: 150 ⁇ Step: 0.05deg ⁇ Time: 0.15sec
  • the vinyl group amount when all the polymers constituting 1.8 parts by weight of the particles produced in Examples and Comparative Examples are monomers is defined as (B) theoretical total vinyl group amount (mol) of the particles. did.
  • Example 1 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 100 g, divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Materials Co., Ltd.
  • EVB ethyl vinyl benzene
  • heptane 200 g 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator
  • KAYAMER registered trademark
  • PM-21 manufactured by Nippon Kayaku Co., Ltd.
  • the oil phase was added to 1,281 g of a 2% by weight aqueous dispersion of magnesium pyrophosphate as the water phase, and dispersed for 5 minutes at 7,000 rpm using a Polytron homogenizer "PT10-35" (manufactured by Central Scientific Trading Co., Ltd.). to prepare a suspension. After heating the obtained suspension at 55° C. for 5 hours, the internal temperature of the polymerization vessel was raised to 80° C. (secondary temperature rise), and the suspension was stirred at 80° C. for 2 hours to conduct polymerization. The reaction was completed.
  • the obtained particles (1) are a mixture of hollow resin particles (1a) in which the hollow surrounded by the shell has one hollow region and hollow resin particles (1b) in which the hollow surrounded by the shell has a porous structure. It was confirmed that The obtained particles (1) had a volume average particle diameter of 11.3 ⁇ m and a coefficient of variation of 33.3%.
  • the 5% weight loss temperature of the obtained particles (1) was 389° C. when the temperature was raised at 10° C./min in a nitrogen atmosphere. Table 1 shows the blending amount and various measurement results.
  • Example 2 Performed in the same manner as in Example 1, except that the amount of "KAYAMER (registered trademark) PM-21" (manufactured by Nippon Kayaku Co., Ltd.) as a radically polymerizable monomer having a phosphate group was changed to 2.00 g. Particles (2) were obtained. A cross-sectional photographic view of the obtained particles (2) is shown in FIG. It was confirmed that the obtained particles (2) were hollow resin particles (having a porous structure) in which the hollow surrounded by the shell consisted of a plurality of hollow regions. The obtained particles (2) had a volume average particle diameter of 12.7 ⁇ m and a coefficient of variation of 35.2%. The 5% weight loss temperature of the obtained particles (2) was 385° C. when the temperature was raised at 10° C./min in a nitrogen atmosphere. Table 1 shows the blending amount and various measurement results.
  • KAYAMER registered trademark
  • PM-21 manufactured by Nippon Kayaku Co., Ltd.
  • Example 3 The amount of reactive low-molecular-weight polyphenylene ether (trade name “Noryl (registered trademark) SA9000-111 resin”, manufactured by SABIC Co., Ltd.) as a compound having an ether structure was changed to 80 g, and divinylbenzene (DVB) 810 (Japan Particles (3) were obtained in the same manner as in Example 1 except that the amount of ethyl vinyl benzene (EVB) (81% content, 19% is ethyl vinyl benzene (EVB) manufactured by Tetsu Chemical & Material Co., Ltd.) was changed to 120 g. A cross-sectional photograph of the obtained particles (3) is shown in FIG.
  • the obtained particles (3) were hollow resin particles (having a porous structure) in which the hollow surrounded by the shell consisted of a plurality of hollow regions.
  • the obtained particles (3) had a volume average particle diameter of 11.3 ⁇ m and a coefficient of variation of 34.9%.
  • the 5% weight loss temperature of the obtained particles (3) was 414° C. when the temperature was raised at 10° C./min in a nitrogen atmosphere. Table 1 shows the blending amount and various measurement results.
  • Example 4 Reactive low-molecular-weight polyphenylene ether (trade name "Noryl (registered trademark) SA9000-111 resin", manufactured by SABIC Co., Ltd.) as a compound having an ether structure
  • a bifunctional polyphenylene ether oligomer as a compound having an ether structure (trade name “OPE-2St 1200”, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used in the same manner as in Example 3 except that 80 g was used to obtain particles (4).
  • a cross-sectional photographic view of the obtained particles (4) is shown in FIG.
  • the obtained particles (4) were hollow resin particles (having a porous structure) in which the hollow surrounded by the shell consisted of a plurality of hollow regions.
  • the obtained particles (4) had a volume average particle diameter of 9.8 ⁇ m and a coefficient of variation of 42.9%.
  • the 5% weight loss temperature of the obtained particles (4) was 362° C. when the temperature was raised at 10° C./min in a nitrogen atmosphere. Table 1 shows the blending amount and various measurement results.
  • Example 5 The oil phase was added to 1,281 g of a 2% by weight aqueous dispersion of magnesium pyrophosphate as the water phase, and dispersed for 5 minutes at 7,000 rpm using a Polytron homogenizer "PT10-35" (manufactured by Central Scientific Trading Co., Ltd.). Instead of preparing a suspension, an oil phase was added to 1,381 g of a 2.5% by weight aqueous dispersion of magnesium pyrophosphate as the aqueous phase, and a polytron homogenizer "PT10-35" (Central Scientific Trading Co., Ltd.
  • the obtained particles (5) had a volume average particle diameter of 4.2 ⁇ m and a coefficient of variation of 35.3%.
  • the 5% weight loss temperature of the obtained particles (5) was 399° C. when the temperature was raised at 10° C./min in a nitrogen atmosphere. Table 1 shows the blending amount and various measurement results.
  • Example 6 Instead of adding the oil phase to 1,381 g of a 2.5 wt % aqueous dispersion of magnesium pyrophosphate as the aqueous phase, 1,381 g of a 2.5 wt % aqueous dispersion of magnesium pyrophosphate as the aqueous phase and lauryldimethylamino Particles (6) were obtained in the same manner as in Example 5, except that the oil phase was added to a mixture of 0.51 g of betaine acetate (pure content: 35%). A cross-sectional photograph of the obtained particles (6) is shown in FIG.
  • the obtained particles (6) were hollow resin particles (having a porous structure) in which the hollow surrounded by the shell consisted of a plurality of hollow regions.
  • the obtained particles (6) had a volume average particle diameter of 4.5 ⁇ m and a coefficient of variation of 31.1%.
  • the 5% weight loss temperature of the obtained particles (6) was 392° C. when the temperature was raised at 10° C./min in a nitrogen atmosphere. Table 1 shows the blending amount and various measurement results.
  • Example 7 The amount of reactive low-molecular-weight polyphenylene ether (trade name “Noryl (registered trademark) SA9000-111 resin”, manufactured by SABIC Co., Ltd.) as a compound having an ether structure was changed to 60 g, and divinylbenzene (DVB) 810 (Japan Particles (7) were obtained in the same manner as in Example 6, except that the amount of ethyl vinyl benzene (EVB) used was changed to 140 g. A cross-sectional photographic view of the obtained particles (7) is shown in FIG. It was confirmed that the obtained particles (7) were hollow resin particles (having a porous structure) in which the hollow surrounded by the shell consisted of a plurality of hollow regions.
  • Noryl (registered trademark) SA9000-111 resin manufactured by SABIC Co., Ltd.
  • the obtained particles (7) had a volume average particle diameter of 3.8 ⁇ m and a coefficient of variation of 29.4%.
  • the 5% weight loss temperature of the obtained particles (7) was 394° C. when the temperature was raised at 10° C./min in a nitrogen atmosphere. Table 1 shows the blending amount and various measurement results.
  • the oil phase was added to 1,281 g of a 2% by weight aqueous dispersion of magnesium pyrophosphate as the water phase, and dispersed for 5 minutes at 7,000 rpm using a Polytron homogenizer "PT10-35" (manufactured by Central Scientific Trading Co., Ltd.). to prepare a suspension. After heating the obtained suspension at 55° C. for 5 hours, the internal temperature of the polymerization vessel was raised to 80° C. (secondary temperature rise), and the suspension was stirred at 80° C. for 2 hours to conduct polymerization. The reaction was completed.
  • the obtained particles (C1) are composed of hollow resin particles (C1a) in which the hollow surrounded by the shell has one hollow region, and hollow resin particles (C1b) in which the hollow surrounded by the shell has a porous structure. A mixture was confirmed.
  • the obtained particles (C1) had a volume average particle diameter of 7.4 ⁇ m 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 raised at 10° C./min in a nitrogen atmosphere.
  • Example 2 The procedure was carried out in the same manner as in Example 1, except that the amount of "KAYAMER (registered trademark) PM-21" (manufactured by Nippon Kayaku Co., Ltd.) as a radically polymerizable monomer having a phosphate group was changed to 4.00 g. . As a result, the particles were crushed, and hollow resin particles could not be obtained. Table 1 shows the blending amount and various measurement results.
  • KAYAMER registered trademark
  • PM-21 manufactured by Nippon Kayaku Co., Ltd.
  • Example 3 Example except that 1.20 g of lauryl phosphoric acid was used instead of 1.20 g of "KAYAMER (registered trademark) PM-21" (manufactured by Nippon Kayaku Co., Ltd.) as a radically polymerizable monomer having a phosphate group.
  • Particles (C3) were obtained in the same manner as in 1.
  • FIG. 9 shows a cross-sectional photograph of the obtained particles (C3). It was confirmed that the resulting particles (C3) were hollow resin particles (having a porous structure) in which the hollow surrounded by the shell consisted of a plurality of hollow regions.
  • the obtained particles (C3) had a volume average particle diameter of 12.3 ⁇ m and a coefficient of variation of 34.5%.
  • the 5% weight loss temperature of the obtained particles (C3) was 392°C when the temperature was raised at 10°C/min in a nitrogen atmosphere. Table 1 shows the blending amount and various measurement results.
  • Example 8 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, divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Materials Co., Ltd.
  • EVB ethyl vinyl benzene
  • the obtained particles (8) show a cross-sectional photograph of the obtained particles (8). It was confirmed that the obtained particles (8) were hollow resin particles having a hollow structure surrounded by a shell and having a porous structure. The obtained particles (8) had a volume average particle diameter of 3.8 ⁇ m and a coefficient of variation of 28.4%. The 5% weight loss temperature of the obtained particles (8) was 403.3° C. when the temperature was raised at 10° C./min in a nitrogen atmosphere. Table 2 shows the compounding amounts and various measurement results.
  • 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 changed to 7.0 g.
  • FIG. 11 shows a cross-sectional photograph of the obtained particles (9). It was confirmed that the obtained particles (9) were hollow resin particles having a hollow structure surrounded by a shell and having a porous structure. The obtained particles (9) had a volume average particle diameter of 3.4 ⁇ m and a coefficient of variation of 22.7%. The 5% weight loss temperature of the obtained particles (9) was 390.9°C when the temperature was raised at 10°C/min in a nitrogen atmosphere. Table 2 shows the compounding amounts and various measurement results.
  • Example 10 Instead of adding the oil phase to 1214 g of a 2.5 wt % aqueous dispersion of magnesium pyrophosphate as the aqueous phase, 1214 g of a 2.5 wt % aqueous dispersion of magnesium pyrophosphate and betaine lauryldimethylaminoacetate (pure Particles (10) were obtained in the same manner as in Example 9, except that the oil phase was added to 0.51 g of the mixture.
  • FIG. 12 shows a cross-sectional photograph of the obtained particles (10). It was confirmed that the obtained particles (10) were hollow resin particles having a hollow structure surrounded by a shell and having a porous structure.
  • the obtained particles (10) had a volume average particle diameter of 3.8 ⁇ m and a coefficient of variation of 28.1%.
  • the 5% weight loss temperature of the obtained particles (10) was 388.5°C when the temperature was raised at 10°C/min in a nitrogen atmosphere.
  • the obtained particles (10) had an elemental phosphorus content of 230 ⁇ g/g and an elemental magnesium content of 89 ⁇ g/g. Table 2 shows the compounding amounts and various measurement results.
  • 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 changed to 14.0 g.
  • FIG. 13 shows a cross-sectional photograph of the obtained particles (11). It was confirmed that the obtained particles (11) were hollow resin particles having a hollow structure surrounded by a shell and having a porous structure. The obtained particles (11) had a volume average particle diameter of 3.6 ⁇ m and a coefficient of variation of 24.8%. The 5% weight loss temperature of the obtained particles (11) was 299.4°C when the temperature was raised at 10°C/min in a nitrogen atmosphere. Table 2 shows the compounding amounts and various measurement results.
  • 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 Kasei Co., Ltd.) was used as the thiol.
  • FIG. 14 shows a cross-sectional photograph of the obtained particles (12). It was confirmed that the obtained particles (12) were hollow resin particles having a hollow structure surrounded by a shell and having a porous structure. The obtained particles (12) had a volume average particle diameter of 3.5 ⁇ m and a coefficient of variation of 24.9%. The 5% weight loss temperature of the obtained particles (12) was 382.7°C when the temperature was raised at 10°C/min in a nitrogen atmosphere. Table 2 shows the compounding amounts and various measurement results.
  • 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.
  • FIG. 15 shows a cross-sectional photograph of the obtained particles (13). It was confirmed that the obtained particles (13) were hollow resin particles having a hollow structure surrounded by a shell and having a porous structure.
  • the obtained particles (13) had a volume average particle diameter of 3.3 ⁇ m and a coefficient of variation of 24.5%.
  • the 5% weight loss temperature of the obtained particles (13) was 375.9°C when the temperature was raised at 10°C/min in a nitrogen atmosphere. Table 2 shows the compounding amounts and various measurement results.
  • Example 14 After dispersing at 7000 rpm for 2 minutes using a Polytron homogenizer "PT10-35" (manufactured by Central Scientific Trading Co., Ltd.), the resulting suspension was heated at 55 ° C. for 5 hours, and 1-octane as a thiol. Add 7.0 g of thiol into the polymerization vessel, raise the internal temperature of the polymerization vessel to 80° C. (secondary temperature rise), and stir the suspension at 80° C. for 2 hours to complete the polymerization reaction. Particles (14) were obtained in the same manner as in Example 8, except that FIG. 16 shows a cross-sectional photograph of the obtained particles (14).
  • the obtained particles (14) were hollow resin particles having a porous structure in which the hollow surrounded by the shell was formed.
  • the obtained particles (14) had an average particle diameter of 10.3 ⁇ m and a coefficient of variation of 38.9%.
  • the 5% weight loss temperature of the obtained particles (14) was 361.8°C when the temperature was raised at 10°C/min in a nitrogen atmosphere. Table 2 shows the compounding amounts and various measurement results.
  • Example 15 Except for using 56 g of a bifunctional polyphenylene ether oligomer (trade name “OPE-2St 1200”, manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a compound having an ether structure and changing the amount of 1-octanethiol used as a thiol to 7.0 g. was carried out in the same manner as in Example 8 to obtain particles (15).
  • FIG. 17 shows a cross-sectional photograph of the obtained particles (15). It was confirmed that the obtained particles (15) were hollow resin particles having a hollow structure surrounded by a shell and having a porous structure.
  • the obtained particles (15) had a volume average particle diameter of 3.7 ⁇ m and a coefficient of variation of 25.8%.
  • the 5% weight loss temperature of the obtained particles (15) was 339.0° C. when the temperature was raised at 10° C./min in a nitrogen atmosphere. Table 2 shows the compounding amounts and various measurement results.
  • Example 16 Reactive low-molecular-weight polyphenylene ether as a compound having an ether structure (trade name "Noryl (registered trademark) SA9000-111 resin", manufactured by SABIC Corporation) 42 g, divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Materials Co., Ltd. , 81% content product, 19% is ethyl vinyl benzene (EVB)) 98 g, 1-octanethiol 7 g as a thiol was added into the polymerization vessel, and the internal temperature of the polymerization vessel was raised to 80 ° C. (secondary temperature rise ), and the suspension was stirred at 80° C.
  • ether structure trade name "Noryl (registered trademark) SA9000-111 resin", manufactured by SABIC Corporation
  • DVD divinylbenzene
  • EVB ethyl vinyl benzene
  • FIG. 18 shows a cross-sectional photograph of the obtained particles (16). It was confirmed that the obtained particles (16) were hollow resin particles having a porous structure in which the hollow space surrounded by the shell was formed. The obtained particles (16) had a volume average particle diameter of 4.6 ⁇ m and a coefficient of variation of 41.2%. The 5% thermal weight loss temperature of the obtained particles (16) was 392.3° C. when the temperature was raised at 10° C./min in a nitrogen atmosphere. Table 2 shows the compounding amounts and various measurement results.
  • Example 17 Reactive low molecular weight polyphenylene ether as a compound having an ether structure (trade name "Noryl (registered trademark) SA9000-111 resin", manufactured by SABIC Corporation) 84 g, divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Materials Co., Ltd. , 81% content product, 19% is ethyl vinyl benzene (EVB)) 56 g, 1-octanethiol 7 g as thiol was added into the polymerization vessel, and the internal temperature of the polymerization vessel was raised to 80 ° C. (secondary temperature rise ), and the suspension was stirred at 80° C.
  • ether structure trade name "Noryl (registered trademark) SA9000-111 resin", manufactured by SABIC Corporation
  • DVD divinylbenzene
  • EVB ethyl vinyl benzene
  • FIG. 19 shows a cross-sectional photograph of the obtained particles (17). It was confirmed that the obtained particles (17) were hollow resin particles having a single hollow structure surrounded by a shell. The average particle size of the obtained particles (17) was 6.4 ⁇ m. The 5% thermal weight loss temperature of the obtained particles (17) was 354.4° C. when the temperature was raised at 10° C./min in a nitrogen atmosphere. Table 2 shows the compounding amounts and various measurement results.
  • the oil phase was added to 1214 g of a 2.5% by weight aqueous dispersion of magnesium pyrophosphate as the water phase, and dispersed at 7000 rpm for 2 minutes using a Polytron homogenizer "PT10-35" (manufactured by Central Scientific Trading Co., Ltd.). A turbid solution was produced. After heating the obtained suspension at 55°C for 5 hours, the internal temperature of the polymerization vessel was raised to 80°C (secondary temperature rise), and the suspension was stirred at 80°C for 2 hours to effect polymerization. The reaction was completed.
  • Bifunctional polyphenylene ether oligomer (trade name “OPE-2St 1200”, manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a compound having an ether structure 56 g, divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Materials Co., Ltd., containing 81% product, 19% is ethyl vinyl benzene (EVB)) 84 g, heptane 140 g, 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator (trade name "V-65”, Fuji Film Wako Jun Yaku Co., Ltd.) and 0.84 g of “KAYAMER (registered trademark) PM-21” (manufactured by Nippon Kayaku Co., Ltd.) as a radically polymerizable monomer having a phosphoric acid group were mixed to prepare an oil phase.
  • 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 planetarily stirred. A deaerator ("Mazerustar KK-250" manufactured by KURABO Co., Ltd.) was used to defoam and stir to prepare a resin composition (1). After applying the resin composition (1) to a glass plate with a thickness of 5 mm using an applicator set to a wet thickness of 250 ⁇ m, the temperature is 60° C. for 30 minutes, 90° C. for 10 minutes, 150° C. for 30 minutes, and 200° C. After removing the ethyl acetate by heating at rt for 30 minutes, the film (1) was obtained by cooling to room temperature.
  • a deaerator (“Mazerustar KK-250" manufactured by KURABO
  • Example 19 Instead of 0.425 g of the hollow resin particles (particles (1)) obtained in Example 1, 0.425 g of the hollow resin particles (particles (5)) obtained in Example 5 were used. A resin composition (5) and a film (5) were obtained in the same manner as in Example 18. A cross-sectional sample of the film (5) was prepared by a cross-section polisher method using a cross-section preparation device "IB-19500CP" (manufactured by JEOL Ltd.), and a scanning electron microscope "S-3400N” manufactured by Hitachi High-Technologies Corporation was used. and observed the cross section. FIG. 22 shows a photograph of the obtained cross section.
  • the white portion means polyimide
  • the spherical substance observed in the white portion means hollow resin particles.
  • black portions inside the hollow resin particles indicate air layers.
  • the inside of the hollow resin particles is observed to be black, it means that the voids of the hollow resin particles can be maintained in the polyimide film, that is, the resin (polyimide) has penetrated into the inside of the hollow resin particles. means not.
  • the white portion means polyimide
  • the spherical substance observed in the white portion means hollow resin particles.
  • black portions inside the hollow resin particles indicate air layers.
  • the resin (polyimide) partially penetrates into the interior of the hollow resin particles and the voids are reduced. means.
  • the hollow resin particles provided by the present invention have the effect of lowering the relative dielectric constant and dielectric loss tangent of the base material. It turns out that it is effective for the purpose.
  • Example 20 0.425 g of the hollow resin particles obtained in Example 9 (Particles (9)), 8.3 g of ethyl acetate, and 1.7 g of solvent-soluble polyimide KPI-MX300F (manufactured by Kawamura Sangyo Co., Ltd.) were planetarily stirred.
  • a deaerator (“Mazerustar KK-250" manufactured by KURABO Co., Ltd.) was used to defoam and stir to prepare a resin composition (9).
  • the temperature is 60° C. for 30 minutes, 90° C. for 10 minutes, 150° C. for 30 minutes, and 200° C.
  • the film (9) was obtained by cooling to room temperature.
  • Example 20 and Comparative Example 8 were evaluated for dielectric constant and dielectric loss tangent by cavity resonance method (measurement frequency: 5.8 GHz). The measurement result was expressed as a relative percentage (%) with the measured value of the film containing no particles set to 100%. Table 4 shows the results.
  • the hollow resin particles provided by the present invention have the effect of lowering the relative dielectric constant and dielectric loss tangent of the base material. It turns out that it is effective for the purpose.
  • Example 21 2.5 g of the hollow resin particles (particles (6)) obtained in Example 6 were added to 10 g of a commercially available water-based paint (manufactured by Asahipen Co., Ltd., trade name "Aqueous Multipurpose Color Clear”), and a planetary stirring deaerator was used. (manufactured by KURABO, Mazerustar KK-250) was used to degas and stir to obtain a coating composition (6-1).
  • a commercially available water-based paint manufactured by Asahipen Co., Ltd., trade name "Aqueous Multipurpose Color Clear”
  • ⁇ Performance evaluation Evaluation of reflection characteristics of ultraviolet, visible, and near-infrared light ⁇ After coating the coating composition (6-1) obtained in Example 21 on the black side of the hiding rate test paper with an applicator set to a wet thickness of 250 ⁇ m, it was sufficiently dried at room temperature, and a sample plate for evaluation was prepared. got The reflectance of the sample plate to ultraviolet light, visible light, and near-infrared light was evaluated by the following procedure.
  • Example 22 2 parts by weight of the hollow resin particles obtained in Example 6 (Particles (6)) and 20 parts by weight of a commercially available acrylic water-based glossy paint (manufactured by Kanpe Papio, trade name "Super Hit") were added to a planetary A coating composition (6-2) was obtained by mixing for 3 minutes and defoaming for 1 minute using a stirring and defoaming machine (manufactured by KURABO, Mazellstar KK-250). The obtained coating composition (6-2) is applied onto an ABS resin (acrylonitrile-butadiene-styrene resin) plate using a coating device having a blade with a clearance of 75 ⁇ m, and then dried to form a coating film. (6-2) was obtained.
  • a commercially available acrylic water-based glossy paint manufactured by Kanpe Papio, trade name "Super Hit"
  • Example 23 7.5 parts by weight of the hollow resin particles obtained in Example 6 (Particles (6)), 30 parts by weight of an acrylic resin (manufactured by DIC, product name "Acrydic A811"), a cross-linking agent (manufactured by DIC, product name “VM-D”) 10 parts by weight and 50 parts by weight of butyl acetate as a solvent are mixed for 3 minutes using a planetary stirring deaerator (manufactured by KURABO, Mazerustar KK-250) and degassed for 1 minute. , to obtain a light diffusing resin composition (6).
  • an acrylic resin manufactured by DIC, product name "Acrydic A811
  • a cross-linking agent manufactured by DIC, product name "VM-D”
  • butyl acetate as a solvent
  • the resulting light diffusible resin composition (6) was applied onto a PET film having a thickness of 125 ⁇ m using a coating device equipped with a blade having a clearance of 50 ⁇ m, and then dried at 70° C. for 10 minutes. A light diffusion film (6) was obtained.
  • Example 24 2.5 g of the hollow resin particles (particles (9)) obtained in Example 9 were added to 10 g of a commercially available water-based paint (manufactured by Asahipen Co., Ltd., trade name "Aqueous Multipurpose Color Clear”), and a planetary stirring deaerator was used. (manufactured by KURABO, Mazerustar KK-250) was used to degas and stir to obtain a coating composition (9-1).
  • a commercially available water-based paint manufactured by Asahipen Co., Ltd., trade name "Aqueous Multipurpose Color Clear”
  • ⁇ Performance evaluation Evaluation of reflection characteristics of ultraviolet, visible, and near-infrared light ⁇ After coating the coating composition (9-1) obtained in Example 24 on the black side of the hiding rate test paper with an applicator set to a wet thickness of 250 ⁇ m, it was sufficiently dried at room temperature, and a sample plate for evaluation was prepared. got The reflectance of the sample plate to ultraviolet light, visible light, and near-infrared light was evaluated by the following procedure.
  • Example 25 2 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 glossy paint (manufactured by Kanpe Papio Co., Ltd., trade name "Super Hit") were added to a planetary A coating composition (9-2) was obtained by mixing for 3 minutes and defoaming for 1 minute using a stirring and defoaming machine (manufactured by KURABO, Mazerustar KK-250). The resulting coating composition (9-2) is applied onto an ABS resin (acrylonitrile-butadiene-styrene resin) plate using a coating device with a blade having a clearance of 75 ⁇ m, and then dried to form a coating film. (9-2) was obtained.
  • a commercially available acrylic water-based glossy paint manufactured by Kanpe Papio Co., Ltd., trade name "Super Hit"
  • Example 26 7.5 parts by weight of the hollow resin particles obtained in Example 9 (Particles (9)), 30 parts by weight of an acrylic resin (manufactured by DIC, product name "Acrydic A811"), a cross-linking agent (manufactured by DIC, product name “VM-D”) 10 parts by weight and 50 parts by weight of butyl acetate as a solvent are mixed for 3 minutes using a planetary stirring deaerator (manufactured by KURABO, Mazerustar KK-250) and degassed for 1 minute. , to obtain a light diffusing resin composition (9).
  • an acrylic resin manufactured by DIC, product name "Acrydic A811
  • a cross-linking agent manufactured by DIC, product name "VM-D”
  • butyl acetate as a solvent
  • the obtained light diffusible resin composition (9) was applied onto a PET film having a thickness of 125 ⁇ m using a coating device equipped with a blade having a clearance of 50 ⁇ m, and then dried at 70° C. for 10 minutes. A light diffusion film (9) was obtained.
  • the hollow resin particles according to the embodiment of the present invention and the hollow resin particles obtained by the manufacturing method according to the embodiment of the present invention can be used for semiconductor materials and the like.
  • 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 applied, for example, to resin compositions for semiconductor members.

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025023151A1 (ja) * 2023-07-21 2025-01-30 積水化成品工業株式会社 樹脂粒子および半導体部材用樹脂組成物
WO2025182834A1 (ja) * 2024-02-26 2025-09-04 日本ゼオン株式会社 中空粒子およびポリマー組成物
WO2025249179A1 (ja) * 2024-05-27 2025-12-04 日本ゼオン株式会社 光拡散フィルム用重合性単量体組成物、光拡散フィルム及びその製造方法

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000313818A (ja) 1999-03-03 2000-11-14 Jsr Corp 架橋樹脂粒子、有機絶縁材用組成物、有機絶縁材、封止材、および回路基板
JP2001139663A (ja) 1999-11-12 2001-05-22 Daicel Chem Ind Ltd 光学的造形用樹脂組成物、その製造方法及び光学的造形物
JP2006083364A (ja) 2004-08-19 2006-03-30 Mitsubishi Gas Chem Co Inc 硬化性樹脂組成物および硬化性フィルムおよびフィルム
JP4171489B2 (ja) 2003-01-28 2008-10-22 松下電工株式会社 中空粒子を含有する樹脂組成物、同組成物を含むプリプレグおよび積層板
JP4445495B2 (ja) 2006-08-17 2010-04-07 積水化学工業株式会社 多孔質中空ポリマー粒子、多孔質中空ポリマー粒子の製造方法、多孔質セラミックフィルタおよび多孔質セラミックフィルタの製造方法
JP4448930B2 (ja) 2000-09-04 2010-04-14 財団法人新産業創造研究機構 中空高分子微粒子及びその製造法
JP2017160399A (ja) * 2016-03-11 2017-09-14 旭化成株式会社 微少空隙を有するポリフェニレンエーテル紛体と製造方法
WO2018025575A1 (ja) * 2016-08-02 2018-02-08 松本油脂製薬株式会社 樹脂中空粒子及びその利用
JP2018095815A (ja) 2016-12-16 2018-06-21 パナソニックＩｐマネジメント株式会社 熱硬化性樹脂組成物、並びに、それを用いた樹脂ワニス、プリプレグ、樹脂付金属箔、樹脂フィルム、金属張積層板及びプリント配線板
JP6513273B1 (ja) 2018-08-31 2019-05-15 三井化学株式会社 樹脂粒子
WO2019177013A1 (ja) * 2018-03-14 2019-09-19 積水化成品工業株式会社 中空粒子分散体
WO2020054816A1 (ja) * 2018-09-14 2020-03-19 積水化成品工業株式会社 中空重合体粒子及びその製造方法
WO2021112117A1 (ja) * 2019-12-06 2021-06-10 日本ゼオン株式会社 中空粒子の製造方法
JP2021514408A (ja) * 2018-02-21 2021-06-10 ダウ グローバル テクノロジーズ エルエルシー 膨張性ポリマー粒子
WO2022131127A1 (ja) * 2020-12-17 2022-06-23 積水化成品工業株式会社 中空樹脂粒子、その製造方法、およびその用途

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0444549A (ja) 1990-06-08 1992-02-14 Tategu Sogo Shosha Futaba:Kk 構築物の壁面構造
JP5376783B2 (ja) * 2007-09-14 2013-12-25 積水化成品工業株式会社 単中空粒子、その製造方法、樹脂組成物及び光拡散板
CN107848248B (zh) * 2015-08-04 2021-04-27 阿科玛股份有限公司 含官能化外壳的空化胶乳粒子
JP6728334B2 (ja) * 2016-03-22 2020-07-22 積水化成品工業株式会社 中空粒子及びその用途
JP2021062524A (ja) * 2019-10-11 2021-04-22 株式会社リコー 印刷物の製造方法及び印刷物の製造装置

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000313818A (ja) 1999-03-03 2000-11-14 Jsr Corp 架橋樹脂粒子、有機絶縁材用組成物、有機絶縁材、封止材、および回路基板
JP2001139663A (ja) 1999-11-12 2001-05-22 Daicel Chem Ind Ltd 光学的造形用樹脂組成物、その製造方法及び光学的造形物
JP4448930B2 (ja) 2000-09-04 2010-04-14 財団法人新産業創造研究機構 中空高分子微粒子及びその製造法
JP4171489B2 (ja) 2003-01-28 2008-10-22 松下電工株式会社 中空粒子を含有する樹脂組成物、同組成物を含むプリプレグおよび積層板
JP2006083364A (ja) 2004-08-19 2006-03-30 Mitsubishi Gas Chem Co Inc 硬化性樹脂組成物および硬化性フィルムおよびフィルム
JP4445495B2 (ja) 2006-08-17 2010-04-07 積水化学工業株式会社 多孔質中空ポリマー粒子、多孔質中空ポリマー粒子の製造方法、多孔質セラミックフィルタおよび多孔質セラミックフィルタの製造方法
JP2017160399A (ja) * 2016-03-11 2017-09-14 旭化成株式会社 微少空隙を有するポリフェニレンエーテル紛体と製造方法
WO2018025575A1 (ja) * 2016-08-02 2018-02-08 松本油脂製薬株式会社 樹脂中空粒子及びその利用
JP2018095815A (ja) 2016-12-16 2018-06-21 パナソニックＩｐマネジメント株式会社 熱硬化性樹脂組成物、並びに、それを用いた樹脂ワニス、プリプレグ、樹脂付金属箔、樹脂フィルム、金属張積層板及びプリント配線板
JP2021514408A (ja) * 2018-02-21 2021-06-10 ダウ グローバル テクノロジーズ エルエルシー 膨張性ポリマー粒子
WO2019177013A1 (ja) * 2018-03-14 2019-09-19 積水化成品工業株式会社 中空粒子分散体
JP6513273B1 (ja) 2018-08-31 2019-05-15 三井化学株式会社 樹脂粒子
WO2020054816A1 (ja) * 2018-09-14 2020-03-19 積水化成品工業株式会社 中空重合体粒子及びその製造方法
WO2021112117A1 (ja) * 2019-12-06 2021-06-10 日本ゼオン株式会社 中空粒子の製造方法
WO2022131127A1 (ja) * 2020-12-17 2022-06-23 積水化成品工業株式会社 中空樹脂粒子、その製造方法、およびその用途

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4480976A4

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025023151A1 (ja) * 2023-07-21 2025-01-30 積水化成品工業株式会社 樹脂粒子および半導体部材用樹脂組成物
WO2025182834A1 (ja) * 2024-02-26 2025-09-04 日本ゼオン株式会社 中空粒子およびポリマー組成物
WO2025249179A1 (ja) * 2024-05-27 2025-12-04 日本ゼオン株式会社 光拡散フィルム用重合性単量体組成物、光拡散フィルム及びその製造方法

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