WO2023162901A1 - 熱膨張性微小球及びその用途 - Google Patents

熱膨張性微小球及びその用途 Download PDF

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WO2023162901A1
WO2023162901A1 PCT/JP2023/005882 JP2023005882W WO2023162901A1 WO 2023162901 A1 WO2023162901 A1 WO 2023162901A1 JP 2023005882 W JP2023005882 W JP 2023005882W WO 2023162901 A1 WO2023162901 A1 WO 2023162901A1
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Prior art keywords
weight
expandable microspheres
heat
hollow particles
temperature
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English (en)
French (fr)
Japanese (ja)
Inventor
捺央弥 清水
朋哉 宇田
準 竹内
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Matsumoto Yushi Seiyaku Co Ltd
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Matsumoto Yushi Seiyaku Co Ltd
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Priority to JP2023544239A priority Critical patent/JP7369329B1/ja
Priority to SE2450866A priority patent/SE547850C2/en
Priority to KR1020247026586A priority patent/KR20240156360A/ko
Priority to US18/840,157 priority patent/US20250163234A1/en
Priority to CN202380021192.1A priority patent/CN118715302A/zh
Publication of WO2023162901A1 publication Critical patent/WO2023162901A1/ja
Anticipated expiration legal-status Critical
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • 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
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/42—Nitriles
    • C08F120/44—Acrylonitrile
    • 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
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/42—Nitriles
    • C08F20/44—Acrylonitrile
    • 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
    • C08F214/00—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 a halogen
    • C08F214/02—Monomers containing chlorine
    • C08F214/04—Monomers containing two carbon atoms
    • C08F214/08—Vinylidene chloride
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or 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 a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/08—Homopolymers or copolymers of vinylidene chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or 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 a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/16—Homopolymers or copolymers or vinylidene fluoride
    • 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
    • C09D131/00—Coating compositions based on homopolymers or 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 acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
    • C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C09D131/04—Homopolymers or copolymers of vinyl acetate
    • 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
    • C09D133/00—Coating compositions based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/18—Homopolymers or copolymers of nitriles
    • C09D133/20—Homopolymers or copolymers of acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/22—Expandable microspheres, e.g. Expancel®

Definitions

  • the present invention relates to thermally expandable microspheres and uses thereof.
  • Thermally expandable microspheres have a structure in which a thermoplastic resin is used as an outer shell and a foaming agent is enclosed therein.
  • Thermally expandable microspheres are microspheres that are characterized by being expanded by heat treatment. These heat-expandable microspheres are used in a wide range of applications. For example, the heat-expandable microspheres are mixed with a base material and then used for heat processing. During heat processing, the heat-expandable microspheres are expanded by the heat treatment applied during processing, which not only reduces the weight of the processed product, but also imparts design and cushioning properties to the processed product.
  • thermoly expandable microspheres having high expansion performance outer shells made of copolymers of monomers selected from acrylonitrile, methacrylonitrile, acrylic acid esters, and methacrylic acid esters are used. , and those using hydrocarbons such as isobutane and isopentane are exemplified as blowing agents.
  • An object of the present invention is to provide heat-expandable microspheres from which hollow particles can be obtained that can reduce leakage of a foaming agent over time, and uses thereof.
  • the composition contains an outer shell containing a thermoplastic resin obtained by polymerizing a specific polymerizable component, and a foaming agent contained in the outer shell and vaporized by heating.
  • the present invention includes the following ⁇ 1> to ⁇ 8> aspects.
  • ⁇ 1> Thermally expandable microspheres containing an outer shell containing a thermoplastic resin and a foaming agent contained therein and vaporized by heating, wherein the thermoplastic resin comprises vinylidene chloride (A), Thermally expandable microspheres which are a polymer of a polymerizable component containing acrylonitrile (B) and satisfy the following conditions 1 and 2.
  • Condition 1 The weight ratio of the vinylidene chloride (A) and the acrylonitrile (B) in the polymerizable component has the relationship of the following formula (I).
  • Condition 2 a temperature (Td (°C)) at which the DTG value is maximized in a differential thermogravimetric curve (DTG) obtained by thermogravimetric analysis (TGA) when the temperature is raised at 10°C/min in a nitrogen atmosphere;
  • TTG differential thermogravimetric curve
  • Ts (°C) The expansion start temperature (Ts (°C)) has the relationship of the following formula (II). Temperature at which the DTG value is maximized (Td (° C.)) ⁇ Expansion start temperature (Ts (° C.)) ⁇ 30° C.
  • Hollow particles which are expanded bodies of the thermally expandable microspheres according to any one of ⁇ 1> to ⁇ 3>.
  • Fine particle-attached hollow particles comprising the hollow particles according to ⁇ 5> and fine particles attached to the outer surface of the outer shell portion of the hollow particles.
  • the heat-expandable microspheres according to any one of ⁇ 1> to ⁇ 3>, the heat-expandable microspheres with attached microparticles according to ⁇ 4>, the hollow particles according to ⁇ 5>, and ⁇ 6> A composition comprising at least one selected from the fine particle-attached hollow particles described above and a base component.
  • ⁇ 8> A molded article obtained by molding the composition according to ⁇ 7>.
  • the composition of the present invention comprises at least one selected from the above heat-expandable microspheres, the heat-expandable microspheres with fine particles, the hollow particles and the hollow particles with fine particles, and a base component. .
  • the molded article of the present invention is obtained by molding the above composition.
  • the heat-expandable microspheres of the present invention are hollow particles that can reduce leakage of the foaming agent over time.
  • the heat-expandable microspheres of the present invention can start expanding at relatively low temperatures.
  • the fine particle-attached heat-expandable microspheres of the present invention can be obtained as fine particle-attached hollow particles that can reduce leakage of the foaming agent over time.
  • the fine particle-attached heat-expandable microspheres of the present invention can start expanding at a relatively low temperature. Since the hollow particles of the present invention are obtained using the heat-expandable microspheres as raw materials, leakage of the foaming agent over time can be reduced.
  • the fine particle-attached hollow particles of the present invention are obtained using at least one selected from the above heat-expandable microspheres and the above-described fine-particle-attached heat-expandable microspheres as a raw material, leakage of the foaming agent over time can be reduced. Since the composition of the present invention contains at least one selected from the heat-expandable microspheres, the hollow particles, and the fine-particle-attached hollow particles, a lightweight molded article can be obtained. The molded article of the present invention is lightweight.
  • FIG. 1 is a schematic diagram showing an example of thermally expandable microspheres
  • FIG. 1 is a schematic diagram showing an example of microparticle-attached hollow particles
  • FIG. It is a schematic diagram showing an example of fine particle-attached thermally expandable microspheres.
  • the heat-expandable microspheres of the present invention comprise an outer shell containing a thermoplastic resin and a foaming agent contained in the outer shell and vaporized by heating. Thermally expandable microspheres exhibit thermal expansibility as a whole (the property that the entire microsphere expands when heated).
  • the heat-expandable microspheres of the present invention have a core-shell structure composed of an outer shell (shell) 6 and a foaming agent (core) 7, as shown in FIG.
  • the thermoplastic resin forming the outer shell constituting the heat-expandable microspheres of the present invention is a polymer obtained by polymerizing the polymerizable component.
  • the polymerizable component is a component that essentially comprises a monomer component and may contain a cross-linking agent.
  • a monomer component means a monomer having one polymerizable carbon-carbon double bond (hereinafter sometimes simply referred to as a monomer), and is a component capable of addition polymerization.
  • a cross-linking agent means a monomer having at least two polymerizable carbon-carbon double bonds, and is a component that introduces a cross-linking structure into the thermoplastic resin.
  • the polymerizable component includes vinylidene chloride (A) (hereinafter sometimes referred to as monomer (A)) and acrylonitrile (B) (hereinafter sometimes referred to as monomer (B)).
  • the polymerizable component contains vinylidene chloride (A), and can be thermally expandable microspheres with excellent expandability even in a relatively low temperature range.
  • the polymerizable component may contain acrylonitrile (B), and the heat-expandable microspheres may have good heat resistance.
  • the heat-expandable microspheres of the present invention satisfy Condition 1 and Condition 2 below.
  • the thermoplastic resin can have gas barrier properties, elasticity at the time of heat softening, stretchability, and heat resistance.
  • Thermally expandable microspheres expand at a relatively low temperature due to the balance of each performance, and the outer shell of the hollow particles produced by expansion has high gas barrier properties, allowing the blowing agent to permeate to the outside of the outer shell. can be reduced, and the foaming agent retention is excellent.
  • the heat-expandable microspheres of the present invention satisfy Condition 1 below.
  • Condition 1 The weight ratios of vinylidene chloride (A) and acrylonitrile (B) in the polymerizable component have the relationship of the following formula (I). Weight ratio of acrylonitrile (B)/weight ratio of vinylidene chloride (A)>1 Formula (I)
  • condition 1 if the monomer (A) and the monomer (B) do not satisfy the above formula (I), that is, "weight ratio of monomer (B) / weight ratio of monomer (A) ( (B)/(A)) ⁇ 1”, the random polymerization of the monomers (A) and (B) in the polymer does not proceed at an appropriate rate, resulting in expansion and production. It is thought that the gas barrier properties of the outer shell of the hollow particles are low, the retention of the foaming agent is reduced, the foaming agent leaks over time, and the expandability at low temperatures is also reduced.
  • the upper limit of (B)/(A) is preferably in the order of (1) 10, (2) 7, (3) 5, (4) 4.5, and (5) 2 (the larger the number in parentheses, the preferable).
  • the lower limit of (B)/(A) is in the order of (1) 1.05, (2) 1.1, (3) 1.14, (4) 1.2, and (5) 1.4 is preferable (the larger the number in parentheses, the more preferable).
  • the ratio (B)/(A) is, for example, preferably greater than 1 to 10, more preferably 1.2 to 4.5, and particularly preferably 1.4 to 2.
  • the weight ratio of the monomer (A) in the polymerizable component is not particularly limited as long as it satisfies the condition 1, but is preferably 5 to 49.9% by weight in terms of exhibiting the effects of the present application. .
  • the upper limit of the weight ratio is more preferably 45% by weight, still more preferably 40% by weight, and particularly preferably 35% by weight.
  • the lower limit of the weight ratio is more preferably 15% by weight, still more preferably 20% by weight, and particularly preferably 25% by weight. Furthermore, for example, 15 to 45% by weight is more preferable, and 25 to 35% by weight is particularly preferable.
  • the weight ratio of the monomer (B) in the polymerizable component is not particularly limited as long as it satisfies the above condition 1, but is preferably 20 to 80% by weight from the viewpoint of achieving the effects of the present application.
  • the upper limit of the weight ratio is more preferably 75% by weight, still more preferably 70% by weight, particularly preferably 65% by weight, and most preferably 60% by weight.
  • the lower limit of the weight ratio is more preferably 25% by weight, still more preferably 30% by weight, particularly preferably 35% by weight, and most preferably 40% by weight.
  • 30 to 75% by weight is more preferable, and 40 to 60% by weight is particularly preferable.
  • the total weight ratio of the monomer (A) and the monomer (B) in the polymerizable component is not particularly limited, but is preferably 55 to 99.9% by weight from the viewpoint of achieving the effects of the present application.
  • the upper limit of the weight ratio is more preferably 96% by weight, still more preferably 93% by weight, and particularly preferably 90% by weight.
  • the lower limit of the weight ratio is more preferably 60% by weight, more preferably 65% by weight, still more preferably 70% by weight. Furthermore, for example, 60 to 96% by weight is more preferable, and 70 to 90% by weight is particularly preferable.
  • the polymerizable component is a monomer (C ) (hereinafter sometimes referred to as monomer (C)).
  • the weight ratio of the monomer (C) in the polymerizable component / the weight ratio of the monomer (A) ((C)/(A) ) is preferably 10 to 200 in order to obtain the effect of the present application.
  • the upper limit of (C)/(A) is more preferably 170, still more preferably 140, particularly preferably 110, and most preferably 70.
  • the lower limit of (C)/(A) is more preferably 15, still more preferably 20, particularly preferably 25, and most preferably 30.
  • the ratio (C)/(A) is more preferably 15-110, particularly preferably 30-70.
  • Other monomers (C) include, for example, nitrile monomers other than acrylonitrile such as methacrylonitrile, fumaronitrile and maleonitrile; vinyl halide monomers such as vinyl chloride; and vinylidene halides other than vinylidene chloride.
  • Vinyl ester monomers such as vinyl acetate, vinyl propionate and vinyl butyrate; unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid and cinnamic acid, maleic acid, Unsaturated dicarboxylic acids such as itaconic acid, fumaric acid, citraconic acid, chloromaleic acid, anhydrides of unsaturated dicarboxylic acids, monomethyl maleate, monoethyl maleate, monobutyl maleate, monomethyl fumarate, monoethyl fumarate, itaconic acid Carboxyl group-containing monomers such as unsaturated dicarboxylic acid monoesters such as monomethyl acid, monoethyl itaconate, and monobutyl itaconate; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth)acrylate,
  • Part or all of the carboxyl groups of the carboxyl group-containing monomer may be neutralized during or after polymerization.
  • acrylic acid and methacrylic acid are sometimes collectively referred to as (meth)acrylic acid, and (meth)acryl means acrylic or methacrylic.
  • the polymerizable component may further contain a (meth)acrylate-based monomer as a monomer component. Further containing a (meth)acrylic ester-based monomer is preferable because the expansion ratio of the heat-expandable microspheres is improved.
  • the weight ratio of the (meth)acrylic ester-based monomer in the polymerizable component is not particularly limited. , preferably 0 to 45% by weight. The upper limit of the weight ratio is more preferably 40% by weight, still more preferably 35% by weight, particularly preferably 30% by weight, and most preferably 25% by weight.
  • the lower limit of the weight ratio is more preferably 3% by weight, still more preferably 7% by weight, particularly preferably 10% by weight, and most preferably 13% by weight. Furthermore, for example, 3 to 40% by weight is more preferable, and 13 to 25% by weight is particularly preferable.
  • the (meth)acrylic acid ester-based monomer preferably contains at least one selected from methyl methacrylate, methyl acrylate, ethyl acrylate and butyl acrylate for improving low-temperature expandability, and from methyl methacrylate and methyl acrylate It is more preferable to contain at least one selected type, and it is even more preferable to contain methyl methacrylate.
  • the total weight ratio of methyl methacrylate in the (meth)acrylic acid ester is not particularly limited, but is preferably 0 in terms of production stability. % by weight or more.
  • the upper limit of the weight ratio is more preferably 100% by weight, still more preferably 97% by weight, and particularly preferably 95% by weight.
  • the lower limit of the weight ratio is more preferably 20% by weight, still more preferably 40% by weight.
  • Especially preferred is 60% by weight. Furthermore, for example, 20 to 100% by weight is more preferable, and 60 to 95% by weight is particularly preferable.
  • the weight ratio of methyl acrylate in the (meth)acrylic acid ester is not particularly limited, but is preferably 0% by weight or more in terms of achieving the effects of the present application. is.
  • the upper limit of the weight ratio is more preferably 100% by weight, still more preferably 65% by weight, and particularly preferably 30% by weight.
  • the lower limit of the weight ratio is more preferably 3% by weight, still more preferably 6% by weight.
  • Especially preferred is 9% by weight.
  • 3 to 65% by weight is more preferable, and 9 to 30% by weight is particularly preferable.
  • the polymerizable component may further contain a nitrile-based monomer other than acrylonitrile as a monomer component. Further containing a nitrile-based monomer other than acrylonitrile is preferable because the solvent resistance of the heat-expandable microspheres is improved.
  • the weight ratio of the nitrile-based monomer other than acrylonitrile in the polymerizable component is not particularly limited. ⁇ 35% by weight. The upper limit of the weight ratio is more preferably 30% by weight, still more preferably 25% by weight, and particularly preferably 20% by weight.
  • Nitrile-based monomers other than acrylonitrile preferably contain methacrylonitrile because the expansion ratio of the thermally expandable microspheres can be adjusted.
  • the weight ratio of methacrylonitrile to the nitrile-based monomer other than acrylonitrile is not particularly limited, but is preferably 0 in terms of exhibiting the effects of the present application. % by weight or more.
  • the upper limit of the weight ratio is more preferably 100% by weight, still more preferably 70% by weight, and particularly preferably 40% by weight.
  • the lower limit of the weight ratio is more preferably 5% by weight, still more preferably 10% by weight. Especially preferred is 15% by weight.
  • 5 to 70% by weight is more preferable, and 15 to 40% by weight is particularly preferable.
  • the polymerizable component may further contain a carboxyl group-containing monomer as a monomer component. It is preferable that the polymerizable component further contains a carboxyl group-containing monomer, because the stretchability of the obtained thermoplastic resin during thermal expansion is improved.
  • the weight ratio of the carboxyl group-containing monomer in the polymerizable component is not particularly limited, but is preferably 0 to 25% by weight in terms of exhibiting the effects of the present application. is.
  • the upper limit of the weight ratio is more preferably 22% by weight, still more preferably 19% by weight, and particularly preferably 16% by weight.
  • the lower limit of the weight ratio is more preferably 2% by weight, still more preferably 4% by weight, and particularly preferably 6% by weight.
  • the polymerizable component may further contain a (meth)acrylamide-based monomer as a monomer component. Further containing a (meth)acrylamide-based monomer is preferable because the heat resistance of the resulting thermoplastic resin during thermal expansion is improved.
  • the weight ratio of the (meth)acrylamide-based monomer in the polymerizable component is not particularly limited, but is preferably 0 to 25% by weight.
  • the upper limit of the weight ratio is more preferably 22% by weight, still more preferably 19% by weight, and particularly preferably 16% by weight.
  • the lower limit of the weight ratio is more preferably 2% by weight, still more preferably 4% by weight, and particularly preferably 6% by weight.
  • the polymerizable component may contain a cross-linking agent, as described above.
  • a cross-linking agent in the polymerizable component, the obtained thermally expandable microspheres can be effectively thermally expanded by suppressing a decrease in the retention rate (encapsulation retention rate) of the encapsulated foaming agent during thermal expansion. possible and preferable.
  • the cross-linking agent is not particularly limited, but examples include aromatic divinyl compounds such as divinylbenzene; ethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di( meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 3-methyl-1,5 pentanediol di(meth)acrylate alkanediol di(meth)acrylates such as acrylates and 2-methyl-1,8 octanediol di(meth)acrylate; diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, PEG#200 di(meth) Acrylate (#200 in the compound name represents that the weight average molecular weight of the polyethylene glycol chain portion
  • the weight ratio of the cross-linking agent in the polymerizable component is not particularly limited, but is preferably 0 to 5.0 parts by weight from the viewpoint of improving the expansion ratio of the thermally expandable microcapsules.
  • the upper limit of the weight ratio is more preferably 3.5% by weight, still more preferably 2.0% by weight, and particularly preferably 1.0% by weight.
  • the lower limit of the weight ratio is more preferably 0.04% by weight, still more preferably 0.07% by weight, and particularly preferably 0.1% by weight.
  • condition 2 a temperature (Td (°C)) at which the DTG value is maximized in a differential thermogravimetric curve (DTG) obtained by thermogravimetric analysis (TGA) when the temperature is raised at 10°C/min in a nitrogen atmosphere;
  • TTG differential thermogravimetric curve
  • TGA thermogravimetric analysis
  • Ts (°C) has the relationship of the following formula (II). Temperature at which the DTG value is maximized (Td (° C.)) ⁇ Expansion start temperature (Ts (° C.)) ⁇ 30° C.
  • condition 2 if the temperature (Td (° C.)) at which the DTG value is maximized and the expansion start temperature (Ts (° C.)) do not satisfy the above formula (II), that is, “Td (° C.) ⁇ Ts (° C. ) ⁇ 30° C.”, the orientation of the polymer does not proceed appropriately when the heat-expandable microspheres are thermally expanded and the outer shell is elongated and thinned, so the hollow produced by expansion It is thought that the gas barrier properties of the outer shell of the particles are low, the foaming agent retention is reduced, and the foaming agent leaks out over time.
  • the temperature (Td (° C.)) at which the DTG value becomes maximum and the expansion start temperature (Ts (° C.)) are according to the method described in the examples of the present invention.
  • the lower limit of the numerical value of Td (°C) - Ts (°C) is preferably 33°C, more preferably 36°C, and still more preferably 40°C.
  • the upper limit of the numerical value is preferably 100°C, more preferably 70°C, still more preferably 55°C.
  • the numerical value of Td (°C) - Ts (°C) is, for example, more preferably 30 to 100°C, still more preferably 33 to 70°C, and particularly preferably 40 to 55°C.
  • Td (° C.) ⁇ Ts (° C.) of the condition 2 is, for example, the content of the vinylidene chloride (A) and the acrylonitrile (B) contained in the polymerizable component, the type and content of the cross-linking agent , the type of initiator, and the method of cooling and depressurizing the reaction solution during polymerization.
  • the temperature (Td (°C)) at which the DTG value is maximized is not particularly limited as long as it satisfies Condition 2 above, but is preferably 105 to 250°C in terms of achieving the effects of the present application.
  • the lower limit of the temperature is more preferably 115°C, still more preferably 125°C, and particularly preferably 130°C.
  • the upper limit of the temperature is more preferably 180°C, still more preferably 160°C, and particularly preferably 150°C.
  • the Td (°C) is, for example, more preferably 115 to 180°C, particularly preferably 130 to 150°C.
  • the expansion start temperature (Ts (° C.)) of the thermally expandable microspheres is not particularly limited as long as it satisfies the condition 2 above, but from 75° C. to 75° C. in terms of good low-temperature expandability of the thermally expandable microspheres. 220°C is preferred.
  • the lower limit of the temperature is more preferably 75°C, still more preferably 78°C, particularly preferably 85°C, most preferably 90°C.
  • the upper limit of the temperature is more preferably 200°C, still more preferably 180°C, particularly preferably 160°C, most preferably 150°C.
  • the Ts (°C) is, for example, more preferably 85 to 180°C, particularly preferably 90 to 150°C.
  • the maximum expansion temperature (Tm (° C.)) of the thermally expandable microspheres is not particularly limited, but is preferably 85 to 350° C. from the viewpoint that the thermally expandable microspheres have good heat resistance.
  • the lower limit of the temperature is more preferably 90°C, still more preferably 95°C, particularly preferably 100°C or higher, and most preferably 105°C.
  • the upper limit of the temperature is more preferably 300°C, still more preferably 250°C, particularly preferably 200°C, most preferably 170°C.
  • the maximum expansion temperature (Tm (°C)) is determined by the method described in Examples of the present invention.
  • the foaming agent is a component that vaporizes when heated.
  • the thermally expandable microspheres as a whole become thermally expandable (the entire microspheres It will show the property of swelling due to
  • the blowing agent is not particularly limited, but linear hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, nonane, decane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nanodecane; isobutane, isopentane , isohexane, isoheptane, isooctane, isononane, isodecane, isododecane, 3-methylundecane, isotridecane, 4-methyldodecane, isotetradecane, isopentadecane, isohexadecane, 2,2,4,4,6,8,8-heptamethyl Branched hydrocarbons such as nonane, isoheptadecane, isooctadecane, is
  • the foaming agent preferably contains a hydrocarbon having 4 or less carbon atoms, particularly isobutane.
  • the encapsulation rate of the foaming agent in the thermally expandable microspheres is defined as the percentage of the weight of the foaming agent encapsulated in the thermally expandable microspheres relative to the weight of the thermally expandable microspheres.
  • the encapsulation rate of the foaming agent is not particularly limited, but is preferably 1 to 50% by weight based on the weight of the heat-expandable microspheres. When the encapsulation rate is within this range, a high internal pressure can be obtained by heating, so that the thermally expandable microspheres can be greatly expanded.
  • the lower limit of the inclusion rate of the foaming agent is preferably in the order of (1) 3% by weight, (2) 5% by weight, (3) 7% by weight, and (4) 10% by weight (the larger the number in parentheses, the more preferable).
  • the upper limit of the inclusion rate is preferably in the order of (1) 40% by weight, (2) 33% by weight, (3) 25% by weight, and (4) 20% by weight (the larger the number in parentheses, the more preferable).
  • 3 to 33% by weight is more preferable, and 10 to 20% by weight is particularly preferable.
  • the average particle size of the heat-expandable microspheres of the present invention is not particularly limited, but is preferably 0.5 to 100 ⁇ m. When the average particle size is 0.5 ⁇ m or more, the expansion performance of the heat-expandable microspheres tends to be high, and when the average particle size is 100 ⁇ m or less, the expansion stability of the heat-expandable microspheres tends to be high. There is The upper limit of the average particle size is more preferably 80 ⁇ m, still more preferably 60 ⁇ m, particularly preferably 40 ⁇ m, and most preferably 20 ⁇ m. The lower limit of the average particle size is more preferably 1 ⁇ m, still more preferably 1.5 ⁇ m, particularly preferably 2 ⁇ m, and most preferably 5 ⁇ m. Incidentally, the average particle size of the heat-expandable microspheres is determined by the method described in the examples of the present invention.
  • the coefficient of variation CV of the particle size distribution of the heat-expandable microspheres is not particularly limited, but is preferably 50% or less, more preferably 45% or less, in order to obtain heat-expandable microspheres with a uniform expansion ratio. Preferably it is 40% or less.
  • the coefficient of variation CV is determined by the method described in Examples. The coefficient of variation CV is calculated by the following formulas (1) and (2).
  • s is the standard deviation of the particle size, ⁇ x> is the average particle size, xi is the i-th particle size, and n is the number of particles.
  • the maximum volumetric expansion ratio of the heat-expandable microspheres is not particularly limited, but is preferably 25 times or more, more preferably 30 times or more, still more preferably 40 times or more, and particularly preferably 50 times in order to achieve the effect of the present application. or more, more preferably 70 times or more.
  • the upper limit of the maximum expansion ratio is preferably 120 times.
  • the maximum expansion ratio of the thermally expandable microspheres is a value obtained by dividing the true specific gravity of the thermally expandable microspheres before thermal expansion by the true specific gravity after maximum expansion.
  • the heat-expandable microspheres of the present invention are produced by dispersing an oily mixture containing a polymerizable component, a foaming agent, and a polymerization initiator in an aqueous dispersion medium, and polymerizing the polymerizable component ( Hereinafter, it may be simply referred to as a polymerization step).
  • the polymerization initiator is not particularly limited, but commonly used peroxides, azo compounds, and the like can be mentioned.
  • peroxides include peroxydicarbonates such as diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, dibenzyl peroxydicarbonate; oxide, di(3,5,5-trimethylhexanoyl) peroxide, diacyl peroxide such as dibenzoyl peroxide; ketone peroxide such as methyl ethyl ketone peroxide and cyclohexanone peroxide; 2,2-bis(t-butyl peroxide); oxy) peroxyketals such as butane; hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide; dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide; Peroxy
  • azo compounds examples include 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4- dimethylvaleronitrile), 2,2'-azobis (2-methylpropionate), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), etc. is mentioned.
  • the weight ratio of the polymerization initiator is not particularly limited, but is preferably 0.02 to 12 parts by weight with respect to 100 parts by weight of the polymerizable component.
  • the upper limit of the weight ratio is preferably (1) 10 parts by weight, (2) 8 parts by weight, (3) 5 parts by weight, and (4) 2 parts by weight (the larger the number in parentheses, the better).
  • the lower limit of the weight ratio is preferably in the order of (1) 0.05 parts by weight, (2) 0.1 parts by weight, (3) 0.2 parts by weight, and (4) 0.4 parts by weight (brackets The higher the number inside, the better).
  • the polymerization initiator may be used singly or in combination of two or more.
  • the aqueous dispersion medium is a medium for dispersing an oily mixture essentially containing a polymerizable component and a foaming agent, and is mainly composed of water such as ion-exchanged water.
  • the aqueous dispersion medium may further contain an alcohol such as methanol, ethanol or propanol, or a hydrophilic organic solvent such as acetone. Hydrophilicity in the present invention means being arbitrarily miscible with water.
  • the amount of the aqueous dispersion medium to be used is not particularly limited, but it is preferable to use 100 to 1500 parts by weight of the aqueous dispersion medium with respect to 100 parts by weight of the polymerizable component.
  • the aqueous dispersion medium may further contain an electrolyte.
  • electrolytes include sodium chloride, magnesium chloride, calcium chloride, sodium sulfate, magnesium sulfate, ammonium sulfate, sodium carbonate and the like. These electrolytes may be used singly or in combination of two or more.
  • the content of the electrolyte is not particularly limited, but is preferably 0 to 50 parts by weight per 100 parts by weight of the aqueous dispersion medium.
  • the aqueous dispersion medium is a water-soluble 1,1-substituted compound having a structure in which a hydrophilic functional group selected from a hydroxyl group, a carboxylic acid (salt) group and a phosphonic acid (salt) group and a heteroatom are bonded to the same carbon atom.
  • potassium dichromate, alkali metal nitrites, metal (III) halides, boric acid, water-soluble ascorbic acids, water-soluble polyphenols, water-soluble B vitamins and water-soluble phosphonic acids (salts) It may contain at least one water-soluble compound.
  • water-soluble as used in the present invention means a state in which 1 g or more is dissolved in 100 g of water.
  • the amount of the water-soluble compound contained in the aqueous dispersion medium is not particularly limited, but is preferably 0.0001 to 1.0 parts by weight with respect to 100 parts by weight of the polymerizable component.
  • the upper limit of the amount of the water-soluble compound is more preferably 0.5 parts by weight, still more preferably 0.1 parts by weight, and particularly preferably 0.05 parts by weight.
  • the lower limit of the amount of the water-soluble compound is more preferably 0.0003 parts by weight, still more preferably 0.001 parts by weight, and particularly preferably 0.02 parts by weight. If the amount of the water-soluble compound is too small, the effects of the water-soluble compound may not be sufficiently obtained. On the other hand, if the amount of the water-soluble compound is too large, the polymerization rate may decrease, or the residual amount of the polymerizable component, which is the starting material, may increase.
  • the aqueous dispersion medium may contain a dispersion stabilizer and a dispersion stabilizing aid in addition to the electrolyte and water-soluble compound.
  • dispersion stabilizers include tribasic calcium phosphate, magnesium pyrophosphate obtained by a metathesis method, calcium pyrophosphate, colloidal silica, alumina sol, and magnesium hydroxide. These dispersion stabilizers may be used alone or in combination of two or more.
  • the amount of the dispersion stabilizer is not particularly limited, but is preferably 0.05 to 35 parts by weight with respect to 100 parts by weight of the polymerizable component in terms of obtaining heat-expandable microspheres with a more uniform particle size.
  • the upper limit of the amount of the dispersion stabilizer is more preferably 30 parts by weight, still more preferably 20 parts by weight, and particularly preferably 10 parts by weight.
  • the lower limit of the amount of the dispersion stabilizer is more preferably 0.1 parts by weight, still more preferably 0.2 parts by weight, and particularly preferably 0.5 parts by weight.
  • the dispersion stabilizing aid is not particularly limited. activators and the like. These dispersion stabilizing aids may be used singly or in combination of two or more.
  • the aqueous dispersion medium is prepared, for example, by blending water (ion-exchanged water) with a water-soluble compound and, if necessary, a dispersion stabilizer and/or a dispersion stabilizing aid.
  • the pH of the aqueous dispersion medium during polymerization is appropriately determined according to the types of water-soluble compound, dispersion stabilizer, and dispersion stabilizing aid.
  • polymerization may be carried out in the presence of sodium hydroxide and zinc chloride.
  • a chain transfer agent, an organic pigment, an inorganic pigment or inorganic particles whose surface is hydrophobically treated, and the like may be further used.
  • the oily mixture is suspended and dispersed in an aqueous dispersion medium so as to prepare spherical oil droplets having a predetermined particle size.
  • a method for suspending and dispersing the oily mixture for example, a method of stirring with a homomixer (for example, manufactured by Primix Co., Ltd.) or a static mixer (for example, manufactured by Noritake Co., Ltd.) or the like is used. method, membrane emulsification method, ultrasonic dispersion method and other general dispersion methods.
  • Suspension polymerization is then initiated by heating an aqueous suspension in which the oily mixture is dispersed as spherical oil droplets in an aqueous dispersion medium. It is preferable to stir the aqueous suspension during the polymerization reaction, and the stirring may be carried out gently enough to prevent floating of the monomer components and sedimentation of the heat-expandable microspheres after polymerization, for example.
  • the polymerization temperature is freely set depending on the type of polymerization initiator, but is preferably controlled within the range of 30 to 100°C, more preferably 40 to 90°C.
  • the time for which the reaction temperature is maintained is preferably about 0.1 to 20 hours.
  • the initial polymerization pressure is not particularly limited, but it is 0 to 5.0 MPa, more preferably 0.1 to 3.0 MPa in terms of gauge pressure.
  • the cooling temperature and depressurizing method of the reaction solution after polymerization there are no particular restrictions on the cooling temperature and depressurizing method of the reaction solution after polymerization. More preferably, after cooling the reaction solution to 40° C. or lower, the pressure in the pressurized reactor is gradually reduced to atmospheric pressure.
  • the obtained slurry is filtered by a centrifugal separator, a pressure press, a vacuum dehydrator, etc., and the wet powder having a moisture content of 10 to 50% by weight, preferably 15 to 45% by weight, more preferably 20 to 40% by weight is obtained.
  • the obtained wet powder is dried by a tray type dryer, an indirect heating dryer, a fluidized bed dryer, a vacuum dryer, a vibration dryer, a flash dryer or the like to obtain a dry powder.
  • the moisture content of the obtained dry powder is preferably 8% by weight or less, more preferably 5% by weight or less.
  • the obtained wet powder or dry powder may be washed with water and/or re-dispersed, filtered again, and dried.
  • the slurry may be dried with a spray dryer, a fluidized bed dryer, or the like to obtain a dry powder.
  • Wet powder and dry powder can be appropriately selected according to the intended use.
  • the fine particle-attached heat-expandable microspheres of the present invention include the heat-expandable microspheres described above and fine particles attached to the outer surface of the outer shell thereof. It is formed of microparticles (11 and 12) adhering to the outer surface of the outer shell (9) of thermally expandable microspheres (8) having a blowing agent (core) (10).
  • the term "adherence” as used herein may simply refer to a state in which the microparticles 11 and 12 are adsorbed to the outer surface of the outer shell 9 of the heat-expandable microsphere (the state of the microparticle 11 in FIG. 3).
  • the fine particles may be embedded in the outer surface of the outer shell of the sphere and fixed (state of the fine particles 12 in FIG. 3).
  • the particle shape of the fine particles may be amorphous or spherical.
  • the fine particle-attached heat-expandable microspheres of the present invention can be obtained, for example, by drying an aqueous dispersion containing heat-expandable microspheres and fine particles.
  • the fine particles can be inorganic or organic.
  • the shape of the fine particles include spherical, needle-like, and plate-like shapes.
  • the inorganic substance constituting the fine particles is not particularly limited. Dolomite, calcium sulfate, barium sulfate, glass flakes, boron nitride, silicon carbide, silica, alumina, mica, titanium dioxide, zinc oxide, magnesium oxide, zinc oxide, hydrosaltite, carbon black, molybdenum disulfide, tungsten disulfide, ceramic beads, glass beads, crystal beads, glass microballoons, and the like.
  • the organic matter constituting the fine particles is not particularly limited, but examples include sodium carboxymethylcellulose, hydroxyethylcellulose, methylcellulose, ethylcellulose, nitrocellulose, hydroxypropylcellulose, sodium alginate, polyvinyl alcohol, polyvinylpyrrolidone, sodium polyacrylate, carboxyvinyl.
  • Polymer polyvinyl methyl ether, magnesium stearate, calcium stearate, zinc stearate, polyethylene wax, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, hydrogenated castor oil, (meth)acrylic resin, polyamide resin, silicone resin , urethane resin, polyethylene resin, polypropylene resin, fluorine-based resin, and the like.
  • Inorganic substances and organic substances constituting fine particles may be treated with surface treatment agents such as silane coupling agents, paraffin wax, fatty acids, resin acids, urethane compounds, and fatty acid esters, or may be untreated.
  • the average particle size of the fine particles is not particularly limited, but is preferably 0.001 to 30 ⁇ m, more preferably 0.005 to 25 ⁇ m, and particularly preferably 0.01 to 20 ⁇ m.
  • the average particle size is a volume-based cumulative 50% particle size value measured by a laser diffraction method.
  • the weight ratio of the fine particles to the entire thermally expandable microspheres having fine particles attached thereto of the present invention is not particularly limited, but is preferably 95% by weight or less, more preferably 90% by weight or less, particularly preferably 90% by weight or less, in terms of exhibiting the effect of the present invention. 85% by weight or less, most preferably 80% by weight or less. If the weight ratio exceeds 95% by weight, the effect of reducing weight is reduced, which may be uneconomical.
  • the lower limit of the weight percentage of fine particles is preferably 10% by weight, more preferably 20% by weight, particularly preferably 30% by weight, and most preferably 40% by weight.
  • the hollow particles of the present invention are particles obtained by heating and expanding the heat-expandable microspheres described above, and are excellent in physical properties when incorporated into a composition or molded article.
  • the hollow particles of the present invention contain an outer shell containing a thermoplastic resin obtained by polymerizing a specific polymerizable component, and a foaming agent contained in the outer shell, and are measured by a specific method. Since the particles are obtained by heating and expanding thermally expandable microspheres exhibiting a specific relationship between the temperature at which the curve reaches its maximum and the temperature at which expansion begins, leakage of the foaming agent over time can be reduced.
  • the hollow particles of the present invention are obtained by heating and expanding the heat-expandable microspheres described above, preferably at 80 to 300°C.
  • the method of thermal expansion is not particularly limited, and may be either a dry thermal expansion method, a wet thermal expansion method, or the like.
  • the dry thermal expansion method includes, for example, the method described in JP-A-2006-213930, especially the internal injection method.
  • Another dry thermal expansion method is the method described in Japanese Patent Application Laid-Open No. 2006-96963.
  • As the wet thermal expansion method there is a method described in JP-A-62-201231.
  • the true specific gravity of the hollow particles of the present invention is not particularly limited, but is preferably 0.001 to 0.60.
  • the true specific gravity is 0.001 or more, the film thickness of the outer shell portion is sufficient, and pressure resistance tends to be improved.
  • the true specific gravity is 0.60 or less, the effect of lowering the specific gravity is sufficiently obtained, and the physical properties of the composition and the molded article can be sufficiently maintained when the composition is prepared using the hollow particles.
  • the upper limit of the true specific gravity is more preferably 0.50, still more preferably 0.40, particularly preferably 0.30, most preferably 0.20.
  • the lower limit of the true specific gravity is more preferably 0.003, still more preferably 0.005, particularly preferably 0.007, most preferably 0.010.
  • the true specific gravity of the hollow particles is determined by the method used in Examples.
  • the fine particle-attached hollow particles of the present invention include the hollow particles described above and fine particles attached to the outer surface of the outer shell thereof.
  • the adhesion here may simply be a state in which the fine particles 4 and 5 are adsorbed to the outer surface of the outer shell 2 of the hollow particle (state of the fine particle 4 in FIG. 2), and the outer shell near the outer surface may be attached.
  • the constituent thermoplastic resin may be melted by heating, and the fine particle filler may be embedded in the outer surface of the outer shell of the hollow particle and fixed (state of fine particles 5 in FIG. 2).
  • the particle shape of the fine particles may be amorphous or spherical.
  • the ratio between the volume average particle diameter of fine particles and the volume average particle diameter of hollow particles is not particularly limited, but the adhesion of fine particles to the surface of hollow particles point, it is preferably 1 or less, more preferably 0.1 or less, and still more preferably 0.05 or less.
  • the weight ratio of the fine particles to the whole fine-particle-attached hollow particles is not particularly limited, but is preferably 95% by weight or less, more preferably 90% by weight or less, particularly preferably 85% by weight or less, and most preferably 80% by weight or less. is. If the weight ratio is more than 95% by weight, the amount to be added becomes large when preparing a composition using fine-particle-attached hollow particles, which may be uneconomical.
  • the lower limit of the weight percentage of fine particles is preferably 10% by weight, more preferably 20% by weight, particularly preferably 30% by weight, and most preferably 40% by weight.
  • the true specific gravity of the microparticle-attached hollow particles is not particularly limited, but is preferably 0.01 to 0.60.
  • the true specific gravity is 0.01 or more, the film thickness of the outer shell portion becomes sufficient, and there is a tendency that permanent set can be suppressed.
  • the true specific gravity is 0.60 or less, the effect of lowering the specific gravity is sufficiently obtained, and the physical properties of the composition and the molded product are sufficiently maintained when the composition is prepared using the fine particle-attached hollow particles. tend to be able to
  • the upper limit of the true specific gravity is more preferably 0.40, particularly preferably 0.30, most preferably 0.20.
  • the lower limit of the true specific gravity is more preferably 0.07, particularly preferably 0.10.
  • the manufacturing method includes, for example, a step of mixing thermally expandable microspheres and fine particles (mixing step), and heating the mixture obtained in the mixing step to a temperature above the softening point.
  • a manufacturing method including a step of heating to expand the heat-expandable microspheres and adhering fine particles to the outer surface of the resulting hollow particles (adhering step) is preferred. It can also be obtained by heating and expanding the fine particle-attached heat-expandable microspheres.
  • the mixing step is a step of mixing the heat-expandable microspheres and the fine particles.
  • the weight ratio of fine particles to the total of heat-expandable microspheres and fine particles in the mixing step is not particularly limited, but is preferably 95% by weight or less, more preferably 90% by weight or less, particularly preferably 85% by weight or less, and most preferably. is 80% by weight or less. When the weight ratio is 95% by weight or less, the resulting fine-particle-adhered hollow particles tend to be lightweight, and a sufficient effect of lowering the specific gravity tends to be obtained.
  • the lower limit of the weight ratio is preferably 5% by weight, more preferably 10% by weight, particularly preferably 20% by weight, and most preferably 30% by weight.
  • the device used to mix the heat-expandable microspheres and the fine particles is not particularly limited, and a device having a very simple mechanism such as a container and stirring blades can be used.
  • a powder mixer capable of general shaking or stirring may be used.
  • powder mixers include powder mixers capable of oscillating or stirring, such as ribbon type mixers and vertical screw type mixers.
  • the adhering step is a step of heating the mixture containing the heat-expandable microspheres and fine particles obtained in the mixing step described above to a temperature above the softening point of the thermoplastic resin forming the outer shell of the heat-expandable microspheres. is.
  • the heat-expandable microspheres are expanded and the microparticles are adhered to the outer surface of the outer shell of the obtained hollow particles.
  • Heating may be performed using a general contact heat transfer type or direct heating type mixing drying apparatus.
  • the function of the mixing-type drying device is not particularly limited, but it is preferable to have a temperature controllable ability to disperse and mix raw materials, and optionally a decompression device or a cooling device for speeding up drying.
  • the device used for heating is not particularly limited.
  • the temperature conditions for heating depend on the type of thermally expandable microspheres, but the optimum expansion temperature is preferred, preferably 70 to 250°C, more preferably 80 to 210°C, further preferably 90 to 170°C. be.
  • composition and molded article The composition of the present invention comprises at least one selected from the above-described heat-expandable microspheres, hollow particles and microparticle-attached hollow particles, and a base component.
  • the base component is not particularly limited, and rubbers such as natural rubber, butyl rubber, silicone rubber, ethylene-propylene-diene rubber (EPDM); thermosetting resins such as unsaturated polyesters, epoxy resins and phenol resins; polyethylene wax.
  • Waxes such as paraffin wax; ethylene-vinyl acetate copolymer (EVA), ionomer, polyethylene, polypropylene, polyvinyl chloride (PVC), acrylic resin, thermoplastic polyurethane, acrylonitrile-styrene copolymer (AS resin), Acrylonitrile-butadiene-styrene copolymer (ABS resin), polystyrene (PS), polyamide resin (nylon 6, nylon 66, etc.), polycarbonate, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyacetal (POM), polyphenylene Thermoplastic resins such as sulfide (PPS); Thermoplastic elastomers such as olefin elastomers and styrene elastomers; Polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride-hexafluoroprop
  • the composition of the present invention can be prepared by mixing at least one selected from heat-expandable microspheres, hollow particles, and microparticle-attached hollow particles with the base component described above. Further, a composition obtained by mixing at least one selected from heat-expandable microspheres, hollow particles, and microparticle-attached hollow particles with a base component is further mixed with another base component to obtain the composition of the present invention. It can also be a composition of In addition, the composition of the present invention may contain at least one selected from heat-expandable microspheres, hollow particles, and microparticle-attached hollow particles, and other components as appropriate depending on the application, in addition to the base component. Other components include, for example, plasticizers, fillers, colorants, high-boiling organic solvents, adhesives, viscosity modifiers, and the like.
  • the total content of the heat-expandable microspheres, hollow particles and microparticle-attached hollow particles is not particularly limited, but is preferably 0.05 to 750 per 100 parts by weight of the base component. weight part.
  • the total content is 0.05 parts by weight or more, there is a tendency that a sufficiently lightweight molded article can be obtained.
  • the total content is 750 parts by weight or less, the uniform dispersibility of at least one selected from heat-expandable microspheres, hollow particles and microparticle-attached hollow particles tends to be further improved.
  • the upper limit of the total content is more preferably 700 parts by weight, still more preferably 600 parts by weight, particularly preferably 500 parts by weight, and most preferably 400 parts by weight.
  • the lower limit of the total content is more preferably 0.1 parts by weight, still more preferably 0.2 parts by weight, particularly preferably 0.5 parts by weight, and most preferably 1 part by weight.
  • the method for preparing the composition of the present invention is not particularly limited, and conventionally known methods may be employed.
  • the method include mixers such as homomixers, static mixers, Henschel mixers, tumbler mixers, planetary mixers, kneaders, rolls, mixing rolls, mixers, single-screw kneaders, twin-screw kneaders, and multi-screw kneaders. and a method of mechanically and uniformly mixing them.
  • the composition of the present invention include rubber compositions, molding compositions, paint compositions, clay compositions, adhesive compositions, and powder compositions.
  • the molded article of the present invention is obtained by molding the composition described above.
  • Examples of the molded article of the present invention include molded articles and coating films.
  • the molded product of the present invention is said to have improved physical properties such as lightness, porosity, sound absorption, heat insulation, low thermal conductivity, low dielectric constant, design, impact absorption, strength, etc., and to have excellent appearance. effect can also be obtained.
  • thermally expandable microspheres examples of the heat-expandable microspheres of the present invention are specifically described below. However, the present invention is not limited to these examples. In the following examples and comparative examples, “%” means “% by weight” and “parts” means “parts by weight” unless otherwise specified. In addition, the physical properties of the thermally expandable microspheres listed in the following examples and comparative examples were measured according to the following procedures, and the performance was further evaluated. Hereinafter, thermally expandable microspheres are sometimes referred to as "microspheres" for simplicity.
  • Average particle size (D50) of heat-expandable microspheres A Microtrac particle size distribution meter (model 9320-HRA) manufactured by Nikkiso Co., Ltd. was used as a measuring device, and the D50 value obtained by volume-based measurement was taken as the average particle size.
  • the positive displacement start temperature was taken as the expansion start temperature (Ts (°C)), and the temperature at which the maximum amount of displacement (H max ) was exhibited was taken as the maximum expansion temperature (Tm (°C)).
  • Td (° C.) at which the DTG value is maximized in the differential thermogravimetric curve (DTG) A calorimeter measuring device (TA Instruments, TGA Q500) was used as a measuring device. 0.001 g of sample microspheres was placed in a 500 ⁇ L ceramic pan and heated from 20° C. to 300° C. at a rate of 10° C./min in a nitrogen atmosphere. The weight loss of the sample during heating was measured to obtain a thermoweight loss curve. A differential thermogravimetric curve (DTG) was obtained by differentiating the obtained thermogravimetric loss curve with respect to time. The temperature of the sample at the time when the obtained differential thermogravimetric curve reaches the maximum value was defined as the temperature (Td (° C.)) at which the DTG value reaches the maximum value.
  • Td ° C.
  • the true specific gravity of the heat-expandable microspheres, hollow particles, or microparticle-attached hollow particles was measured by the following measuring method.
  • the true specific gravity was measured by a liquid immersion method (Archimedes method) using isopropyl alcohol in an atmosphere with an environmental temperature of 25° C. and a relative humidity of 50%. Specifically, a volumetric flask with a capacity of 100 mL was emptied, and after drying, the volumetric flask weight (WB1) was measured.
  • the weight (WB2) of the volumetric flask filled with 100 mL of isopropyl alcohol was weighed.
  • a volumetric flask with a volume of 100 mL was emptied, and after drying, the volumetric flask weight (WS1) was measured.
  • About 50 mL of the particle sample was filled into a weighed volumetric flask, and the weight (WS2) of the volumetric flask filled with the particle sample was weighed. Then, the volumetric flask filled with the particle sample was accurately filled with isopropyl alcohol up to the meniscus without air bubbles, and then the weight (WS3) was weighed.
  • Foaming agent retention rate (%) C3 / C2 x 100
  • Condition A normal temperature
  • Condition B high temperature
  • Foaming agent retention rate is 90% or more and 100% or less, and leakage reduction of foaming agent over time is excellent.
  • the foaming agent retention rate is 80% or more and less than 90%, and the leakage reduction property of the foaming agent over time is slightly excellent.
  • the foaming agent retention rate is 70% or more and less than 80%, and the ability to reduce leakage of the foaming agent over time is slightly inferior.
  • the foaming agent retention rate is 0% or more and less than 70%, and the ability to reduce leakage of the foaming agent over time is poor.
  • Example 1 1.0 parts of polyvinylpyrrolidone, 0.05 parts of carboxymethylated polyethyleneimine Na salt and 65 parts of colloidal silica (effective concentration 20%) are added to 500 parts of ion-exchanged water, and the pH is adjusted to 3.0. A dispersion medium was prepared. Separately, 175 parts of acrylonitrile, 13 parts of methyl methacrylate, 112 parts of vinylidene chloride, 0.8 parts of ethylene glycol dimethacrylate, 41 parts of isobutane, 2 parts of di-2-ethylhexyl peroxydicarbonate (70% purity), 1 part of diisopropyl peroxydicarbonate was mixed to obtain an oily mixture.
  • the aqueous dispersion medium and the oily mixture are mixed, and the resulting mixed solution is run with a homomixer (manufactured by Primix Co., Ltd.) at a rotation speed of 10,000 rpm until the droplet size of the oily mixture reaches the target size of the thermally expandable microspheres.
  • Dispersed to prepare an aqueous suspension The obtained aqueous suspension was transferred to a pressurized reactor having a capacity of 1.5 liters, and after nitrogen substitution, the initial reaction pressure was set to 0.5 MPa, and the polymerization reaction was carried out at a polymerization temperature of 60° C. for 20 hours while stirring at 80 rpm. . After the polymerization, the reaction liquid was cooled to 40° C.
  • Examples 2 to 17 heat-expandable microspheres of Examples 2 to 17 were obtained in the same manner as in Example 1, except that the conditions were changed as shown in Tables 1 and 2. .
  • Comparative example 1 1.0 parts of polyvinylpyrrolidone, 0.05 parts of carboxymethylated polyethyleneimine Na salt and 65 parts of colloidal silica (effective concentration 20%) are added to 500 parts of ion-exchanged water, and the pH is adjusted to 3.0. A dispersion medium was prepared. Separately, 90 parts of acrylonitrile, 15 parts of methyl methacrylate, 195 parts of vinylidene chloride, 4.7 parts of diethylene glycol dimethacrylate, 48 parts of isobutane, and 3 parts of diisopropyl peroxydicarbonate were mixed to prepare an oily mixture.
  • the aqueous dispersion medium and the oily mixture are mixed, and the resulting mixed solution is run with a homomixer (manufactured by Primix Co., Ltd.) at a rotation speed of 10,000 rpm until the droplet size of the oily mixture reaches the target size of the thermally expandable microspheres. Dispersed to prepare an aqueous suspension.
  • the obtained aqueous suspension was transferred to a pressurized reactor having a capacity of 1.5 liters, and after nitrogen substitution, the initial reaction pressure was set to 0.35 MPa, and the polymerization reaction was carried out at a polymerization temperature of 60° C. for 20 hours while stirring at 80 rpm. .
  • the reaction liquid was cooled to 50° C., and the pressure in the pressure reactor was reduced to atmospheric pressure to obtain a dispersion liquid containing a product.
  • the product was filtered from the dispersion containing the product and dried to obtain thermally expandable microspheres.
  • the physical properties of the obtained heat-expandable microspheres were measured and evaluated in the same manner as in Example 1. Table 3 shows the results.
  • Comparative Examples 2 to 16 heat-expandable microspheres of Comparative Examples 2 to 13 were obtained in the same manner as in Comparative Example 1 except that the conditions in Comparative Example 1 were changed as shown in Tables 3 to 4. .
  • the physical properties of each thermally expandable microsphere obtained were measured and evaluated in the same manner as in Example 1. The results are shown in Tables 3-4.
  • Example 18 The heat-expandable microspheres obtained in Example 15 were heated at 120° C. for 5 minutes to obtain hollow particles having a true specific gravity of 0.02. 70 parts by weight of the obtained hollow particles, 200 parts by weight of polyvinyl alcohol, 800 parts by weight of vinyl acetate, 20 parts by weight of boric acid, and 1000 parts by weight of water were mixed using a universal mixer for 10 minutes to obtain a clay composition. Obtained. The obtained clay composition was light in weight and had a good appearance with little unevenness on the surface.
  • Example 19 A clay composition was obtained in the same manner as in Example 18, except that the heat-expandable microspheres used in Example 18 were changed to the heat-expandable microspheres obtained in Example 12. At this time, the true specific gravity of the obtained hollow particles was 0.015. In addition, the obtained clay composition was light in weight and had a good appearance with little unevenness on the surface.
  • Example 20 100 parts by weight of the heat-expandable microspheres obtained in Example 15 and 10 parts by weight of silica were dispersed in water and dried at 70°C using a mixer dryer to obtain fine-particle-attached heat-expandable microspheres. .
  • the fine particle-attached heat-expandable microspheres thus obtained were heated at 120° C. for 5 minutes to obtain fine particle-attached hollow particles having a true specific gravity of 0.03.
  • PVC paste manufactured by Kaneka, PCH-175) 100 parts by weight, DINP (manufactured by Shinnihon Rika, Sanso Cizer) 100 parts by weight, and calcium carbonate (manufactured by Bihoku Funka Kogyo, Whiten Aka) 200 parts by weight were mixed.
  • a vinyl chloride resin binder was mixed with 1 part by weight of the fine particle-attached hollow particles to prepare a vinyl chloride resin coating composition.
  • the prepared coating composition was applied to an electrodeposition coated plate (thickness: 2 mm) and heated at 140°C for 20 minutes to obtain a molded body.
  • the molded article obtained was light in weight and had a good appearance with few irregularities on the surface.
  • Example 21 A coating composition and a molded article were obtained in the same manner as in Example 20, except that the heat-expandable microspheres used in Example 20 were changed to the heat-expandable microspheres obtained in Example 12.
  • the true specific gravity of the microparticle-attached hollow particles obtained at this time was 0.025.
  • the molded article obtained was light in weight and had a good appearance with little unevenness on the surface.
  • thermally expandable microspheres containing an outer shell containing a thermoplastic resin and a foaming agent contained therein and vaporized by heating, wherein the thermoplastic resin is chloride
  • the thermally expandable microspheres which are polymers of polymerizable components containing vinylidene (A) and acrylonitrile (B) and satisfy the conditions 1 and 2, prevent leakage of the foaming agent over time. Hollow particles are obtained which can be reduced and can begin to expand at relatively low temperatures.
  • the heat-expandable microspheres of the present invention can be used, for example, as putty, paint, ink, sealant, mortar, paper clay, pottery, and the like as a lightweight material. Molding such as molding and press molding can be performed to produce a molded product having excellent sound insulation, heat insulation, heat insulation, sound absorption, and the like.

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