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WO2025154555A1 - Microsphères thermo-expansibles et utilisation de celles-ci - Google Patents

Microsphères thermo-expansibles et utilisation de celles-ci

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Publication number
WO2025154555A1
WO2025154555A1 PCT/JP2025/000005 JP2025000005W WO2025154555A1 WO 2025154555 A1 WO2025154555 A1 WO 2025154555A1 JP 2025000005 W JP2025000005 W JP 2025000005W WO 2025154555 A1 WO2025154555 A1 WO 2025154555A1
Authority
WO
WIPO (PCT)
Prior art keywords
expandable microspheres
heat
weight
monomer
meth
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/000005
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English (en)
Japanese (ja)
Inventor
由春 岸口
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Matsumoto Yushi Seiyaku Co Ltd
Original Assignee
Matsumoto Yushi Seiyaku Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Matsumoto Yushi Seiyaku Co Ltd filed Critical Matsumoto Yushi Seiyaku Co Ltd
Priority to JP2025518187A priority Critical patent/JP7778992B1/ja
Publication of WO2025154555A1 publication Critical patent/WO2025154555A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • 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
    • 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

Definitions

  • the present invention relates to heat-expandable microspheres and their uses.
  • Thermally expandable microspheres which are fine particles having a thermoplastic resin outer shell and a foaming agent encapsulated therein, have the characteristic of expanding when heated. These heat-expandable microspheres are used in a wide range of applications, for example, when they are blended with a substrate. By heat treatment during molding, the heat-expandable microspheres expand simultaneously with molding, and can not only reduce the weight of the molded article but also impart design properties, cushioning properties, etc. to the molded article.
  • Patent Document 1 discloses such heat-expandable microspheres, which have an outer shell made of a thermoplastic resin obtained by polymerizing a polymerizable component consisting essentially of a methacrylic acid ester monomer and a carboxyl group-containing monomer, and in which a nitrile monomer is present in an amount of 0 to 30 parts by weight per 100 parts by weight of the total amount of the methacrylic acid ester monomer and the carboxyl group-containing monomer, and in which the encapsulated blowing agent is essentially a hydrocarbon having 8 or more carbon atoms.
  • Patent Document 2 discloses a thermally expandable microcapsule having a shell made of a polymer and a volatile expansion agent encapsulated as a core agent, the shell being formed by polymerizing a monomer composition containing a nitrile monomer, a monomer having an amide group, and a compound having a glycidyl group in the molecule, the monomer having an amide group containing at least one type selected from acrylamide and methacrylamide, and the monomer composition containing 0.9 to 20% by weight of the monomer having an amide group and 0.1 to 15% by weight of the compound having a glycidyl group.
  • the heat-expandable microspheres disclosed in Patent Document 1 are nearly spherical, have excellent expandability, and are easy to work with when mixed with a resin.
  • the heat-expandable microspheres disclosed in Patent Document 2 have a high expansion ratio and durability at high temperatures, and are unlikely to produce coloration or odor when used in expansion molding.
  • the heat-expandable microspheres disclosed in the above-mentioned patent documents are expanded, there is a problem that the expansion characteristics change significantly over a wide temperature range, and when such heat-expandable microspheres are used to produce molded articles, there is also a problem that the quality of the obtained molded articles is not stable.
  • the object of the present invention is therefore to provide heat-expandable microspheres that exhibit minimal change in expansion properties over a wide temperature range, and uses thereof.
  • the present invention relates to heat-expandable microspheres which contain an outer shell containing a thermoplastic resin (A) and a blowing agent encapsulated in the outer shell and vaporized by heating, and which satisfy the following condition 1:
  • Condition 1 The glass transition point (Tg 0 ) of a thermoplastic resin (A1) obtained by immersing heat-expandable microspheres in tetrahydrofuran and the glass transition point (Tg 1 ) of a thermoplastic resin (A2) obtained by heating the heat-expandable microspheres for 10 minutes at a temperature 20 ° C. higher than their maximum expansion temperature and immersing the treated product in tetrahydrofuran satisfy the following formula (I): (Tg 1 )-(Tg 0 )>0°C Formula (I)
  • the heat-expandable microspheres of the present invention preferably further satisfy at least one of the following requirements 1) to 5).
  • the thermoplastic resin (A) is a polymer of a polymerizable component, and the polymerizable component contains a carboxyl group-containing monomer (a1).
  • the polymerizable component further comprises a monomer (a2) containing a group reactive with a carboxyl group.
  • the weight ratio of the monomer (a1) in the polymerizable component is 20 to 70% by weight.
  • the weight ratio of the monomer (a2) in the polymerizable component is 0.1 to 10% by weight.
  • the weight ratio of the nitrile monomer (a3) in the polymerizable component is 40% by weight or less.
  • the hollow particles of the present invention are the expanded form of the above-mentioned heat-expandable microspheres.
  • the heat-expandable microspheres of the present invention exhibit little change in expansion properties over a wide temperature range.
  • the hollow particles of the present invention are lightweight because they are expanded products of the above-mentioned heat-expandable microspheres. Since the composition of the present invention contains at least one selected from the group consisting of the heat-expandable microspheres and the hollow particles, it is possible to stably produce lightweight molded articles.
  • the molded article of the present invention is lightweight since it is obtained by molding the above composition.
  • the heat-expandable microspheres of the present invention contain a shell containing a thermoplastic resin (A) and a blowing agent that vaporizes when heated, and the microspheres as a whole exhibit heat expandability (the property that the entire microsphere expands when heated).
  • the heat-expandable microspheres preferably have a core-shell structure consisting of a shell containing a thermoplastic resin and a core that essentially contains a blowing agent.
  • the above Tg 0 indicates the glass transition point of the thermoplastic resin constituting the outer shell of the heat-expandable microspheres that are not heated and not expanded.
  • the above Tg 1 indicates the glass transition point of the thermoplastic resin constituting the outer shell of the expanded body obtained when the expanded body is heated for 10 minutes at a temperature 20° C. higher than the temperature at maximum expansion.
  • the maximum expansion temperature (T max ) of the heat-expandable microspheres of the present invention is not particularly limited, but is preferably 155° C. or higher. When the maximum expansion temperature is 155° C. or higher, the change in expandability tends to be suppressed.
  • the maximum expansion temperature is more preferably 155 to 250° C., further preferably 160 to 230° C., particularly preferably 165 to 210° C., and most preferably 170 to 200° C.
  • the expansion starting temperature (T s ) and maximum expansion temperature (T max ) of the heat-expandable microspheres are measured by the method described in the Examples.
  • the polymerizable component is not particularly limited, but it is preferable to contain a carboxyl group-containing monomer (hereinafter sometimes referred to as monomer (a1)) as a monomer component in order to improve heat resistance and solvent resistance, and also to easily obtain heat-expandable microspheres satisfying the above formula (I).
  • monomer (a1) a carboxyl group-containing monomer
  • the weight ratio of the carboxyl group-containing monomer in the polymerizable component is not particularly limited, but is preferably 20 to 70% by weight, more preferably 25 to 65% by weight, further preferably 30 to 60% by weight, and particularly preferably 35 to 55% by weight.
  • the weight ratio is 20% by weight or more, the change in expandability tends to be suppressed.
  • the weight ratio is 70% by weight or less, the expandability and the solvent resistance tend to be improved.
  • the polymerizable component contains a carboxyl group-containing monomer
  • the polymerizable component further contains a monomer (a2) containing a group reactive with a carboxyl group (hereinafter, sometimes referred to as monomer (a2)) as a monomer component, since this is believed to improve the cohesive energy of the polymer and to further suppress the change in expandability.
  • monomer (a2) a group reactive with a carboxyl group
  • the group reactive with a carboxyl group is not particularly limited, and examples thereof include a methylol group, a hydroxyl group, an amino group, an epoxy group, an isocyanate group, etc., and may be composed of one or more types.
  • the monomer containing a group reactive with a carboxyl group is not particularly limited, but examples thereof include N-methylol (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, vinyl glycidyl ether, propenyl glycidyl ether, glycidyl (meth)acrylate, glycerin mono(meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, p-hydroxystyrene, etc. These monomers may be used alone or in combination of two or more.
  • the weight ratio of the nitrile monomer as a monomer component in the polymerizable component is not particularly limited, but it is preferable that it is 40% by weight or less in that yellowing of the resulting heat-expandable particles and their expanded bodies is suppressed. In addition, when the weight ratio is within the above range, heat-expandable microspheres that satisfy the above condition 1 are easily obtained, which is preferable.
  • the weight ratio is more preferably 30% by weight or less, even more preferably 20% by weight or less, particularly preferably 10% by weight or less, and most preferably 0% by weight.
  • the polymerizable component may contain, as a monomer component, a (meth)acrylic acid monomer having no group reactive with a carboxyl group, which is preferable in that the expansion property of the heat-expandable microspheres can be adjusted.
  • the polymerizable component contains a (meth)acrylic acid-based monomer having no group reactive with a carboxyl group as a monomer component
  • the weight ratio of the (meth)acrylic acid-based monomer having no group reactive with a carboxyl group in the polymerizable component is not particularly limited, but is preferably 3 to 70% by weight, more preferably 5 to 65% by weight, even more preferably 10 to 60% by weight, and particularly preferably 15 to 55% by weight.
  • the polymerizable component may contain a crosslinking agent, which improves the density of the outer shell of the heat-expandable microspheres and allows the heat-expandable microspheres to expand effectively.
  • the crosslinking agent is not particularly limited, and examples thereof include alkanediol di(meth)acrylates such as ethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 1,9-nonanediol di(meth)acrylate; diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, PEG#200 di(meth)acrylate, and PEG#400 di(meth)acrylate.
  • Polyalkylene glycol di(meth)acrylates such as acrylate, PEG #600 di(meth)acrylate, PEG #1000 di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol #400 di(meth)acrylate, and polypropylene glycol #700 di(meth)acrylate; ethoxylated bisphenol A di(meth)acrylate (EO addition 2-30); Propoxylated bisphenol A di(meth)acrylate; Propoxylated ethoxylated bisphenol A di(meth)acrylate; Glycerin di(meth)acrylate; Polybutadiene di(meth)acrylate; Polyisoprene di(meth)acrylate; 2-hydroxy-3-acryloyloxypropyl methacrylate; Dimethylol-tricyclodecane di(meth)acrylate; Divinylbenzene; Ethoxylated glycer
  • the weight ratio of the crosslinking agent in the polymerizable component is not particularly limited, but is preferably 0.1 to 10% by weight, more preferably 0.15 to 5% by weight, even more preferably 0.2 to 3% by weight, particularly preferably 0.2 to 2% by weight, and most preferably 0.3 to 1.5% by weight.
  • the polymerization initiator is not particularly limited, but examples thereof include peroxides and azo compounds.
  • peroxides include peroxydicarbonates such as diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and dibenzyl peroxydicarbonate; diacyl peroxides such as dilauroyl peroxide and dibenzoyl peroxide; ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; peroxy ketals such as 2,2-bis(t-butylperoxy)butane; hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide; dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide; and peroxy esters such as t-hexyl peroxypivalate
  • the aqueous dispersion medium used in the polymerization step is a medium mainly composed of water such as ion-exchanged water for dispersing the oily mixture, and may further contain an alcohol such as methanol, ethanol, propanol, etc., or a hydrophilic organic solvent such as acetone, etc.
  • hydrophilicity means a state in which it can be arbitrarily mixed with water.
  • the amount of the aqueous dispersion medium used is not particularly limited, but is preferably 100 to 1000 parts by weight based on 100 parts by weight of the polymerizable component.
  • the aqueous dispersion medium is prepared, for example, by mixing water (ion-exchanged water) with electrolytes, water-soluble compounds, dispersion stabilizers, dispersion stabilization assistants, etc., as necessary.
  • the pH of the aqueous dispersion medium during polymerization is appropriately determined depending on the types of water-soluble compounds, dispersion stabilizers, and dispersion stabilization assistants.
  • Examples of methods for suspending and dispersing the oily mixture include general dispersion methods such as a stirring method using a homomixer (e.g., manufactured by Primix Corporation) or the like, a method using a static dispersion device such as a static mixer (e.g., manufactured by Noritake Engineering Co., Ltd.), a membrane suspension method, and an ultrasonic dispersion method.
  • the suspension polymerization is then initiated by heating the dispersion in which the oily mixture is dispersed in the aqueous dispersion medium as oil globules.
  • the dispersion is preferably stirred, and the stirring may be carried out gently enough to prevent the floating of the oil globules and the settling of the heat-expandable microspheres after polymerization.
  • the hollow particles of the present invention are expanded bodies obtained by heating and expanding the above-described heat-expandable microspheres.
  • the hollow particles are lightweight and have excellent material properties when contained in a composition or molded article.
  • the hollow particles of the present invention are expanded bodies obtained by heating and expanding the heat-expandable microspheres having the above-mentioned specific properties, and have excellent stability of specific gravity and may be inhibited from yellowing.
  • the average particle size of the hollow particles of the present invention can be freely designed depending on the application, and is not particularly limited, but is preferably 3 to 1000 ⁇ m, more preferably 5 to 300 ⁇ m, further preferably 10 to 200 ⁇ m, and particularly preferably 20 to 150 ⁇ m.
  • the coefficient of variation (CV) of the particle size distribution of the hollow particles of the present invention is not particularly limited, but is preferably 40% or less, more preferably 35% or less. The coefficient of variation is preferably 10% or more, and more preferably 15% or more.
  • the true specific gravity of the hollow particles of the present invention is not particularly limited, but in terms of achieving the effects of the present application, it is preferably 0.001 to 0.6 g/mL, more preferably 0.0015 to 0.4 g/mL, and even more preferably 0.002 to 0.3 g/mL. If the true specific gravity is 0.001 g/mL or more, the stability of the specific gravity tends to improve. Also, if the true specific gravity is 0.6 g/mL or less, the weight reduction effect tends to improve.
  • the average particle size of the microparticles is selected appropriately depending on the hollow particles that compose them, and is not particularly limited, but is preferably 0.001 to 30 ⁇ m, more preferably 0.005 to 25 ⁇ m, and even more preferably 0.01 to 20 ⁇ m.
  • the average particle size of the microparticles is preferably 1/10 or less of the average particle size of the hollow particles to which the microparticles are attached.
  • the average particle size means the average particle size of the primary particles.
  • fine particles can be used, and may be made of either inorganic or organic materials.
  • the shape of the fine particles may be spherical, needle-like, plate-like, or the like.
  • the organic matter constituting the fine particles is not particularly limited, but examples thereof include metal soaps such as magnesium stearate, calcium stearate, zinc stearate, barium stearate, and lithium stearate; synthetic waxes such as polyethylene wax, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, and hydrogenated castor oil; and organic polymers such as polyacrylamide, polyimide, nylon, polymethyl methacrylate, polyethylene, and polytetrafluoroethylene.
  • the true specific gravity of the fine particle-coated hollow particles is not particularly limited, but is preferably 0.01 to 0.6 g/mL, more preferably 0.03 to 0.5 g/mL, even more preferably 0.05 to 0.4 g/mL, and particularly preferably 0.07 to 0.3 g/mL. If the true specific gravity is 0.01 g/mL or more, the durability of the hollow particles tends to improve. If the true specific gravity is 0.6 g/mL or less, the weight reduction effect tends to improve.
  • the composition of the present invention contains at least one selected from the above-described heat-expandable microspheres and hollow particles, and a base component.
  • the base material component is not particularly limited, and examples thereof include rubbers such as natural rubber, butyl rubber, silicone rubber, and ethylene-propylene-diene rubber (EPDM); thermosetting resins such as unsaturated polyester, epoxy resin, and phenolic resin; waxes such as polyethylene wax and paraffin wax; thermoplastic resins such as 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 terephthal
  • thermoplastic elastomers such as olefin elastomers and styrene elastomers
  • bioplastics such as polylactic acid (PLA), cellulose acetate, polybutylene succinate (PBS), polyhydroxyalkanoate (PHA), and starch resins
  • sealing materials such as silicones, modified silicones, polysulfides, modified polysulfides, urethanes, acrylics, polyisobutylenes, and butyl rubbers
  • liquid components such as urethane, ethylene-vinyl acetate copolymers, vinyl chloride, and acrylic emulsions and plastisols
  • inorganic materials such as cement, mortar, and cordierite
  • organic fibers such as cellulose, kenaf, bran, aramid fibers, phenolic fibers, polyester fibers, acrylic fibers, polyolefin fibers such as polyethylene and polypropylene, polyvinyl alcohol fibers, and rayon.
  • the composition of the present invention can be prepared by mixing at least one selected from heat-expandable microspheres and hollow particles with a base component.
  • the composition obtained by mixing at least one selected from heat-expandable microspheres and hollow particles with a base component can also be mixed with another base component to prepare the composition of the present invention.
  • the composition of the present invention may contain other components in addition to the heat-expandable microspheres, hollow particles and base component depending on the intended use.
  • the weight ratio of at least one selected from heat-expandable microspheres and hollow particles in the composition is not particularly limited, but is preferably 0.01 to 70% by weight, more preferably 0.05 to 60% by weight, even more preferably 0.1 to 50% by weight, and particularly preferably 0.3 to 40% by weight. If the weight ratio is within the above range, a composition that is lightweight and maintains the physical properties of the base component can be obtained.
  • the composition of the present invention may be prepared by a conventionally known method, and examples of the method include a method of mechanically mixing the components uniformly using a mixer such as a homomixer, a static mixer, a Henschel mixer, a tumbler mixer, a planetary mixer, a kneader, a roll, a mixing roll, a mixer, a single-screw kneader, a twin-screw kneader, or a multi-screw kneader.
  • a mixer such as a homomixer, a static mixer, a Henschel mixer, a tumbler mixer, a planetary mixer, a kneader, a roll, a mixing roll, a mixer, a single-screw kneader, a twin-screw kneader, or a multi-screw kneader.
  • a mixer such as a homomixer, a
  • composition of the present invention particularly when it contains, together with the heat-expandable microspheres, a compound and/or a thermoplastic resin having a melting point lower than the expansion-initiation temperature of the heat-expandable microspheres as a base component, can be used as a masterbatch for molding resin and/or rubber.
  • thermoplastic resin constituting the base component contained in the masterbatch is not particularly limited, and examples thereof include waxes such as polyethylene wax and paraffin wax, thermoplastic resins such as ethylene-vinyl acetate copolymer (EVA), polyethylene, modified polyethylene, polypropylene, modified polypropylene, modified polyolefin, polyvinyl chloride (PVC), acrylic resin, thermoplastic polyurethane, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polystyrene (PS), polycarbonate, polyethylene terephthalate (PET), and polybutylene terephthalate (PBT); ionomer resins such as ethylene-based ionomers, urethane-based ionomers, styrene-based ionomers, and fluorine-based ionomers; and thermoplastic elastomers such as
  • the molding masterbatch is utilized in injection molding, extrusion molding, press molding, etc., and is suitably used as an air bubble introducing agent.
  • the base material component used in resin molding or rubber molding is not particularly limited as long as it is selected from the above-mentioned base material components.
  • the base material component examples include ethylene-vinyl acetate copolymer (EVA), polyethylene, modified polyethylene, polypropylene, modified polypropylene, modified polyolefin, 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.), modified polyamide, polycarbonate, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyacetal (POM), polyolefin, etc.
  • EVA ethylene-vinyl acetate copolymer
  • PVC polyvinyl chloride
  • AS resin acrylonitrile-styrene copolymer
  • ABS resin acrylonitrile-butadiene-styrene copolymer
  • the rubber composition examples include phenylene sulfide (PPS), polyphenylene ether (PPE), modified polyphenylene ether, ionomer resin, olefin-based elastomer, styrene-based elastomer, polyester-based elastomer, polylactic acid (PLA), cellulose acetate, polybutylene succinate (PBS), polyhydroxyalkanoate (PHA), starch resin, natural rubber, isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), nitrile rubber (NBR), butyl rubber, silicone rubber, acrylic rubber, urethane rubber, fluororubber, and ethylene-propylene-diene rubber (EPDM). These rubber compositions may be used alone or in combination of two or more.
  • PPS phenylene sulfide
  • PPE polyphenylene ether
  • composition of the present invention may contain other components as described above.
  • other components include fibrous materials such as glass fiber, carbon fiber, and natural fiber; inorganic powders such as talc, titanium oxide, silica, and inorganic pigments; polymeric fine particles such as acrylic fine particles, styrene fine particles, urethane fine particles, and silicone fine particles; organic pigments; organic powders; flame retardants; and chemical foaming agents.
  • the molded article of the present invention is obtained by molding the composition described above, and has little change in expansion ratio or specific gravity, excellent foaming stability, and is lightweight. Also, yellowing may be suppressed.
  • Examples of the molded article of the present invention include molded articles such as coating films and molded articles.
  • the molded article of the present invention has improved physical properties such as light weight, porosity, sound absorption, heat insulation, low thermal conductivity, low dielectric constant, design, impact absorption, strength, and chipping resistance.
  • the molded article is expected to have effects such as stabilization against sink marks and warping, reduction in molding shrinkage rate, and dimensional stability.
  • the molded body containing an inorganic substance as a base component can be further fired to obtain a ceramic filter or the like.
  • heat-expandable microspheres of the present invention will now be described in detail with reference to examples. 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. Furthermore, hereinafter, heat-expandable microspheres may be simply referred to as "microspheres”.
  • T s expansion start temperature
  • T max maximum expansion temperature
  • thermoplastic resins (A1) and (A2) 0.5 g of the microspheres were placed in a stainless steel evaporating dish with a diameter of 80 mm and a depth of 15 mm, 30 mL of tetrahydrofuran was added to disperse the microspheres uniformly, and the dish was left to stand at room temperature for 2 hours to immerse the microspheres in tetrahydrofuran. The dish was then heated in a far-infrared dryer at 110° C. for 2 hours to evaporate the tetrahydrofuran, producing a residual thermoplastic resin A1.
  • a box with a flat bottom, 12 cm long, 13 cm wide, and 9 cm high was made from aluminum foil, 0.5 g of microspheres were placed uniformly in it, and the box was covered with aluminum foil. This was placed in a gear oven and heated for 10 minutes at a temperature 20° C. higher than the maximum expansion temperature (T max ) of the microspheres to produce a heat-treated product.
  • T max maximum expansion temperature
  • 0.5 g of the resulting treated product was placed in a stainless steel evaporating dish with a diameter of 80 mm and a depth of 15 mm, 30 mL of tetrahydrofuran was added to disperse the treated product uniformly, and the treated product was immersed in tetrahydrofuran. The product was then heated in a far-infrared dryer at 110° C. for 2 hours to evaporate tetrahydrofuran, producing a residual thermoplastic resin A2.
  • the glass transition points Tg 0 and Tg 1 of the obtained thermoplastic resins A1 and A2 were measured in accordance with JIS K7121: 2012. Specifically, the measurement was performed as follows. 10 mg of the obtained thermoplastic resin was placed in an aluminum cup having an inner diameter of 3.5 mm and a depth of 1.63 mm, and an aluminum lid having a diameter of 2.88 mm and a thickness of 0.1 mm was placed on top of the thermoplastic resin and the lid was closed with a hand press to prepare a sample. Next, a PerkinElmer differential scanning calorimeter (Jade DSC) was used as the measuring device, and the prepared sample was held at 60° C.
  • Jade DSC PerkinElmer differential scanning calorimeter
  • thermoplastic resin for 3 minutes, and then heated from 60° C. to 300° C. at a rate of 10° C./min to obtain a DSC curve.
  • Alumina was used as the reference material.
  • Tg glass transition point
  • a 100 mL volumetric flask was emptied, dried, and the weight (WB1) of the volumetric flask was weighed.
  • the weighed volumetric flask was filled with isopropyl alcohol exactly up to the meniscus, and the weight (WB2) of the volumetric flask filled with 100 mL of isopropyl alcohol was weighed.
  • a 100 mL volumetric flask was emptied, dried, and the weight (WS1) of the volumetric flask was weighed.
  • the weighed volumetric flask was filled with about 50 mL of particle sample, and the weight (WS2) of the volumetric flask filled with the particle sample was weighed.
  • the weight (WS3) of the volumetric flask filled with the particle sample was weighed after the volumetric flask was filled with isopropyl alcohol exactly up to the meniscus without introducing air bubbles.
  • the obtained WB1, WB2, WS1, WS2 and WS3 were then introduced into the following formula to calculate the true specific gravity (d) of the particle sample.
  • d (g/mL) ⁇ (WS2-WS1) ⁇ (WB2-WB1)/100 ⁇ / ⁇ (WB2-WB1)-(WS3-WS2) ⁇
  • the measured true specific gravity was judged based on the following evaluation criteria, with a score of ⁇ or higher being considered a pass.
  • ⁇ The true specific gravity of the hollow particles obtained at the heating temperature (1) is less than 0.02 g/mL, and the ratio of the true specific gravity of the hollow particles obtained at the heating temperature (3) to the true specific gravity of the hollow particles obtained at the heating temperature (1) ((3)/(1)) is less than 1.7, and the hollow particles have excellent expandability and are excellent at suppressing changes in expandability over a wide temperature range.
  • Good The ratio of the true specific gravity of the hollow particles obtained at the heating temperature (3) to the true specific gravity of the hollow particles obtained at the heating temperature (1) ((3)/(1)) is less than 1.7, and the hollow particles are somewhat excellent in suppressing changes in expansiveness over a wide temperature range.
  • ⁇ The ratio of the true specific gravity of the hollow particles obtained at the heating temperature (3) to the true specific gravity of the hollow particles obtained at the heating temperature (1) ((3)/(1)) is 1.7 or more, and the expansion change cannot be suppressed over a wide temperature range.
  • Example 1 To 230 parts of ion-exchanged water, 60 parts of sodium chloride, 19 parts of colloidal silica containing 20% active ingredient, 0.6 parts of polyvinylpyrrolidone, 0.8 parts of an aqueous solution of ethylenediaminetetraacetic acid tetraNa salt containing 5% active ingredient, and 0.2 parts of an aqueous solution of aluminum chloride containing 10% active ingredient were added, and the pH of the resulting mixture was adjusted to 2.8 to 3.2 to prepare an aqueous dispersion medium.
  • the suspension was transferred to a 1.5-liter pressurized reaction vessel and purged with nitrogen, and then the initial reaction pressure was set to 0.3 MPa, and polymerization reaction was carried out at a polymerization temperature of 60° C. for 15 hours while stirring at 100 rpm. After polymerization, the product was filtered and dried to obtain heat-expandable microspheres 1. The physical properties of the resulting heat-expandable microspheres are shown in Table 1.
  • Example B Plate-shaped molded products were obtained by injection molding in the same manner as in Example A, except that the heat-expandable microspheres used in Example A were microspheres 9 and the molding temperature was changed to the maximum expansion temperature of the microspheres 9, a temperature 10° C. higher than the maximum expansion temperature, and a temperature 20° C. higher than the maximum expansion temperature.
  • the physical properties of the obtained molded products were evaluated in the same manner as in Example A. The results are shown in Table 3.

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Abstract

La présente invention a pour objet : des microsphères thermo-expansibles qui présentent peu de changement d'expansibilité sur une large plage de température ; et l'utilisation de celles-ci.　À cet effet, l'invention porte sur des microsphères thermo-expansibles qui comprennent chacune : une enveloppe externe qui contient une résine thermoplastique (A) ; et un agent moussant qui est contenu dans l'enveloppe externe et qui est vaporisé par chauffage. Les microsphères thermo-expansibles satisfont à la condition 1 décrite ci-dessous. Condition : Le point de transition vitreuse (Tg0) d'une résine thermoplastique (A1) qui est obtenue par immersion des microsphères thermo-expansibles dans du tétrahydrofurane et le point de transition vitreuse (Tg1) d'une résine thermoplastique (A2) qui est obtenue par immersion d'un matériau transformé, qui est obtenu par chauffage des microsphères thermo-expansibles à une température de 20 °C supérieure à leur température maximale d'expansion pendant 10 minutes, dans du tétrahydrofurane satisfont à la relation représentée par la formule (I). Formule (I) : (Tg1) - (Tg0) > 0 °C
PCT/JP2025/000005 2024-01-17 2025-01-06 Microsphères thermo-expansibles et utilisation de celles-ci Pending WO2025154555A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015178329A1 (fr) * 2014-05-23 2015-11-26 松本油脂製薬株式会社 Microsphères à dilatation thermique, leur procédé de production et d'utilisation
WO2016084612A1 (fr) * 2014-11-26 2016-06-02 松本油脂製薬株式会社 Microsphères thermo-expansibles et leur utilisation
WO2016190178A1 (fr) * 2015-05-27 2016-12-01 松本油脂製薬株式会社 Microsphères thermiquement dilatables et leur utilisation
WO2017141653A1 (fr) * 2016-02-19 2017-08-24 松本油脂製薬株式会社 Microsphères thermo-expansibles et leurs utilisations

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015178329A1 (fr) * 2014-05-23 2015-11-26 松本油脂製薬株式会社 Microsphères à dilatation thermique, leur procédé de production et d'utilisation
WO2016084612A1 (fr) * 2014-11-26 2016-06-02 松本油脂製薬株式会社 Microsphères thermo-expansibles et leur utilisation
WO2016190178A1 (fr) * 2015-05-27 2016-12-01 松本油脂製薬株式会社 Microsphères thermiquement dilatables et leur utilisation
WO2017141653A1 (fr) * 2016-02-19 2017-08-24 松本油脂製薬株式会社 Microsphères thermo-expansibles et leurs utilisations

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