Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
  • B01J13/02—Making microcapsules or microballoons
  • B01J13/06—Making microcapsules or microballoons by phase separation
  • B01J13/14—Polymerisation; cross-linking
  • B01J13/18—In situ polymerisation with all reactants being present in the same phase
  • B01J13/185—In situ polymerisation with all reactants being present in the same phase in an organic phase
• • 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
  • C08J9/20—Making expandable particles by suspension polymerisation in the presence of the blowing agent
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
  • B01J13/02—Making microcapsules or microballoons
  • B01J13/06—Making microcapsules or microballoons by phase separation
  • B01J13/14—Polymerisation; cross-linking
  • B01J13/18—In situ polymerisation with all reactants being present in the same phase
• • 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
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
• • 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
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
  • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
• • 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
  • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
• • 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
  • C08J9/12—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 physical blowing agent
  • C08J9/14—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 physical blowing agent organic
• • 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
  • C08J9/22—After-treatment of expandable particles; Forming foamed products
  • C08J9/228—Forming foamed products
  • C08J9/232—Forming foamed products by sintering 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
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2201/00—Foams characterised by the foaming process
  • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
  • C08J2201/03—Extrusion of the foamable blend
• • 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®
• • 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
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
• • 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
  • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2423/04—Homopolymers or copolymers of ethene
  • C08J2423/06—Polyethene

Definitions

• the present invention relates to a thermally expandable microcapsule, an expandable masterbatch using the thermally expandable microcapsule, and a foam molded article.
• foaming agents have been used to foam materials with the aim of reducing the weight and increasing the functionality of resin materials.
• foaming agents include thermally expandable microcapsules and chemical foaming agents.
• Thermally expandable microcapsules are used in a wide range of applications as designability-imparting agents and weight-weighting agents, and are also used in paints for the purpose of weight reduction, such as foaming inks and wallpapers.
• thermally expandable microcapsules those in which a thermoplastic shell polymer contains a volatile expanding agent that becomes gaseous at a temperature below the softening point of the shell polymer are widely known.
• Patent Literature 1 describes that in microspheres in which a foaming agent is enclosed in the outer shell, the average particle size of the microspheres and the amount of the foaming agent are set to a predetermined relational expression.
• Patent Document 2 describes a resin composition containing hollow particles and an organic base resin, in which the volume ratio of the amount of air contained in the hollow particles is 30% or more of the total hollow particles. It is
• thermally expandable microcapsules have a problem of uniformity after foaming.
• the surface of the resulting foamed molded article becomes rough unless the foam is uniformly expanded, causing surface unevenness and significantly impairing the surface properties.
• the foaming ratio is low and the foaming ratio varies, resulting in poor functionality such as light weight.
• the present disclosure (1) is a thermally expandable microcapsule in which a volatile expanding agent is encapsulated as a core agent in the shell, and a volumetric particle size is integrated under a sieve using a laser diffraction/scattering particle size distribution analyzer.
• a volumetric particle size is integrated under a sieve using a laser diffraction/scattering particle size distribution analyzer.
• D10/D50 is 0.6 or more and 1.0 and a D99/D50 of 1.0 or more and 2.0 or less.
• the volume conversion ratio of D99 and D50 [(D99) 3 /(D50) 3 ] is 1.0 or more and 8.0 or less
• the thermally expandable microcapsule according to the present disclosure (1) is.
• the value obtained by dividing the difference between D99 and D10 by D50 [(D99-D10)/D50] is 0 or more and 1.4 or less
• the heat according to (1) or (2) of the present disclosure It is an expandable microcapsule.
• the present disclosure (4) is the thermally expandable microcapsule according to any one of the present disclosure (1) to (3), having a D99 of 15 ⁇ m or more and 80 ⁇ m or less.
• the present disclosure (5) is the thermally expandable microcapsule according to any one of the present disclosure (1) to (4), wherein the shell is made of a polymer of a monomer composition containing a nitrile monomer.
• the present disclosure (6) is the thermally expandable microcapsule according to any one of the present disclosure (1) to (5), wherein the shell thickness ratio (minimum shell thickness/maximum shell thickness) is 0.4 or more. be.
• the present disclosure (7) is an expandable masterbatch containing the thermally expandable microcapsules according to any one of the present disclosures (1) to (6) and a thermoplastic resin.
• the present disclosure (8) uses the thermally expandable microcapsules according to any one of the present disclosure (1) to (6) or the foamable masterbatch according to the present disclosure (7), a foamed molded product is.
• the present invention will be described in detail below.
• the thermally expandable microcapsules of the present invention are composed of a shell and a volatile expanding agent enclosed as a core agent.
• the shell constituting the thermally expandable microcapsule of the present invention preferably contains a polymer compound.
• the polymer compound is preferably a polymer containing a unit derived from a nitrile-based monomer, and a unit derived from a nitrile-based monomer, a monomer having a carboxyl group, and / or a (meth)acrylic acid ester monomer.
• the polymer compound is preferably a polymer of a monomer composition containing a nitrile-based monomer, and a monomer containing a nitrile-based monomer and a monomer having a carboxyl group and/or a (meth)acrylic acid ester monomer. It is preferably a polymer of the composition.
• the nitrile-based monomer is not particularly limited, and examples thereof include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -ethoxyacrylonitrile, fumaronitrile, and mixtures thereof. Among these, acrylonitrile and methacrylonitrile are particularly preferred. These may be used alone or in combination of two or more.
• the preferable lower limit of the nitrile-based monomer content in the monomer composition is 20% by weight, and the preferable upper limit is 99% by weight. By making it 20% by weight or more, the gas barrier property of the shell can be enhanced and the foaming ratio can be improved. By making it 99% by weight or less, heat resistance can be improved and yellowing can be prevented. A more preferable lower limit is 30% by weight, and a more preferable upper limit is 98% by weight.
• a radically polymerizable unsaturated carboxylic acid monomer having a carboxyl group and having 3 to 8 carbon atoms can be used.
• Specific examples thereof include unsaturated dicarboxylic acids, anhydrides thereof, monoesters of unsaturated dicarboxylic acids, and derivatives thereof. These may be used alone or in combination of two or more.
• Examples of the unsaturated dicarboxylic acid include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid and cinnamic acid, maleic acid, itaconic acid, fumaric acid, citraconic acid and chloromaleic acid. .
• monoesters of unsaturated dicarboxylic acids include monomethyl maleate, monoethyl maleate, monobutyl maleate, monomethyl fumarate, monoethyl fumarate, monomethyl itaconate, monoethyl itaconate, and monobutyl itaconate.
• acrylic acid, methacrylic acid, maleic acid, maleic anhydride, and itaconic acid are particularly preferred.
• a preferred lower limit to the content of the carboxyl group-containing monomer in the monomer composition is 5% by weight, and a preferred upper limit is 50% by weight. By making it 5% by weight or more, the maximum foaming temperature can be raised, and by making it 50% by weight or less, it is possible to improve the expansion ratio.
• a more preferable lower limit is 10% by weight, and a more preferable upper limit is 30% by weight.
• (meth)acrylic acid ester is preferable, and in particular, methyl methacrylate, ethyl methacrylate, methacrylic acid alkyl esters such as n-butyl methacrylate, or cyclohexyl methacrylate, methacrylic acid Alicyclic/aromatic/heterocyclic ring-containing methacrylic acid esters such as benzyl acid and isobornyl methacrylate are preferred.
• a preferable lower limit of the content of the (meth)acrylate monomer in the monomer composition is 0.1% by weight, and a preferable upper limit thereof is 25% by weight.
• the content of the other monomer 0.1% by weight or more, the dispersibility of the composition using the thermally expandable microcapsules can be improved, and by making it 25% by weight or less, the cell wall It is possible to improve the gas barrier property of the material and improve the thermal expansion property.
• a more preferable lower limit to the content of the (meth)acrylate monomer is 0.3% by weight, and a more preferable upper limit is 22% by weight.
• the monomer composition preferably contains a crosslinkable monomer having two or more double bonds in the molecule.
• the crosslinkable monomer has a role as a crosslinker.
• crosslinkable monomer examples include monomers having two or more radically polymerizable double bonds, and specific examples thereof include divinylbenzene, di(meth)acrylate, trifunctional or higher (meth)acrylate, and the like.
• di(meth)acrylate examples include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di (Meth)acrylate and the like.
• a di(meth)acrylate of polyethylene glycol having a weight average molecular weight of 200 to 600 may be used.
• trifunctional (meth)acrylate examples include trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and triallylformal tri(meth)acrylate. mentioned. Moreover, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are mentioned as said tetra- or more functional (meth)acrylate. Among these, a trifunctional one such as trimethylolpropane tri(meth)acrylate and a bifunctional (meth)acrylate such as polyethylene glycol can be crosslinked relatively uniformly in the acrylonitrile-based shell. applied.
• a preferable lower limit of the content of the crosslinkable monomer in the monomer composition is 0.1% by weight, and a preferable upper limit thereof is 1.0% by weight.
• a preferable upper limit thereof is 1.0% by weight.
• the monomer composition preferably contains a monomer other than the nitrile-based monomer, the monomer having a carboxyl group, the (meth)acrylic acid ester monomer, and the crosslinkable monomer.
• a monomer other than the nitrile-based monomer the monomer having a carboxyl group
• the (meth)acrylic acid ester monomer the crosslinkable monomer.
• the miscibility between the thermally expandable microcapsules and the matrix resin such as a thermoplastic resin is improved, and the foamed molded article using the thermally expandable microcapsules has an excellent appearance.
• examples of other monomers include vinyl monomers such as vinyl chloride, vinylidene chloride, vinyl acetate, and styrene. These may be used alone or in combination of two or more.
• the monomer composition may contain a thermosetting resin in addition to the nitrile-based monomer, the monomer having a carboxyl group, the (meth)acrylic acid ester monomer, the crosslinkable monomer, and other monomers.
• a thermosetting resin examples include epoxy resin, phenol resin, melamine resin, urea resin, polyimide resin, and bismaleimide resin. Among these, epoxy resins and phenol resins are preferred.
• the epoxy resin is not particularly limited, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, glycidylamine type epoxy resin, and the like. mentioned.
• the phenol resins include novolac-type phenol resins, resol-type phenol resins, and benzylic ether-type phenol resins. Among these, novolak type phenolic resins are preferred.
• the thermosetting resin preferably has two or more functional groups that react with carboxyl groups in one molecule. By having two or more functional groups that react with the carboxyl group, the curability of the thermosetting resin can be made stronger.
• the monomer composition contains a monomer having a carboxyl group
• the carboxyl group and the thermosetting resin are more strongly bonded by the heat generated during heating and foaming, thereby greatly improving heat resistance and durability. It is possible to
• the thermosetting resin preferably does not have a radically polymerizable double bond.
• Examples of functional groups that react with the carboxyl groups include glycidyl groups, phenol groups, methylol groups, and amino groups. Among them, a glycidyl group is preferred.
• the functional group that reacts with the carboxyl group the same type may be used, or two or more types may be used.
• a preferable lower limit of the content of the thermosetting resin in the monomer composition is 0.01% by weight, and a preferable upper limit thereof is 30% by weight.
• a preferable lower limit of the content of the thermosetting resin in the monomer composition is 0.01% by weight, and a preferable upper limit thereof is 30% by weight.
• a polymerization initiator is added to the monomer composition to polymerize the monomers.
• the polymerization initiator for example, dialkyl peroxide, diacyl peroxide, peroxyester, peroxydicarbonate, azo compound and the like are preferably used. Specific examples include, for example, methyl ethyl peroxide, di-t-butyl peroxide, dialkyl peroxide such as dicumyl peroxide; isobutyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5 , 5-trimethylhexanoyl peroxide and other diacyl peroxides.
• t-butyl peroxypivalate t-hexyl peroxypivalate, t-butyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate noate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate and the like.
• peroxyesters such as cumyl peroxyneodecanoate, ( ⁇ , ⁇ -bis-neodecanoylperoxy)diisopropylbenzene; bis(4-t-butylcyclohexyl)peroxydicarbonate, di-n-propyl - oxydicarbonate, diisopropyl peroxydicarbonate and the like.
• peroxydicarbonates such as di(2-ethylethylperoxy)dicarbonate, dimethoxybutylperoxydicarbonate, and di(3-methyl-3-methoxybutylperoxy)dicarbonate are included.
• a preferable lower limit of the weight average molecular weight of the polymer compound constituting the shell is 100,000, and a preferable upper limit thereof is 2,000,000. If it is less than 100,000, the strength of the shell may decrease, and if it exceeds 2,000,000, the strength of the shell may become too high and the expansion ratio may decrease.
• the shell may further contain a stabilizer, an ultraviolet absorber, an antioxidant, an antistatic agent, a flame retardant, a silane coupling agent, a coloring agent, and the like, if necessary.
• the thermally expandable microcapsules of the present invention contain a volatile expanding agent as a core agent in the shell.
• the volatile expanding agent is a substance that becomes gaseous at a temperature below the softening point of the polymer that constitutes the shell, and is preferably a low boiling point organic solvent.
• volatile swelling agent examples include hydrocarbons having less than 8 carbon atoms, hydrocarbons having 8 or more carbon atoms, petroleum ether, chlorofluorocarbons, tetraalkylsilanes, and the like.
• hydrocarbons having less than 8 carbon atoms include ethane, ethylene, propane, propene, n-butane, isobutane, butene, isobutene, n-pentane, isopentane, neopentane, n-hexane, and heptane.
• hydrocarbons having 8 or more carbon atoms examples include isooctane, octane, decane, isododecane, dodecane, and hexanedecane.
• chlorofluorocarbon examples include CCl 3 F, CCl 2 F 2 , CClF 3 , CClF 2 —CClF 2 and the like.
• tetraalkylsilane include tetramethylsilane, trimethylethylsilane, trimethylisopropylsilane, and trimethyl-n-propylsilane.
• isobutane, n-butane, n-pentane, isopentane, n-hexane, and mixtures thereof are preferred.
• These volatile swelling agents may be used in combination of two or more.
• hydrocarbons having less than 8 carbon atoms and hydrocarbons having 8 or more carbon atoms may be used in combination.
• pentane and isooctane it is preferable to use a combination of pentane and isooctane.
• a thermally decomposable compound that is thermally decomposed by heating into a gaseous state may be used.
• the content of the core agent is preferably 15 to 30% by weight. Within the above range, the foaming ratio can be improved while being excellent in durability against shearing during molding. A more preferable lower limit to the core agent content is 18% by weight, and a more preferable upper limit is 24% by weight.
• the preferred lower limit of the foaming start temperature (Ts) is 110°C, and the preferred upper limit is 250°C.
• Ts foaming start temperature
• the resin temperature will cool during the core-back foaming process. It is possible to prevent the foaming ratio from increasing.
• a more preferable lower limit is 120°C, and a more preferable upper limit is 180°C.
• the maximum foaming temperature (Tmax) preferably has a lower limit of 130°C and a preferred upper limit of 270°C.
• Tmax preferably has a lower limit of 130°C and a preferred upper limit of 270°C.
• heat resistance can be enhanced, and bursting and shrinkage of the thermally expandable microcapsules can be prevented in a high temperature region or during molding.
• foaming due to shearing does not occur during the production of masterbatch pellets, and unfoamed masterbatch pellets can be produced stably.
• a more preferable lower limit is 150°C
• a still more preferable lower limit is 160°C
• a more preferable upper limit is 230°C
• a further preferable upper limit is 225°C.
• the maximum foaming temperature is the temperature at which the diameter of the thermally expandable microcapsules is maximized (maximum displacement) when the diameter of the thermally expandable microcapsules is measured while being heated from room temperature. means temperature.
• the maximum displacement (Dmax) preferably has a lower limit of 300 ⁇ m and a preferred upper limit of 2000 ⁇ m. Within the above range, a moderate expansion ratio can be obtained, and desired foaming performance can be obtained.
• the thermally expandable microcapsules of the present invention have a particle diameter of D10 at a cumulative frequency of 10 vol% and a D10/D50 is 0.6 or more and 1.0 or less, where D50 is the particle diameter and D99 is the particle diameter at a cumulative frequency of 99% by volume.
• D10/D50 is 0.6 or more, the proportion of fine powder contained in the thermally expandable microcapsules can be reduced, and the foamability can be increased.
• a preferable lower limit of D10/D50 is 0.62, a more preferable lower limit is 0.63, a still more preferable lower limit is 0.65, and a preferable upper limit is 1.0, for example, 0.9 or less.
• the thermally expandable microcapsules of the present invention have a particle diameter of D10 at a cumulative frequency of 10 vol% and a D99/D50 is 1.0 or more and 2.0 or less, where D50 is the particle diameter and D99 is the particle diameter at a cumulative frequency of 99% by volume.
• the preferred upper limit of D99/D50 is 2.0, the more preferred upper limit is 1.9, the still more preferred upper limit is 1.8, the even more preferred upper limit is 1.75, and the preferred lower limit is 1.2, such as 1.3. That's it.
• the above “D10/D50” and “D99/D50” are calculated from the particle size based on the cumulative frequency, and the CV value (standard deviation / average value), which is an index of general variation, is a numerical value. They differ in meaning and calculation method.
• the above "D50” is a particle diameter based on a cumulative frequency of 50% by volume, and is different from the average particle diameter (arithmetic mean value of particle diameters) usually used.
• heat-expandable microcapsules are granulated by a method such as suspension polymerization, so there is generally a discrepancy between "D50” and "average particle size.”
• D50 heat-expandable microcapsules
• average particle size there is generally a discrepancy between "D50” and "average particle size.”
• D99 instead of "D90” it can be used as a standard for obtaining the effects of the present invention rather than as a mere measure of variation.
• the thermally expandable microcapsules of the present invention have a particle diameter of D50 at a cumulative frequency of 50% by volume and a cumulative frequency of 99% by volume in the cumulative distribution under the sieve of the volume-based particle diameter using a laser diffraction/scattering particle size distribution analyzer.
• the volume conversion ratio of D99 and D50 [(D99) 3 /(D50) 3 ] is preferably 1.0 or more.
• the volume conversion ratio of D99 to D50 is, for example, 2 or more, preferably 8.0 or less, more preferably 7.5 or less, and still more preferably 7.0 or less.
• (D99) 3 /(D50) 3 is equal to or less than the upper limit, the molded product using the thermally expandable microcapsules can have a smoother surface.
• the thermally expandable microcapsules of the present invention have a particle diameter of D10 at a cumulative frequency of 10 vol% and a
• the value obtained by dividing the difference between D99 and D10 by D50 [(D99 ⁇ D10)/D50] is preferably 0 or more, for example 0. It is 5 or more, preferably 1.4 or less, more preferably 1.3 or less, and still more preferably 1.2 or less.
• the (D99-D10)/D50 is equal to or less than the upper limit, the molded product using the thermally expandable microcapsules can have a smoother surface.
• the preferred lower limit of D10 is 1.0 ⁇ m, the more preferred lower limit is 5.0 ⁇ m, the still more preferred lower limit is 8.0 ⁇ m, the preferred upper limit is 40 ⁇ m, the more preferred upper limit is 30 ⁇ m, and the more preferred lower limit is 30 ⁇ m.
• the upper limit is 25 ⁇ m.
• the preferred lower limit of D50 is 5 ⁇ m, the more preferred lower limit is 8 ⁇ m, the more preferred lower limit is 10 ⁇ m, the preferred upper limit is 60 ⁇ m, the more preferred upper limit is 50 ⁇ m, and the further preferred upper limit is 40 ⁇ m.
• An even more preferred upper limit is 30 ⁇ m.
• the thermally expandable microcapsules of the present invention have a preferred lower limit of D99 of 10 ⁇ m, a more preferred lower limit of 15 ⁇ m, a still more preferred lower limit of 20 ⁇ m, a preferred upper limit of 80 ⁇ m, a more preferred upper limit of 70 ⁇ m, and a further preferred upper limit of 60 ⁇ m. be.
• D99 is equal to or higher than the lower limit
• good foamability can be obtained
• the D99 is equal to or lower than the upper limit
• good surface properties can be obtained.
• the above “D10” means that the cumulative frequency of distribution from the small particle side reaches 10% by volume in the integrated distribution under the sieve of the volume-converted particle diameter using a laser diffraction/scattering particle size distribution analyzer. is the particle size of
• “D50” is the particle diameter at which the cumulative frequency of distribution reaches 50% by volume
• “D99” is the particle diameter at which the cumulative frequency of distribution reaches 99% by volume. That is. D10, D50, and D99 can be measured using, for example, a laser diffraction/scattering particle size distribution analyzer (LA-950, manufactured by Horiba, Ltd.).
• the shell thickness ratio (minimum shell thickness/maximum shell thickness) has a preferred lower limit of 0.3, a more preferred lower limit of 0.4, a preferred upper limit of 1.0, and a more preferred upper limit of 0.9. Within the above range, gas generated from the volatile expanding agent during foaming is less likely to escape, and foamability is improved.
• the shell thickness ratio can be measured by observing the cross section of the thermally expandable microcapsule with an SEM or the like and calculating the minimum shell thickness/maximum shell thickness.
• the intermediate shell thickness [(maximum shell thickness + minimum shell thickness)/2] preferably has a lower limit of 1 ⁇ m, a more preferred lower limit of 2 ⁇ m, a preferred upper limit of 10 ⁇ m, and a more preferred upper limit of 6 ⁇ m. is.
• the “intermediate shell thickness” can be calculated from the “maximum shell thickness” and the “minimum shell thickness” measured by the "shell thickness ratio".
• the method for producing the thermally expandable microcapsules of the present invention is not particularly limited.
• a step of preparing an aqueous medium, a monomer composition containing a nitrile monomer, a monomer having a carboxyl group, a crosslinkable monomer, and other monomers, and an oily mixture containing a volatile swelling agent. can be produced by performing a step of dispersing in an aqueous medium and a step of polymerizing the above monomer.
• microcapsules can be produced.
• the first step is to prepare an aqueous medium.
• an aqueous dispersion medium containing a dispersion stabilizer is prepared by adding water, a dispersion stabilizer, and, if necessary, a co-stabilizer to a polymerization reactor. Also, if necessary, alkali metal nitrite, stannous chloride, stannic chloride, potassium dichromate, etc. may be added.
• dispersion stabilizer examples include silica such as colloidal silica, calcium phosphate, magnesium hydroxide, aluminum hydroxide, ferric hydroxide, barium sulfate, calcium sulfate, sodium sulfate, calcium oxalate, calcium carbonate, barium carbonate, Magnesium carbonate etc. are mentioned.
• silica such as colloidal silica, calcium phosphate, magnesium hydroxide, aluminum hydroxide, ferric hydroxide, barium sulfate, calcium sulfate, sodium sulfate, calcium oxalate, calcium carbonate, barium carbonate, Magnesium carbonate etc. are mentioned.
• the amount of the dispersion stabilizer to be added is not particularly limited, and is appropriately determined depending on the type of the dispersion stabilizer, the particle size of the microcapsules, etc., but the preferred lower limit is 0.1 parts by weight with respect to 100 parts by weight of the monomer.
• the upper limit is 20 parts by weight.
• co-stabilizer examples include a condensation product of diethanolamine and an aliphatic dicarboxylic acid, and a condensation product of urea and formaldehyde. Also included are water-soluble nitrogen-containing compounds, polyethylene oxide, polyethyleneimine, tetramethylammonium hydroxide, gelatin, methylcellulose, polyvinyl alcohol, dioctylsulfosuccinate, sorbitan ester, various emulsifiers and the like.
• water-soluble nitrogen-containing compound examples include polydialkylaminoalkyl (meth)acrylates represented by polyvinylpyrrolidone, polyethyleneimine, polyoxyethylenealkylamine, polydimethylaminoethyl methacrylate and polydimethylaminoethyl acrylate. . Also included are polydialkylaminoalkyl(meth)acrylamides represented by polydimethylaminopropylacrylamide and polydimethylaminopropylmethacrylamide, polyacrylamide, polycationic acrylamide, polyaminesulfone, polyallylamine, and the like. Among these, polyvinylpyrrolidone is preferably used.
• the combination of the dispersion stabilizer and the co-stabilizer is not particularly limited, and examples include a combination of colloidal silica and a condensation product, a combination of colloidal silica and a water-soluble nitrogen-containing compound, and magnesium hydroxide or calcium phosphate. A combination with an emulsifier and the like are included. Among these, a combination of colloidal silica and a condensation product is preferred. Further, the condensation product is preferably a condensation product of diethanolamine and an aliphatic dicarboxylic acid, particularly preferably a condensation product of diethanolamine and adipic acid or a condensation product of diethanolamine and itaconic acid.
• the amount of colloidal silica to be added is appropriately determined according to the particle diameter of the thermally expandable microcapsules, but the preferred lower limit is 1 part by weight and the preferred upper limit is 10 parts by weight with respect to 100 parts by weight of the oil phase. A more preferable lower limit is 2 parts by weight, and a more preferable upper limit is 5 parts by weight. Also, the amount of the condensation product or water-soluble nitrogen-containing compound is appropriately determined depending on the particle size of the thermally expandable microcapsules, but the preferable lower limit is 0.05 parts by weight with respect to 100 parts by weight of the oil phase. The upper limit is 1 part by weight.
• Inorganic salts such as sodium chloride and sodium sulfate may be added in addition to the dispersion stabilizer and co-stabilizer. By adding an inorganic salt, thermally expandable microcapsules having a more uniform particle shape can be obtained.
• the amount of the inorganic salt added is preferably 0 to 100 parts by weight per 100 parts by weight of the monomer.
• the aqueous dispersion medium containing the dispersion stabilizer is prepared by blending the dispersion stabilizer and co-stabilizer with deionized water, and the pH of the aqueous phase at this time is determined by the type of dispersion stabilizer and co-stabilizer used. can be determined as appropriate.
• the type of dispersion stabilizer and co-stabilizer used can be determined as appropriate.
• silica such as colloidal silica
• polymerization is carried out in an acidic medium. ⁇ 4.
• magnesium hydroxide or calcium phosphate the polymerization is carried out in an alkaline medium.
• a monomer composition containing a nitrile monomer, a monomer having a carboxyl group, a crosslinkable monomer, and other monomers, and a volatile expanding agent are included.
• a step of dispersing the oily mixture in an aqueous medium is performed.
• the monomer composition and the volatile swelling agent may be separately added to the aqueous dispersion medium to prepare an oily mixture in the aqueous dispersion medium, but usually the two are mixed in advance to form an oily mixture. and then added to the aqueous dispersion medium.
• an oily mixed solution and an aqueous dispersion medium are prepared in advance in separate containers, and the oily mixed solution is dispersed in the aqueous dispersion medium by stirring and mixing in another container, and then added to the polymerization reaction vessel. You may add.
• a polymerization initiator is used to polymerize the monomers. The polymerization initiator may be added in advance to the oily mixture, and the aqueous dispersion medium and the oily mixture are placed in a polymerization reaction vessel. may be added after stirring and mixing.
• the monomer composition contains a polymerization initiator for polymerizing the monomers.
• a polymerization initiator for example, dialkyl peroxide, diacyl peroxide, peroxyester, peroxydicarbonate, azo compound and the like are preferably used.
• t-butyl peroxypivalate or 2,2'-azobisisobutyronitrile is preferably used as a polymerization initiator in order to preferentially polymerize acrylonitrile. This makes it possible to increase the proportion of polyacrylonitrile with high plasticizer resistance compared to polymethacrylonitrile.
• a method for dispersing the oily mixture in the aqueous dispersion medium a method of stirring with a homogenizer (manufactured by Tokushu Kika Kogyo Co., Ltd.) or the like, or a method of using a line mixer or an element block type static disperser (static mixer). Examples include a method of passing through a stationary dispersing device.
• the static dispersing device may be supplied with the aqueous dispersion medium and the polymerizable mixture separately, or may be supplied with a previously mixed and stirred dispersion.
• an element block type static disperser (hereinafter simply referred to as a block type static disperser) It is preferable to disperse by using (also called).
• a block type static disperser In the conventional suspension polymerization by stirring and mixing using a stirring blade or a batch-type high-speed rotation high-shear disperser, the mixing becomes locally non-uniform, and thermally expandable microcapsules containing coarse particles are obtained. There is a problem. Thermally expandable microcapsules with less coarse particles and less fine powder can be provided by polymerizing the droplets obtained by adjusting the pore size and flow rate using the block-type static disperser.
• an oil mixture and an aqueous dispersion medium are previously prepared in separate containers as a primary dispersion, and then put into the block-type static disperser under pressure.
• a block-type static disperser static mixer
• a plurality of plate-like blocks having a large number of holes formed therein are mounted in a tubular body having both ends opened.
• a plurality of adjacent plate-like blocks are superimposed so that the centers of the holes of the adjacent plate-like blocks do not align with each other, but at least a part of the mutual openings face each other. It is structured.
• the number of blocks When dispersion is carried out using the block-type static disperser, it is preferable to set the number of blocks, the number of holes present in the block (the number of holes in the block), and the hole diameter of the block, in addition to the flow rate.
• the flow rate when using the block-type static disperser is preferably 50 to 200 L/min.
• the number of blocks is preferably 10 or more and 20 or less.
• the block hole diameter is preferably 1 mm or more and 3 mm or less.
• the number of block holes is preferably 65 or more and 85 or less.
• the rotation speed is preferably 6000 rpm or more and 12000 rpm or less, more preferably 8000 rpm or more and 10000 rpm or less.
• the stirring time is preferably 5 minutes or more and 60 minutes or less, more preferably 6 minutes or more and 25 minutes or less.
• the thermally expandable microcapsules of the present invention can be produced by, for example, heating the dispersion liquid obtained through the above-described steps to polymerize the monomers.
• the polymerization temperature is preferably 50 to 90°C.
• the polymerization temperature may be a constant temperature during the polymerization, or may be increased stepwise in a plurality of times.
• the polymerization pressure is preferably 0.5 to 1.0 MPa when pressurized with nitrogen.
• the polymerization pressure is set to the above, it is preferable to perform nitrogen substitution or vacuum operation before that.
• a classification step may be performed after performing the above steps.
• the classification process include vibrating screen classifier, electromagnetic vibration classifier, sonic classifier, sieve classification using a JIS standard sieve, dry classification (air force classification), wet classification, and the like. be done.
• dry classification air classification refers to a method of classifying particles using an air flow.
• the above wet classification includes gravity classification (classification based on the sedimentation velocity difference in the liquid), hydraulic classification (classification by adding water flow in the direction opposite to the sedimentation direction of the particles), centrifugal classification (sedimentation velocity difference in the Classification using ) and the like.
• a foamable masterbatch containing the thermally expandable microcapsules of the present invention and a thermoplastic resin (base resin) is also one aspect of the present invention.
• thermoplastic resin used for the base resin is not particularly limited, and thermoplastic resins used for ordinary foam molding can be used.
• specific examples of the thermoplastic resin include, for example, polyolefins such as low-density polyethylene (LDPE) and polypropylene (PP), ethylene-vinyl acetate copolymer (EVA), vinyl chloride, polystyrene, thermoplastic elastomers, ethylene- Examples include methyl methacrylate copolymer (EMMA).
• thermoplastic elastomer examples include a styrene thermoplastic elastomer (abbreviated as SBC; hereinafter, abbreviated symbols are shown in parentheses), an olefinic thermoplastic elastomer (TPO), an olefinic dynamically crosslinked elastomer (TPV), Urethane-based thermoplastic elastomer (TPU), ester-based thermoplastic elastomer (TPEE), amide-based thermoplastic elastomer (TPAE), and the like are included.
• SBC styrene thermoplastic elastomer
• TPO olefinic thermoplastic elastomer
• TPV olefinic dynamically crosslinked elastomer
• TPU Urethane-based thermoplastic elastomer
• TPEE ester-based thermoplastic elastomer
• TPAE amide-based thermoplastic elastomer
• styrene-based thermoplastic elastomer examples include styrene-isobutylene block copolymer (SIB), styrene-isobutylene-styrene block copolymer (SIBS), styrene-isoprene-styrene block copolymer (SIS), styrene- Butadiene-styrene block copolymer (SBS), styrene-butadiene/butylene-styrene block copolymer (SBBS), styrene-ethylene/propylene-styrene block copolymer (SEPS), styrene-ethylene/butene-styrene block copolymer polymer (SEBS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), and the like.
• SIB styrene-isobuty
• the content of the thermally expandable microcapsules in the foamable masterbatch is not particularly limited, but the preferred lower limit is 10 parts by weight and the preferred upper limit is 90 parts by weight with respect to 100 parts by weight of the thermoplastic resin.
• the method for producing the foamable masterbatch is not particularly limited, but for example, raw materials such as a base resin such as a thermoplastic resin and various additives are kneaded in advance using a co-rotating twin-screw extruder or the like. Next, the kneaded product obtained by heating to a predetermined temperature, adding a foaming agent such as a thermally expandable microcapsule, and further kneading is cut into a desired size by a pelletizer to form a master.
• a batch method and the like can be mentioned.
• a pellet-shaped masterbatch may be produced by kneading raw materials such as a base resin such as a thermoplastic resin and thermally expandable microcapsules with a batch-type kneader and then granulating the mixture with a granulator.
• the kneader is not particularly limited as long as it can knead the heat-expandable microcapsules without breaking them, and examples thereof include a pressure kneader and a Banbury mixer.
• a foamed molded product using the thermally expandable microcapsules and foaming masterbatch of the present invention is also one aspect of the present invention.
• the heat-expandable microcapsules of the present invention have excellent surface properties, so that a foamed sheet having a high appearance quality such as an uneven shape can be obtained, and can be suitably used for residential wallpaper and the like.
• the thermally expandable microcapsules of the present invention or an expandable masterbatch containing the thermally expandable microcapsules of the present invention are kneaded with a matrix resin and molded to obtain a foamed molded product.
• the method for molding the foam molded article is not particularly limited, and examples thereof include kneading molding, calendar molding, extrusion molding, injection molding and the like.
• the method is not particularly limited, and the short-short method, in which a part of the resin material is put into the mold and foamed, or the core-back method, in which the mold is fully filled with the resin material and then opened to the desired foaming point. etc.
• the matrix resin the same resin as the base resin can be used.
• the thermally expandable microcapsules, the expandable masterbatch and the foamed molded product of the present invention are, for example, in the above-described forms, automotive interior materials such as door trims and instrument panels, automotive exterior materials such as bumpers, wallpaper, and wood powder. It can be advantageously used for building materials such as plastics, shoe soles, artificial cork, and the like. It can also be used as a paint or an adhesive. Furthermore, it can also be used for thermal release tapes and the like in the field of semiconductors.
• the thermally expandable microcapsule from which a foamed molded article having a uniform surface and excellent lightness can be produced. Also, a foamable masterbatch and a foamed molded article can be obtained using the thermally expandable microcapsules. Furthermore, when forming a foam thin film with a thickness of about 0.5 mm, the problem of surface roughness is more likely to occur than the problem of foamability, and when forming a foam molded product with a thickness of about 3 mm, the problem of surface roughness Also, the problem of foamability becomes remarkable.
• the thermally expandable microcapsules of the present invention can improve both the problems of surface roughness and foamability, and can be used regardless of the thickness of the resulting molded product. In addition, according to the present invention, it is possible to improve not only the uniformity of the surface shape, but also the unevenness of the surface.
• composition 1 [aqueous dispersion medium, oily mixture]) After adding 300 g of colloidal silica having a solid content of 20% by weight, 7 g of polyvinylpyrrolidone, and 600 g of sodium chloride to 2,000 g of ion-exchanged water and mixing, the pH was adjusted to 3.5 to prepare an aqueous dispersion medium. 160 g of acrylonitrile, 180 g of methacrylonitrile, 250 g of methacrylic acid, 160 g of methyl methacrylate, and 6 g of trimethylolpropane trimethacrylate were mixed to obtain a uniform monomer composition. To this, 10 g of 2,2'-azobisisobutyronitrile, 200 g of normal pentane and 50 g of isooctane were added and mixed in an autoclave to obtain an oily mixture.
• composition 2 [aqueous dispersion medium, oily mixture]
• Composition 2 [aqueous dispersion medium, oily mixture] was obtained in the same manner as composition 1 except that the composition shown in Table 1 was mixed with the oily mixture and the aqueous dispersion medium.
• the unit in Table 1 is g
• Example 1 (Production of thermally expandable microcapsules)
• the oily mixture obtained in composition 1 was placed in tank 1, and the aqueous dispersion medium was placed in tank 2.
• the oily mixture in tank 1 was placed in tank 2 and mixed to obtain a primary dispersion.
• the resulting primary dispersion was passed through a static block disperser at a flow rate of 120 L/min.
• the liquid that passed through was fed into the autoclave.
• the block-type stationary disperser used was a plate-like block with 70 holes and a hole diameter of 2 mm.
• the number of blocks was set to 20. Thereafter, the atmosphere was purged with nitrogen and reacted at a reaction temperature of 60° C. for 15 hours.
• the reaction pressure was 0.5 MPa, and the stirring was performed at 200 rpm. Furthermore, 8000 L of the obtained polymerized slurry is divided and supplied to the compression dehydrator, and after dehydration, a predetermined amount of washing water is supplied to the dehydrator. got
• Example 6 The oily mixture obtained in Composition 1 and the aqueous dispersion medium were put into a tank and mixed using a homogenizer (Homomixer manufactured by Primix) at a rotation speed of 10000 rpm and a stirring time of 10 minutes. Thereafter, the atmosphere was purged with nitrogen and reacted at a reaction temperature of 60° C. for 15 hours. The reaction pressure was 0.5 MPa, and the stirring was performed at 200 rpm. Further, 8000 L of the obtained polymerized slurry was divided and supplied to the dehydrating press, and after dehydration, a predetermined amount of washing water was supplied to the dehydrator, washed, and then dried.
• a homogenizer Homomixer manufactured by Primix
• thermally expandable microcapsule, an expandable masterbatch, and an expanded molded product were obtained in the same manner as in Example 1, except that the classification step was performed using an air force classifier (Donaserec, manufactured by Aisin Nano Technologies Co., Ltd.). .
• an air force classifier Donaserec, manufactured by Aisin Nano Technologies Co., Ltd.
• Example 7 Comparative Examples 2 to 6
• a thermally expandable microcapsule, an expandable masterbatch, and an expanded molded product were prepared in the same manner as in Example 6, except that the rotation speed and stirring time in dispersion using a homogenizer, and the presence or absence of the classification step were changed to those shown in Table 2.
• Example 7 The thermally expandable microcapsules, the foamable masterbatch and the foamed material were prepared in the same manner as in Example 6, except that the classification step was performed by classifying using a vibrating screen classifier (manufactured by DALTON, vibrating screen). A compact was obtained.
• a vibrating screen classifier manufactured by DALTON, vibrating screen.
• Example 8 Thermally expandable microcapsules were obtained in the same manner as in Example 1, except that the oily mixture and the aqueous dispersion medium obtained in Composition 2 were used instead of Composition 1.
• a styrene-butadiene-styrene block copolymer (SBS, manufactured by JSR, TR1600, density 0.96 g/cm 3 ) was used, except that the molding temperature was 170°C.
• SBS styrene-butadiene-styrene block copolymer
• Example 9 Thermally expandable microcapsules were obtained in the same manner as in Example 6, except that the oily mixture obtained in Composition 2 and the aqueous dispersion medium were used instead of Composition 1.
• a styrene-butadiene-styrene block copolymer (SBS, manufactured by JSR, TR1600, density 0.96 g/cm 3 ) was used, except that the molding temperature was 170°C.
• SBS styrene-butadiene-styrene block copolymer
• Ts foaming start temperature
• Tmax maximum foaming temperature
• 25 ⁇ g of the sample was placed in an aluminum container with a diameter of 7 mm and a depth of 1 mm, and was heated from 80° C. to 250° C. at a rate of 5° C./min while applying a force of 0.1 N from above. Then, the displacement in the vertical direction of the measuring terminal was measured, and the temperature at which the displacement started to rise was taken as the foaming start temperature. Also, the expansion ratio was measured, and the temperature at which the expansion ratio reached the maximum was defined as the maximum expansion temperature.
• the heat-expandable microcapsule which has a uniform surface, is hard to produce surface unevenness, and can manufacture a foaming molding excellent in lightness can be provided. Moreover, it is possible to provide an expandable masterbatch and an expanded molded article using the thermally expandable microcapsules.

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