WO2022230994A1 - Microcapsules thermiquement expansibles - Google Patents

Microcapsules thermiquement expansibles Download PDF

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Publication number
WO2022230994A1
WO2022230994A1 PCT/JP2022/019389 JP2022019389W WO2022230994A1 WO 2022230994 A1 WO2022230994 A1 WO 2022230994A1 JP 2022019389 W JP2022019389 W JP 2022019389W WO 2022230994 A1 WO2022230994 A1 WO 2022230994A1
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Prior art keywords
thermally expandable
weight
black
expandable microcapsules
compound
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PCT/JP2022/019389
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English (en)
Japanese (ja)
Inventor
秀平 大日方
武司 脇屋
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積水化学工業株式会社
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Priority to JP2022529559A priority Critical patent/JP7168821B1/ja
Publication of WO2022230994A1 publication Critical patent/WO2022230994A1/fr

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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
    • 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
    • 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
    • C08J9/32—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 provides a thermally expandable microcapsule that has excellent foamability, high dispersibility, and is capable of obtaining a foamed molded article with a good appearance, an expandable masterbatch using the thermally expandable microcapsule, and It relates to a foam molded article.
  • 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 are widely known 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.
  • thermally expandable microcapsules for example, in Patent Document 1, a (meth)acryloyl group and a reactive carbon-carbon double bond containing a polymer composed of a crosslinkable monomer having a molecular weight of 500 or more. Thermally expandable microspheres are disclosed. Further, Patent Document 2 discloses a modifier for an adhesive composition containing heat-expandable microspheres with wax adhered to their surfaces.
  • the present invention provides a thermally expandable microcapsule that has excellent foamability, high dispersibility, and is capable of obtaining a foamed molded article with a good appearance, an expandable masterbatch using the thermally expandable microcapsule, and
  • An object of the present invention is to provide a foam molded article.
  • the present disclosure 1 is a thermally expandable microcapsule in which a shell contains a volatile expanding agent as a core agent, and the shell contains a compound having an acetal group.
  • Present Disclosure 2 is the thermally expandable microcapsule according to Present Disclosure 1, wherein the compound having an acetal group is a polyvinyl acetal resin.
  • This disclosure 3 is the thermally expandable microcapsule according to this disclosure 2, wherein the polyvinyl acetal resin is a polyvinyl butyral resin.
  • Present Disclosure 4 is the thermally expandable microcapsule according to Present Disclosure 1, 2 or 3, wherein the shell further contains a polymer compound.
  • the present disclosure 5 the content of the compound having an acetal group is 0.001% by weight or more, 20% by weight or less with respect to the entire thermally expandable microcapsule, present disclosure 1, 2, 3 or 4 heat according to It is an expandable microcapsule.
  • This disclosure 6 is the thermally expandable microcapsule according to this disclosure 1, 2, 3, 4, or 5, wherein the shell contains a black material.
  • Present Disclosure 7 is the thermally expandable microcapsule according to Present Disclosure 6, wherein the black material is present inside the thermally expandable microcapsule.
  • the present disclosure 8 is the thermally expandable microcapsule according to the present disclosure 6 or 7, wherein the black material is a black pigment.
  • Present Disclosure 9 is the thermally expandable microcapsule according to Present Disclosure 6, 7 or 8, wherein the content of the compound having an acetal group is 3% by weight or more and 10000% by weight or less with respect to the black material. 10. The content of the black material is 0.01% by weight or more and 30% by weight or less with respect to the entire thermally expandable microcapsule. It's a capsule. Disclosure 11 is an expandable masterbatch containing the thermally expandable microcapsules according to any one of Disclosures 1 to 10 and a thermoplastic resin.
  • a 12th aspect of the present disclosure is a foam molded article using the thermally expandable microcapsules according to any one of the 1st to 10th aspects of the present disclosure or the foamable masterbatch according to the 11th aspect of the present disclosure. The present invention will be described in detail below.
  • the shell constituting the thermally expandable microcapsule which is one embodiment of the present invention contains a compound having an acetal group.
  • the "compound having an acetal group” is not particularly limited as long as it has an "acetal group”. Examples thereof include compounds containing a structural unit having an acetal group represented by the following formula (1).
  • R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • the acetal group-containing compound examples include polyvinyl acetal resins and copolymers containing structural units having an acetal group. Among them, polyvinyl acetal resin is preferred. By containing the above polyvinyl acetal resin, the thermally expandable microcapsules of the present invention have excellent dispersibility, making it possible to obtain a molded product with good appearance.
  • the polyvinyl acetal resin can be produced, for example, by a method of acetalizing polyvinyl alcohol using aldehyde.
  • R is preferably an alkyl group having 1 to 10 carbon atoms, particularly preferably a methyl group or a propyl group.
  • the compound having the acetal group particularly the polyvinyl acetal resin, has a preferable lower limit of number average molecular weight of 5,000 and a preferable upper limit of 500,000.
  • the number average molecular weight of the acetal group-containing compound is 5,000 or more, it is possible to suppress appearance defects in the resulting molded article.
  • the number average molecular weight of the acetal group-containing compound is 500,000 or less, excellent dispersibility can be exhibited, and a molded article with good appearance can be obtained.
  • the more preferable lower limit of the number average molecular weight of the compound having the acetal group is 8,000, the more preferable lower limit is 10,000, the more preferable upper limit is 300,000, and the more preferable upper limit is 100,000.
  • the number average molecular weight can be measured by gel permeation chromatography (GPC). For example, a polyvinyl acetal resin is dissolved in tetrahydrofuran at a concentration of 0.2% by weight, and measurement is performed using a GPC device (HLC-8220, manufactured by Tosoh Corporation). Using the molecular weight calibration curve obtained, the number average molecular weight (Mn), (weight average molecular weight (Mw), Mw/Mn) can be calculated. Column TSKgel SuperHZM-H (manufactured by Tosoh Corporation) can be used as the column used in the above measurement.
  • GPC gel permeation chromatography
  • the compound having an acetal group particularly polyvinyl acetal resin, has a preferable lower limit of viscosity measured at 20° C. using a rotational viscometer of 5 mPa ⁇ s and a preferable upper limit of 250 mPa ⁇ s.
  • a rotational viscometer of 5 mPa ⁇ s
  • a preferable upper limit of 250 mPa ⁇ s.
  • a more preferable lower limit of the viscosity is 8 mPa ⁇ s, and a more preferable upper limit is 60 mPa ⁇ s.
  • the content ratio of the structural unit having an acetal group in the polyvinyl acetal resin (hereinafter also referred to as "acetal group content”) is either when the aldehyde is used alone or when two or more types are used in combination.
  • the preferred lower limit is 50 mol %
  • the preferred upper limit is 85 mol %.
  • the acetal group content of the polyvinyl acetal resin is 50 mol % or more, excellent dispersibility can be exhibited, and a molded article having a good appearance can be obtained.
  • the amount of acetal groups in the polyvinyl acetal resin is 85 mol % or less, excellent dispersibility can be exhibited, and a molded article with good appearance can be obtained.
  • the more preferable lower limit of the acetal group content of the polyvinyl acetal resin is 54 mol%, the more preferable lower limit is 58 mol%, the more preferable upper limit is 82 mol%, and the more preferable upper limit is 79 mol%.
  • the method for calculating the amount of acetal groups since the acetal groups of the polyvinyl acetal resin are obtained by acetalizing two hydroxyl groups of polyvinyl alcohol, the method counts the two acetalized hydroxyl groups. to adopt.
  • the preferable lower limit of the content ratio of the structural unit having a hydroxyl group represented by the following formula (2) in the polyvinyl acetal resin (hereinafter also referred to as "hydroxyl group amount”) is 16 mol%, and the preferable upper limit is 45 mol%.
  • the amount of hydroxyl groups in the polyvinyl acetal resin is 16 mol % or more, excellent dispersibility can be exhibited, and a molded article with good appearance can be obtained.
  • the amount of hydroxyl groups in the polyvinyl acetal resin is 45 mol % or less, excellent dispersibility can be exhibited, and a molded article with good appearance can be obtained.
  • a more preferable lower limit of the amount of hydroxyl groups in the polyvinyl acetal resin is 20 mol %, a still more preferable lower limit is 22 mol %, and a more preferable upper limit is 40 mol %.
  • the preferable lower limit of the content ratio of the structural unit having an acetyl group represented by the following formula (3) in the polyvinyl acetal resin (hereinafter also referred to as "acetyl group amount”) is 0.1 mol%, and the preferable upper limit is 30 mol%. .
  • acetyl group amount is 0.1 mol%, and 30 mol % or less, excellent dispersibility can be exhibited, and a molded article with good appearance can be obtained.
  • the more preferable lower limit of the acetyl group content of the polyvinyl acetal resin is 0.2 mol%, the more preferable lower limit is 0.3 mol%, the more preferable upper limit is 24 mol%, the more preferable upper limit is 20 mol%, and the more preferable upper limit is 20 mol%.
  • the upper limit is 18 mol%.
  • the polyvinyl acetal resin is preferably a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol having a degree of saponification of 80 mol % or more. By using such a polyvinyl acetal resin, excellent dispersibility can be exhibited, and a molded article having a good appearance can be obtained. A more preferable lower limit of the degree of saponification of the polyvinyl alcohol is 85 mol %.
  • Examples of the acetalization method include a method of adding an aldehyde to an aqueous solution of polyvinyl alcohol in the presence of an acid catalyst such as hydrochloric acid.
  • aldehyde examples include formaldehyde (including paraformaldehyde), acetaldehyde (including paraacetaldehyde), propionaldehyde, butyraldehyde, amylaldehyde, hexylaldehyde, heptylaldehyde, 2-ethylhexylaldehyde, cyclohexylaldehyde, furfural, glyoxal, glutaraldehyde, benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenylacetaldehyde, ⁇ -phenylpropionaldehyde and the like.
  • formaldehyde including paraformaldehyde
  • acetaldehyde including paraacetaldehyde
  • the polyvinyl acetal resin is preferably a polyvinyl butyral resin in which the acetal group is a butyral group, or a polyvinyl acetoacetal resin in which the acetal group is an acetoacetal group, more preferably a polyvinyl butyral resin, from the viewpoint of foamability and appearance of the molded article. .
  • the compound having an acetal group is a copolymer containing a structural unit having an acetal group (also referred to as an acetal group-containing copolymer), structural units other than the structural unit having an acetal group are described later.
  • Structural units derived from nitrile-based monomers, monomers having a carboxyl group, and crosslinkable monomers are included.
  • the glass transition temperature (Tg) of the acetal group-containing compound is not particularly limited, but is preferably 60° C. or higher and 120° C. or lower. When the glass transition temperature (Tg) of the acetal group-containing compound is within the above range, excellent dispersibility can be exhibited, and a molded article with good appearance can be obtained.
  • the glass transition temperature (Tg) of the acetal group-containing compound is more preferably 120° C. or lower, and preferably 60° C. or higher.
  • the glass transition temperature (Tg) of the acetal group-containing compound can be determined, for example, by differential scanning calorimetry.
  • the content of the compound having an acetal group in the thermally expandable microcapsules which is one embodiment of the present invention has a preferred lower limit of 0.001% by weight and a preferred upper limit of 20% by weight with respect to the entire thermally expandable microcapsules. be.
  • the content of the acetal group-containing compound relative to the entire thermally expandable microcapsules is within the above range, excellent dispersibility can be exhibited, and a molded product with good appearance can be obtained.
  • a more preferable lower limit for the content of the compound having an acetal group with respect to the entire thermally expandable microcapsule is 0.01% by weight, a more preferable lower limit is 0.1% by weight, a more preferable upper limit is 10% by weight, and a further preferable upper limit is 5.
  • the content of the compound having an acetal group is preferably 0.5% by weight or more and 10000% by weight or less with respect to the black material described later.
  • the content of the compound having an acetal group is within the above range, excellent dispersibility can be exhibited, and a molded article with good appearance can be obtained.
  • the content of the acetal compound relative to the black material is 0.5% by weight or more, the dispersibility of the thermally expandable microcapsules and the black material can be improved to prevent deterioration of the foaming performance.
  • the shell of the thermally expandable microcapsule has a uniform structure, and the foaming performance can be improved.
  • the more preferable lower limit of the content of the acetal group-containing compound relative to the black material is 1% by weight, the more preferable lower limit is 2% by weight, the even more preferable lower limit is 3% by weight, the more preferable upper limit is 5000% by weight, and the more preferable upper limit is 3000% by weight, an even more preferred upper limit of 2000% by weight, a particularly preferred upper limit of 1000% by weight, a particularly preferred upper limit of 80% by weight, a particularly preferred upper limit of 60% by weight, a very preferred upper limit of 40% by weight, such as 30% by weight. It is below.
  • the content of the compound having an acetal group is preferably 0.01% by weight or more and 10% by weight or less with respect to the polymerizable compound described later.
  • the content of the acetal group-containing compound relative to the polymerizable compound is within the above range, excellent dispersibility can be exhibited, and a molded article with good appearance can be obtained.
  • the content of the acetal compound relative to the polymerizable compound is 0.01% by weight or more, the dispersibility of the thermally expandable microcapsules can be improved, and deterioration of the appearance of the molded article can be prevented.
  • the shell of the thermally expandable microcapsule has a uniform structure, and the foaming performance can be improved.
  • the content of the compound having an acetal group with respect to the polymerizable compound is preferably 0.1% by weight or more and 5% by weight or less.
  • Various contents of the compound having an acetal group can be measured by, for example, NMR, pyrolysis GC/MS, IR, LC/MS, and the like. Also, the various contents of the compound having an acetal group may be calculated from the added amount of the compound having an acetal group and each raw material.
  • the shell constituting the thermally expandable microcapsule which is one embodiment of the present invention may further contain a polymer compound.
  • the polymer compound is different from the acetal group-containing compound.
  • the polymer compound is preferably a polymer of a monomer composition containing a nitrile-based monomer and a monomer having a carboxyl group.
  • 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 40% by weight, and the preferable upper limit is 90% by weight.
  • the gas barrier property of the shell can be enhanced and the expansion ratio can be improved.
  • heat resistance can be improved and yellowing can be suppressed.
  • a more preferred lower limit is 45% by weight, a still more preferred lower limit is 50% by weight, and a more preferred upper limit is 80% 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, a more preferable upper limit is 40% by weight, and a further preferable upper limit is 30% by weight.
  • the monomer composition may contain an amide group-containing monomer, an epoxy group-containing monomer, and the like.
  • the amide group-containing monomer include (meth)acrylamide, N-ethyl(meth)acrylamide, N-isopropylacrylamide, N-methyl(meth)acrylamide, N-butyl(meth)acrylamide and the like. Glycidyl (meth)acrylate etc. are mentioned as said epoxy group containing monomer.
  • 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 carboxyl group-containing monomer, the amide group-containing monomer, the epoxy group-containing monomer, and the crosslinkable monomer.
  • a monomer other than the nitrile-based monomer the carboxyl group-containing monomer, the amide group-containing monomer, the epoxy group-containing monomer, and 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, in addition to (meth)acrylic acid esters. These may be used alone or in combination of two or more.
  • (meth)acrylic acid esters are preferable, and in particular, methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate and n-butyl methacrylate, or fatty acids such as cyclohexyl methacrylate, benzyl methacrylate and isobornyl methacrylate.
  • Ring/aromatic ring/heterocyclic ring-containing methacrylic acid esters are preferred.
  • a preferable lower limit of the content of the other monomer in the monomer composition is 0.1% by weight, and a preferable upper limit thereof is 25% by weight.
  • a preferable lower limit of the content of the other monomer in the monomer composition is 0.1% by weight, and a preferable upper limit thereof is 25% by weight.
  • the monomer composition may contain a thermosetting resin in addition to the nitrile-based monomer, the monomer having a carboxyl group, the crosslinkable monomer, and other monomers.
  • thermosetting resin 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 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 constituting the thermally expandable microcapsule which is one embodiment of the present invention preferably contains a black material.
  • a black material when a black material is added, the dispersibility of the black material is low. is lowered, and there is a problem that white spots originating from the thermally expandable microcapsules are generated on the surface of the molded product (whitening/defective appearance).
  • the dispersibility of the black material can be enhanced, and the occurrence of white spots in the resulting molded article can be suppressed.
  • the black material exhibits black color by absorbing all rays of sunlight including the visible light region.
  • Common black pigments absorb light in the visible light range (approximately 380 to 780 nm) and show black color, but in reality, the near-infrared region includes the wavelength range of 800 to 1,400 nm, which contributes significantly to heat. It also absorbs light in the area.
  • a preferable lower limit of the OD value of the black material is 1.5, and a preferable upper limit thereof is 5.0. Within the above range, it is possible to obtain a black coating film and a black matrix that achieve both high light-shielding properties and jet-blackness.
  • the OD value of the black material is the OD value obtained by measuring the acrylic resin containing 50% by weight of the black material (the coating thickness is 50 ⁇ m).
  • black material examples include black pigments, black dyes, and black conductive polymers.
  • a black pigment is preferable from the viewpoint of the appearance of the foam molded article.
  • the black pigment include inorganic black pigments such as carbon-based black pigments and oxide-based black pigments, as well as organic black pigments. Among them, at least one selected from the group consisting of carbon-based black pigments and oxide-based black pigments is preferable.
  • the carbon black pigment include carbon black, graphite, activated carbon, and graphene.
  • oxide-based black pigments titanium black, iron oxide, magnetite, cuprous oxide (cuprous oxide), copper and chromium, copper and manganese, copper and iron and manganese, cobalt and chromium and iron are mainly used.
  • Composite oxide black pigments with metal components and the like can be mentioned.
  • organic black pigment include aniline black (C.I. Pigment Black 1). Among them, carbon black is more preferable because it has excellent heat resistance, has excellent dispersibility in the resin, and can impart a uniform black color.
  • black dye examples include inorganic black dyes and organic black dyes. Among them, organic black dyes are preferred.
  • examples of the inorganic black dyes include metal complex salt azo black dyes.
  • Examples of the metal complex azo black dye include NeoSuper Black C-832 (trade name: Solvent Black 27, manufactured by Chuo Gosei Kagaku Co., Ltd.).
  • Examples of the organic black dyes include disazo black dyes, azine black dyes, phthalocyanine black dyes, anthraquinone black dyes, and indigoid black dyes.
  • Examples of the disazo-based black dye include Chuo Sudan Black 141 (trade name: Solvent Black 3, manufactured by Chuo Gosei Kagaku Co., Ltd.).
  • Examples of the azine-based black dye include Chuo Black F5 (trade name: Solvent Black 7, manufactured by Chuo Gosei Kagaku Co., Ltd.).
  • black conductive polymer examples include polythiophene, polydopamine, polypyrrole, polyaniline, polyphenylenevinylene, polyphenylene, polyacetylene, polyquinoxaline, polyoxadiazole, polybenzothiadiazole, and polymers having a plurality of these conductive skeletons. be done.
  • polythiophene and derivatives thereof are preferred, such as poly(3,4-ethylenedioxythiophene) [PEDOT], poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) [PEDOT/PSS], Polythienothiophene is particularly preferred.
  • black particles in the form of fine particles are preferred.
  • the black fine particles preferably have an average particle size of 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, still more preferably 0.4 ⁇ m or less, and even more preferably 0.3 ⁇ m or less. By setting it within the above range, the black fine particles are dispersed in the resin, and the hue (black) becomes uniform.
  • the average particle size can be measured by observation using a particle size distribution analyzer (eg, ELSZ-2000ZS, manufactured by Otsuka Electronics Co., Ltd.).
  • the black fine particles preferably have a primary average particle size of 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, still more preferably 0.1 ⁇ m or less, even more preferably 80 nm or less, preferably 1 nm or more, and 5 nm or more. More preferably, it is 10 nm or more.
  • the average primary particle size can be measured by observation using a scanning electron microscope (Regulus 8220, manufactured by Hitachi High-Technologies Corporation).
  • the "average particle size” means the average particle size of real particles (including secondary particles), and particularly means the hydrodynamic diameter in a liquid.
  • the “average primary particle size” means the average particle size of the smallest unit particles (primary particles).
  • a preferable lower limit of the content of the black material is 0.01% by weight, and a preferable upper limit thereof is 30% by weight with respect to the entire thermally expandable microcapsule.
  • the amount is 0.01% by weight or more, it is possible to suppress fusion between the thermally expandable microcapsules in the resin during molding. By making it 30% by weight or less, the dispersibility can be improved, and the appearance performance can be further enhanced.
  • a more preferable lower limit is 0.1% by weight, a more preferable upper limit is 20% by weight, and a further preferable upper limit is 10% by weight.
  • the content of the black material can be determined, for example, by raising the temperature of the thermally expandable microcapsules to 600° C.
  • the black material preferably has a specific surface area of 500 m 2 /g or less, more preferably 5 to 300 m 2 /g, still more preferably 10 to 200 m 2 /g. By setting it within the above range, the black material is dispersed in the resin, and the hue (black) becomes uniform.
  • the above specific surface area is obtained by measuring the adsorption isotherm of nitrogen using a surface area / pore size analyzer (NOVA4200e, manufactured by Quantachrome Instruments), and from the measurement results, in accordance with the BET method, the specific surface area of the black material can be measured by calculating
  • the black material preferably has a DBP absorption of 10 to 200 cm 3 /100 g.
  • the above DBP absorption is preferably 30 to 150 cm 3 /100 g.
  • the DBP absorption amount (cm 3 /100 g) is the volume of dibutyl phthalate (DBP) that can be adsorbed by 100 g of carbon black, and is measured according to JIS K 6217.
  • the black material a material whose surface is not coated may be used, or a material whose surface is coated may be used.
  • the surface-coated substrate include those coated with a polymer or a low-molecular-weight compound.
  • the black material may exist on the surface of the thermally expandable microcapsule or may exist inside.
  • the black material may be present inside the shell of the thermally expandable microcapsule, or may be present at the inner interface (core-shell interface) of the shell.
  • the black material is preferably present inside the shell of the thermally expandable microcapsule.
  • the thermally expandable microcapsules may have an outermost layer, and the outermost layer may contain a black material.
  • the thermally expandable microcapsules having a black material inside the shell can be produced by using a black material whose surface is not coated.
  • Thermally expandable microcapsules in which a black material exists on the inner interface of the shell can be produced by using a black material whose surface is coated with a polymer or a low-molecular-weight compound.
  • the position of the black material can be confirmed by using a transmission electron microscope or the like after forming a thin film so as to pass through the vicinity of the center of the thermally expandable microcapsules dispersed in the embedding resin.
  • the shell constituting the thermally expandable microcapsule which is one embodiment of the present invention preferably further contains at least one inorganic compound selected from the group consisting of Si-based compounds and Mg-based compounds.
  • at least one inorganic compound selected from the group consisting of Si-based compounds and Mg-based compounds.
  • the Si-based compound and Mg-based compound preferably contain oxides, hydroxides, carbonates, or hydrogencarbonates of silicon and magnesium. These Si-based compounds and Mg-based compounds may be used alone or in combination of two or more.
  • Examples of the Si-based compound include colloidal silica, silicic acid sol, and the like, as well as No. 3 water glass, sodium orthosilicate, sodium metasilicate, and the like. Among them, colloidal silica is preferred.
  • Examples of the Mg-based compound include magnesium oxide, magnesium hydroxide, magnesium oxide hydroxide, hydrotalcite, dihydrotalcite, magnesium carbonate, basic magnesium carbonate, magnesium calcium carbonate, magnesium phosphate, magnesium hydrogen phosphate, and pyroline. Examples include magnesium acid and magnesium borate. Among them, magnesium hydroxide is preferable.
  • inorganic compounds that may be added include calcium phosphate, aluminum hydroxide, ferric hydroxide, barium sulfate, calcium sulfate, sodium sulfate, calcium oxalate, calcium carbonate, and barium carbonate.
  • inorganic salts such as sodium chloride and sodium sulfate, alkali metal nitrite salts, stannous chloride, stannic chloride, potassium dichromate, and the like may be added.
  • the inorganic compound fine particles are preferable.
  • the primary particle size is preferably 0.5 ⁇ m or less, more preferably 5 to 100 nm. Within the above range, fusion between the thermally expandable microcapsules in the resin can be suppressed during molding.
  • the primary particle size can be measured by observation using a scanning electron microscope (Regulus 8220, manufactured by Hitachi High-Technologies Corporation).
  • the content of the inorganic compound is 0.01% by weight with respect to the entire thermally expandable microcapsule, and the preferred upper limit is 7% by weight.
  • the amount is 0.01% by weight or more, it is possible to suppress fusion between the thermally expandable microcapsules in the resin during molding. By making it 7% by weight or less, the dispersibility of the resin during molding can be further enhanced.
  • a more preferable lower limit is 0.3% by weight, and a more preferable upper limit is 5% by weight.
  • the weight ratio of the inorganic compound to the black material is preferably 0.001 to 300. By making it 0.001 or more, fusion between the thermally expandable microcapsules in the resin can be suppressed during molding. By making it 300 or less, the dispersibility of the resin during molding can be further improved, and the light shielding property and appearance performance can be further improved. A more preferable lower limit is 0.3, and a more preferable upper limit is 100.
  • 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.
  • a thermally expandable microcapsule which is one embodiment of the present invention, contains 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 expanding agent examples include ethane, ethylene, propane, propene, n-butane, isobutane, butene, isobutene, n-pentane, isopentane, neopentane, n-hexane, heptane, petroleum ether, isooctane, octane, Examples include low molecular weight hydrocarbons such as decane, isododecane, dodecane, and hexanedecane.
  • Chlorofluorocarbons such as CCl 3 F, CCl 2 F 2 , CClF 3 and CClF 2 -CClF 2 ; tetraalkylsilanes such as tetramethylsilane, trimethylethylsilane, trimethylisopropylsilane and trimethyl-n-propylsilane; be done.
  • isobutane, n-butane, n-pentane, isopentane, n-hexane, isooctane, isododecane and mixtures thereof are preferred.
  • These volatile swelling agents may be used alone or in combination of two or more.
  • a thermally decomposable compound that is thermally decomposed by heating into a gaseous state may be used.
  • thermoly expandable microcapsules of one embodiment of the present invention it is preferable to use a low-boiling hydrocarbon having 5 or less carbon atoms among the volatile expanding agents described above.
  • a hydrocarbon having 5 or less carbon atoms among the volatile expanding agents described above.
  • the volatile expansion agent a thermally decomposable compound that is thermally decomposed by heating into a gaseous state may be used.
  • the preferred lower limit of the maximum foaming temperature (Tmax) of the thermally expandable microcapsules is 150°C.
  • Tmax maximum foaming temperature
  • 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 thermally expandable microcapsules of one embodiment of the present invention have a preferred lower limit of maximum displacement (Dmax) measured by thermomechanical analysis of 10 ⁇ m. If it is less than 10 ⁇ m, the foaming ratio may be lowered, and desired foaming performance may not be obtained.
  • Dmax maximum displacement
  • a more preferable lower limit is 20 ⁇ m, a still more preferable lower limit is 100 ⁇ m, and a still more preferable lower limit is 300 ⁇ m.
  • a preferred upper limit of the maximum displacement amount is 2000 ⁇ m, a more preferred upper limit is 1800 ⁇ m, and a further preferred upper limit is 1500 ⁇ m.
  • the maximum amount of displacement is the value when the diameter of the entire predetermined amount of thermally expandable microcapsules becomes maximum when the diameter is measured while heating a predetermined amount of thermally expandable microcapsules from room temperature. .
  • the preferable upper limit of foaming start temperature (Ts) is 175 degreeC.
  • Ts foaming start temperature
  • the thermally expandable microcapsules which are one embodiment of the present invention, preferably have a lower limit of 0.1% by weight and a preferred upper limit of 20% by weight of the content of high-temperature combustibles. By setting the content within the above range, it is possible to obtain a foam molded article having excellent foamability, high dispersibility, and good appearance.
  • the content of the above-mentioned high-temperature combustibles was measured by using a simultaneous differential thermogravimetric measurement device (TA7200, manufactured by Hitachi High-Tech Science), and 1.0 mg of the obtained thermally expandable microcapsules was heated to 600°C under a nitrogen atmosphere at 10°C/ After the temperature was raised at 10 min and held for 10 minutes, the temperature was lowered to 400° C. at 10° C./min and held for 10 minutes. Thereafter, the atmosphere is switched to air, the temperature is raised to 1000° C. under air, and the weight loss at 400° C. to 1000° C. is obtained when the temperature is maintained at 1000° C. for 10 minutes.
  • TA7200 simultaneous differential thermogravimetric measurement device
  • a preferable lower limit of the volume average particle size of the thermally expandable microcapsules which is one embodiment of the present invention, is 3 ⁇ m, and a preferable upper limit thereof is 45 ⁇ m.
  • the resulting molded article has a sufficient foaming ratio without too small cells, and when it is 45 ⁇ m or less, the resulting coating does not have too large cells and has an excellent appearance. becomes.
  • a more preferable lower limit is 5 ⁇ m, a still more preferable lower limit is 10 ⁇ m, and a more preferable upper limit is 35 ⁇ m.
  • the volume average particle size can be measured using a laser diffraction/scattering particle size distribution analyzer or the like.
  • the method for producing the thermally expandable microcapsules which is one embodiment of the present invention, is not particularly limited, the following method can be used.
  • a monomer composition those containing the above-mentioned nitrile-based monomer, a monomer having a carboxyl group, a crosslinkable monomer, and other monomers can be used.
  • the first step is to prepare an aqueous dispersion medium.
  • an aqueous dispersion medium containing an inorganic compound is prepared by adding water, an inorganic compound, and, if necessary, a co-stabilizer to a polymerization reactor.
  • co-stabilizer examples include a condensation product of diethanolamine and an aliphatic dicarboxylic acid, a condensation product of urea and formaldehyde, and the like. Also included are polyvinylpyrrolidone, polyethylene oxide, polyethyleneimine, tetramethylammonium hydroxide, gelatin, methylcellulose, polyvinyl alcohol, dioctylsulfosuccinate, sorbitan ester, and various emulsifiers.
  • Condensation products and water-soluble nitrogen compounds may also be added in addition to co-stabilizers.
  • a condensation product of diethanolamine and an aliphatic dicarboxylic acid is preferable, and a condensation product of diethanolamine and adipic acid and a condensation product of diethanolamine and itaconic acid are particularly preferable.
  • water-soluble nitrogen 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 aqueous dispersion medium containing the above inorganic compound and co-stabilizer is prepared by blending with deionized water, and the pH of the aqueous phase at this time is appropriately determined depending on the type of inorganic compound and co-stabilizer used. .
  • a Si-based compound such as colloidal silica
  • the polymerization is performed using an acidic aqueous dispersion medium. is added to adjust the pH of the system to 3-4.
  • an Mg-based compound such as magnesium hydroxide or calcium phosphate
  • an alkaline aqueous dispersion medium adjusted to pH 8-11 is used for polymerization.
  • an oily mixture containing a monomer composition, a volatile expanding agent, a compound containing an acetal group, and optionally a black material and a dispersant is added to an aqueous dispersion medium.
  • Perform the dispersing step Specifically, a step of dispersing an oily mixture containing a monomer composition, a volatile swelling agent, a compound containing an acetal group, and optionally a black material and a dispersant in an aqueous dispersion medium is carried out.
  • 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. may be added.
  • 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 aqueous dispersion medium contains a black material and optionally a dispersant, the used black material can be present inside the thermally expandable microcapsules.
  • a method of emulsifying and dispersing the above oily mixture in an aqueous dispersion medium to have a predetermined particle size a method of stirring with a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd., for example) or the like, a line mixer or an element type static disperser. and a method of passing through a static dispersing device such as.
  • 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.
  • the thermally expandable microcapsules which is one embodiment of the present invention, are produced by performing a step of polymerizing the monomers by heating the dispersion liquid obtained through the above-described steps, and a step of washing. can be done.
  • the thermally expandable microcapsules produced by such a method have a high maximum foaming temperature, excellent heat resistance, and do not burst or shrink even during coating in a high temperature range.
  • a foamable masterbatch containing the above thermally expandable microcapsules 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).
  • LDPE, EVA, EMMA and the like are preferable because they have a low melting point and are easy to process. These may be used alone or in combination of two or more.
  • 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 obtained using the above-mentioned thermally expandable microcapsules and foamable masterbatch is also one aspect of the present invention.
  • the thermally expandable microcapsules can be used to obtain a foamed sheet having a high appearance quality such as an uneven shape, and can be suitably used for applications such as residential wallpaper.
  • the thermally expandable microcapsules or the expandable masterbatch containing the thermally expandable microcapsules are kneaded with a matrix resin, and the mixture is 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.
  • thermally expandable microcapsule having excellent foamability, high dispersibility, and capable of obtaining a foam molded article having a good appearance, and an expandable master using the thermally expandable microcapsule Batch and foam moldings are possible.
  • Example 1 Production of thermally expandable microcapsules
  • a polymerization reaction vessel 250 parts by weight of water, 35 parts by weight of colloidal silica (manufactured by Asahi Denka Co., Ltd.) and 0.8 parts by weight of polyvinylpyrrolidone (manufactured by BASF) as a dispersion stabilizer, and 1.8 parts by weight of 1N hydrochloric acid were added. were added to prepare an aqueous dispersion medium.
  • the monomer composition consists of 20 parts by weight of acrylonitrile, 30 parts by weight of methacrylonitrile, 35 parts by weight of methacrylic acid and 15 parts by weight of methyl methacrylate, and the volatile swelling agent consists of 15 parts by weight of isopentane and 10 parts by weight of isooctane.
  • PVB1 manufactured by Sekisui Chemical Co., Ltd.
  • the resulting dispersion was stirred and mixed with a homogenizer, charged into a nitrogen-substituted pressurized polymerization vessel, and reacted at 60° C. for 20 hours while pressurizing (0.5 MPa) to obtain a reaction product.
  • the resulting reaction product was repeatedly filtered and washed with water, and then dried to obtain thermally expandable microcapsules.
  • Examples 2-5) Thermally expandable microcapsules were obtained in the same manner as in Example 1, except that the amount of polyvinyl butyral (PVB1) added was changed to the amount shown in Table 1.
  • PVB1 polyvinyl butyral
  • Example 6 (Production of thermally expandable microcapsules)
  • a polymerization reaction vessel 250 parts by weight of water, 35 parts by weight of colloidal silica (20% by weight, manufactured by Asahi Denka Co., Ltd.) and 0.8 parts by weight of polyvinylpyrrolidone (manufactured by BASF) as a dispersion stabilizer, and 1.8 parts by weight of 1N hydrochloric acid were added. , to prepare an aqueous dispersion medium.
  • the monomer composition of Table 1 a volatile expanding agent, polyvinyl butyral (PVB1) 1.25 parts by weight, carbon black (CB1, primary average particle diameter 24 nm, specific surface area 110 m 2 /g, DBP absorption 100 cm) as a black material 3/100 g, average particle size 150 nm in the oily mixture) 0.013 parts by weight, and an oily mixture comprising a polymerization initiator were irradiated with ultrasonic waves and then added to the aqueous dispersion medium. Then, it was suspended to prepare a dispersion.
  • PVB1 polyvinyl butyral
  • CB1 primary average particle diameter 24 nm, specific surface area 110 m 2 /g, DBP absorption 100 cm
  • an oily mixture comprising a polymerization initiator were irradiated with ultrasonic waves and then added to the aqueous dispersion medium. Then, it was suspended to prepare a dispersion.
  • the monomer composition consists of 20 parts by weight of acrylonitrile, 30 parts by weight of methacrylonitrile, 35 parts by weight of methacrylic acid and 15 parts by weight of methyl methacrylate, and the volatile swelling agent consists of 15 parts by weight of isopentane and 10 parts by weight of isooctane. It is. Further, the polymerization initiator consists of 0.8 parts by weight of (2,2'-azobisisobutyronitrile) and 0.6 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile). be.
  • the average particle size of carbon black in the oily mixture after ultrasonic irradiation was 150 nm.
  • the resulting dispersion was stirred and mixed with a homogenizer, charged into a nitrogen-substituted pressurized polymerization vessel, and reacted at 60° C. for 21 hours while pressurizing (0.5 MPa) to obtain a reaction product.
  • the resulting reaction product was repeatedly filtered and washed with water, and then dried to obtain thermally expandable microcapsules.
  • the resulting thermally expandable microcapsules were added to an embedding resin (Technovit 4000, manufactured by Kulzer) so that the content of the particles was 3% by weight, and dispersed to obtain a thermally expandable microcapsule embedding resin. was made.
  • a thin film was prepared with a microtome (EM UC7, manufactured by LEICA) so as to pass through the vicinity of the center of the thermally expandable microcapsules dispersed in the embedding resin, and a black material was observed with a transmission electron microscope (JEM-2100, manufactured by JEOL Ltd.). As a result of confirming the existence position of , it was confirmed that there was a black material inside the shell. The position of the black material was similarly confirmed for the thermally expandable microcapsules to be produced later.
  • Table 1 when the black material exists on the surface of the thermally expandable microcapsules, it is referred to as "particle surface", and when the black material exists on the inner interface of the shell, it is referred to as "core-shell interface".
  • Example 7 to 14 Thermally expandable microcapsules were obtained in the same manner as in Example 6, except that the amounts of polyvinyl butyral (PVB1) and carbon black added were changed to the amounts shown in Table 1.
  • PVB1 polyvinyl butyral
  • Examples 15-20 Thermally expandable microcapsules were obtained in the same manner as in Example 6, except that polyvinyl butyral (PVB1) was changed to polyvinyl butyral (PVB2 to PVB7) shown in Table 1. The following materials were used as PVB2 to PVB7.
  • PVB1 polyvinyl butyral
  • PVB2 to PVB7 polyvinyl butyral
  • PVB2 viscosity: average 20 mPa s, number average molecular weight: 19000, hydroxyl group content: 36 mol%, acetyl group content: 1 mol%, acetal group content (butyral group content): 63 mol%, glass transition temperature: 70°C PVB3: viscosity: average 17 mPa s, number average molecular weight: 20000, hydroxyl group content: 30 mol%, acetyl group content: 1 mol%, acetal group content (butyral group content): 69 mol%, glass transition temperature: 68°C PVB4: viscosity: average 23 mPa s, number average molecular weight: 23000, hydroxyl group content: 23 mol%, acetyl group content: 5 mol%, acetal group content (butyral group content): 72 mol%, glass transition temperature: 66°C PVB5: viscosity: average 34 mPa s, number average
  • Examples 21-23 Instead of carbon black (CB1, average primary particle size 24 nm, specific surface area 110 m 2 /g, DBP absorption 100 cm 3 /100 g, average particle size in oily mixture 150 nm), CB2 shown in Table 1 (average primary particle size 13 nm, specific surface area 370 m 2 /g, DBP absorption 77 cm 3 /100 g, average particle diameter in oily mixture 80 nm), CB3 (primary average particle diameter 30 nm, specific surface area 74 m 2 /g, DBP absorption 113 cm 3 /100 g) , average particle size in oily mixture 200 nm), CB4 (average primary particle size 55 nm, specific surface area 36 m 2 /g, DBP absorption 93 cm 3 /100 g, average particle size in oily mixture 350 nm) Thermally expandable microcapsules were obtained in the same manner as in Example 6.
  • Example 24 Example except that 3.75 parts by weight of carbon black (CB5, Aqua Black #001, manufactured by Tokai Carbon Co., Ltd., average particle size: 160 nm) was added as a black material to the aqueous dispersion medium, and carbon black was not added to the oily mixture. Thermally expandable microcapsules were obtained in the same manner as in Example 9.
  • carbon black CB5, Aqua Black #001, manufactured by Tokai Carbon Co., Ltd., average particle size: 160 nm
  • Example 25 Instead of carbon black (CB1, average primary particle size 24 nm, specific surface area 110 m 2 /g, DBP absorption 100 cm 3 /100 g, average particle size in oily mixture 150 nm), CB6 shown in Table 1 (average primary particle size Thermally expandable microcapsules were obtained in the same manner as in Example 6, except that carbon black having a particle size of 24 nm, an average particle size in an oily mixture of 150 nm, and a surface coated with a polymer or a low-molecular-weight compound) was used.
  • CB6 average primary particle size Thermally expandable microcapsules were obtained in the same manner as in Example 6, except that carbon black having a particle size of 24 nm, an average particle size in an oily mixture of 150 nm, and a surface coated with a polymer or a low-molecular-weight compound
  • Example 26 (Preparation of masterbatch pellets) 100 parts by weight of low-density polyethylene (LDPE, melting point 103° C.) and 10 parts by weight of stearic acid as a lubricant were kneaded in a Banbury mixer, and when the temperature reached about 100° C., the thermally expandable microcapsules obtained in Example 9 were obtained. 100 parts by weight of the mixture was added, kneaded for 30 seconds, extruded and simultaneously pelletized to obtain a masterbatch pellet.
  • LDPE low-density polyethylene
  • stearic acid stearic acid
  • the content of the high-temperature combustible material of the same thermally expandable microcapsules that do not contain the black material is measured separately, and the content of the high-temperature combustible material when the black material is contained and the high-temperature combustible material when the black material is not contained are measured. The content and the difference were calculated as the black material content.
  • the difference is less than 0.5: ⁇
  • the difference is 0.5 or more and less than 1: ⁇
  • the difference is 1 or more and less than 2: ⁇
  • the difference is 2 or more and less than 3: ⁇ Difference of 3 or more: ⁇
  • thermally expandable microcapsule having excellent foamability, high dispersibility, and capable of obtaining a foam molded article having a good appearance, and an expandable master using the thermally expandable microcapsule Batch and foam moldings can be provided.

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Abstract

La présente invention concerne : des microcapsules thermiquement expansibles qui présentent une excellente expansibilité et une dispersibilité élevée, et qui permettent d'obtenir un corps moulé en mousse qui présente un bon aspect ; et un mélange maître expansible et un corps moulé en mousse, chacun d'entre eux utilisant les microcapsules thermiquement expansibles. La présente invention concerne des microcapsules thermiquement expansibles comprenant chacune : une enveloppe ; et un agent d'expansion volatil qui est enfermé en tant qu'agent principal dans l'enveloppe. L'enveloppe contient un composé qui comprend un groupe acétal.
PCT/JP2022/019389 2021-04-30 2022-04-28 Microcapsules thermiquement expansibles WO2022230994A1 (fr)

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CN116004046A (zh) * 2023-02-07 2023-04-25 上海正欧实业有限公司 一种防腐微粒及应用、防腐聚氨酯地坪涂料及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004150924A (ja) * 2002-10-30 2004-05-27 Toppan Printing Co Ltd 酸素インジケーター及び酸素インジケーター付き包装体
JP2004536172A (ja) * 2001-05-25 2004-12-02 アパーチェ・プロダクツ・カンパニー 発泡体断熱のための膨張性ミクロスフェアおよび方法
JP2005087956A (ja) * 2003-09-19 2005-04-07 Sekisui Chem Co Ltd 熱膨張性マイクロカプセルおよびその製造方法
JP6825168B1 (ja) * 2019-03-28 2021-02-03 三井化学東セロ株式会社 粘着性フィルムの製造方法および電子装置の製造方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61242023A (ja) * 1985-04-19 1986-10-28 Sanyo Electric Co Ltd 微細パタ−ンの形成方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004536172A (ja) * 2001-05-25 2004-12-02 アパーチェ・プロダクツ・カンパニー 発泡体断熱のための膨張性ミクロスフェアおよび方法
JP2004150924A (ja) * 2002-10-30 2004-05-27 Toppan Printing Co Ltd 酸素インジケーター及び酸素インジケーター付き包装体
JP2005087956A (ja) * 2003-09-19 2005-04-07 Sekisui Chem Co Ltd 熱膨張性マイクロカプセルおよびその製造方法
JP6825168B1 (ja) * 2019-03-28 2021-02-03 三井化学東セロ株式会社 粘着性フィルムの製造方法および電子装置の製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116004046A (zh) * 2023-02-07 2023-04-25 上海正欧实业有限公司 一种防腐微粒及应用、防腐聚氨酯地坪涂料及其制备方法
CN116004046B (zh) * 2023-02-07 2023-10-20 上海正欧实业有限公司 一种防腐微粒及应用、防腐聚氨酯地坪涂料及其制备方法

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