WO2020111144A1 - Method for producing latex, and latex - Google Patents

Method for producing latex, and latex Download PDF

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Publication number
WO2020111144A1
WO2020111144A1 PCT/JP2019/046431 JP2019046431W WO2020111144A1 WO 2020111144 A1 WO2020111144 A1 WO 2020111144A1 JP 2019046431 W JP2019046431 W JP 2019046431W WO 2020111144 A1 WO2020111144 A1 WO 2020111144A1
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WIPO (PCT)
Prior art keywords
water
elastomer
latex
polyvinyl alcohol
mol
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PCT/JP2019/046431
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French (fr)
Japanese (ja)
Inventor
友貴 坂井
小林 直紀
英博 松田
智加子 斉藤
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デンカ株式会社
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Priority to JP2020557791A priority Critical patent/JPWO2020111144A1/en
Publication of WO2020111144A1 publication Critical patent/WO2020111144A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/02Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/07Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00Compositions of unspecified rubbers
    • C08L21/02Latex
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D109/00Coating compositions based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C09D109/02Copolymers with acrylonitrile
    • C09D109/04Latex
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D111/00Coating compositions based on homopolymers or copolymers of chloroprene
    • C09D111/02Latex
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D153/00Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D153/02Vinyl aromatic monomers and conjugated dienes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02Emulsion paints including aerosols
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J109/00Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C09J109/02Copolymers with acrylonitrile
    • C09J109/04Latex
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J111/00Adhesives based on homopolymers or copolymers of chloroprene
    • C09J111/02Latex
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02Vinyl aromatic monomers and conjugated dienes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets

Definitions

  • the present invention relates to a latex manufacturing method and a latex. More specifically, a method for producing a latex having one or more water phases inside and producing an elastomer particle in which the water phase forms voids by drying, and one or more water phases inside And a latex containing elastomer particles whose aqueous phase forms voids upon drying.
  • Particles with voids inside have basic properties such as weight reduction (low specific gravity), heat insulation and sound insulation, and low dielectric loss, low electrical conduction, reflection/scattering abnormality, impact resistance, rigidity improvement, texture It is known that a unique property is also expressed from the viewpoint of application. For these reasons, particles having voids in the interior have hitherto been used in various molded articles, wallpaper, paints, building materials, sealing agents, adhesives, shoe soles, synthetic leather, tires, paper, cement, tiles, FRP, capacitors, etc. Is used in an extremely wide range of fields.
  • the particles having voids inside are, for example, hollow granules made of fine particle titanium oxide surface-treated with silicic acid anhydride (Patent Document 1). Also proposed are hollow silica-based fine particles (Patent Documents 2 and 3) and hollow particles of metal oxide produced by removing a polymer after forming a coating layer made of a metal oxide on the surface of spherical polymer fine particles. (Patent Document 4). Furthermore, hollow fine particles of fullerene-like boron nitride obtained by reacting carbon nanotubes with boron oxide at high temperature have also been proposed (Patent Document 5). However, these particles have poor flexibility in a room temperature environment and may not be suitable for a product field requiring flexibility.
  • Patent Document 6 a hollow microcapsule composed of a styrene-based thermoplastic elastomer containing a polystyrene block and a polyolefin block and having a porosity of 10 to 95%.
  • Patent Document 7 an elastomer particle having an glass transition point of ⁇ 100 to 0° C. and having at least one void has been proposed.
  • the present invention provides a method for producing a latex, which has one or more water phases inside and can improve the yield of elastomer particles in which the water phase forms voids by drying.
  • the main purpose is.
  • the present invention is Water in which polyvinyl alcohol having a saponification degree of 60 to 97 mol% is dissolved, An elastomer solution in which an elastomer is dissolved in a poorly water-soluble organic solvent having a specific gravity at 20°C of 0.8 or more and a boiling point of 95°C or less, There is provided a method for producing a latex, which comprises the step of mixing and stirring.
  • a surfactant having an HLB of 8.0 or less may be dissolved in the poorly water-soluble organic solvent.
  • the present invention is water and, An elastomer solution in which an elastomer and a surfactant having an HLB of 8.0 or less are dissolved in a poorly water-soluble organic solvent having a specific gravity at 20°C of 0.8 or more and a boiling point of 95°C or less, After mixing and stirring, Provided is a method for producing a latex, which comprises a step of adding water in which polyvinyl alcohol having a saponification degree of 60 to 97 mol% is dissolved and stirring the mixture.
  • the surfactant having an HLB of 8.0 or less may be at least one selected from the group consisting of sorbitan monooleate, sorbitan trioleate and glycerol monostearate.
  • the polyvinyl acetate is at least one selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, maleic acid monoester, fumaric acid monoester and itaconic acid monoester, It may be a copolymer with vinyl acetate.
  • the elastomer may be chloroprene rubber, nitrile rubber, or styrene block copolymer.
  • the poorly water-soluble organic solvent may be a halogen-based organic solvent.
  • the present invention is Elastomer particles having one or more aqueous phases therein, and the aqueous phases forming voids when dried,
  • a latex containing water in which polyvinyl alcohol having a saponification degree of 60 to 97 mol% is dissolved is provided.
  • the latex may contain a surfactant having an HLB of 8.0 or less.
  • the latex may contain at least one of polyvinyl alcohol having a saponification degree of 20 to 59 mol% and carboxy-modified polyvinyl acetate.
  • a cast film produced using the above latex according to the following production conditions may have a thermal conductivity of 0.100 W/mk or less, a breaking strength of 3.5 MPa or more, and a breaking elongation of 180% or more.
  • Manufacturing conditions The latex is poured on a glass plate placed horizontally and dried at room temperature for 3 days to form a film film having a thickness of 0.5 mm, and then vacuum dried at room temperature for 1 day to evaporate water, 100 mm in length, 50 mm in width. And molded into a cast film.
  • the latex may be for water-based adhesives or water-based paints.
  • the present invention also provides a water-based adhesive or water-based coating material using the latex.
  • a method for producing a latex that has one or more aqueous phases inside and can improve the yield of elastomer particles in which the aqueous phase forms voids when dried. ..
  • a method for producing a latex according to an embodiment of the present invention is a method for producing a latex for producing an elastomer particle having one or more voids inside. Further, the method for producing a latex according to the present embodiment may also be a method for producing a latex containing elastomer particles having one or more water phases inside and drying the water phase to form voids. ..
  • the elastomer particles having one or more water phase inside and forming a void in the water phase when dried have one water phase inside and are dried to have a water phase of 1
  • a mononuclear elastomer particle forming one void and a multi-hollow elastomer particle having a plurality of aqueous phases therein and the aqueous phase forming a plurality of voids when dried are included.
  • the manufacturing method of this embodiment is roughly classified into a manufacturing method I and a manufacturing method II described later.
  • the yield is high. It is preferably used.
  • the manufacturing method I and the manufacturing method II will be described in detail.
  • the elastomer is dissolved in water in which polyvinyl alcohol having a saponification degree of 60 to 97 mol% is dissolved, and a poorly water-soluble organic solvent having a specific gravity at 20°C of 0.8 or more and a boiling point of 95°C or less.
  • a method for producing a latex which comprises a step of mixing the above-mentioned elastomer solution and stirring.
  • the step of mixing and stirring the water and the elastomer solution is preferably mixing and stirring the water and the elastomer solution, and the elastomer solution in the water as fine droplets having an aqueous phase inside. This is a step of obtaining a finely dispersed dispersion liquid.
  • the “fine droplet” means a droplet having a number average particle diameter of 10.0 ⁇ m or less.
  • the production method I is not particularly limited as long as it includes the step of performing stirring as described above, but the following production method is preferable:
  • a method for producing a latex comprising:
  • the dispersion liquid is a W/O/W type emulsion in which the elastomer solution is finely dispersed in water as fine droplets having an aqueous phase inside.
  • the production method I stabilizes the aqueous phase (internal aqueous phase) inside the fine droplets in the dispersion (W/O/W type emulsion) by using a specific polyvinyl alcohol and a specific poorly water-soluble organic solvent. It is possible to form a stable W/O/W type emulsion.
  • the stability of the internal aqueous phase is the “aqueous core” that forms the void structure when the aqueous phase (internal aqueous phase) inside the fine droplets is fixed inside the elastomer particles and then dried. Influences the yield of elastomer particles having voids inside.
  • the synthetic rubber is preferably chloroprene rubber (CR), styrene-butadiene rubber (SBR), acrylic rubber (ACM), nitrile rubber (NBR), epichlorohydrin rubber (ECO), butadiene rubber (BR), ethylene-propylene-diene rubber. (EPDM), natural rubber (NR) and isoprene rubber (IR).
  • the thermoplastic elastomer is preferably a styrene block copolymer.
  • “Styrene-based block copolymer” means a block copolymer of styrene and a monomer copolymerizable with styrene.
  • the monomer copolymerizable with styrene include isoprene, butadiene, chloroprene and the like.
  • the styrene block copolymer include styrene-isoprene-styrene triblock copolymer (SIS), styrene-butadiene-styrene triblock copolymer (SBS), styrene-ethylenebutylene-styrene triblock copolymer.
  • SEBS styrene-ethylene propylene-styrene triblock copolymer
  • SEPS styrene-chloroprene-styrene triblock copolymer
  • the elastomer is more preferably chloroprene rubber, nitrile rubber or styrene block copolymer, and even more preferably chloroprene rubber. These elastomers may be used alone or in combination of two or more.
  • the water-insoluble organic solvent has a specific gravity at 20° C. of 0.8 or more, more preferably 0.9 or more, and its upper limit is not particularly limited, but preferably 1.8 or less, and preferably Is 1.6 or less. If the specific gravity at 20° C. is less than 0.8, the elastomer solution will float when the water in which the polyvinyl alcohol is dissolved and the elastomer solution are stirred, and the elastomer solution will be stably finely dispersed in water. Difficult to do.
  • the upper limit of the boiling point of the poorly water-soluble organic solvent is 95°C or lower, preferably 90°C or lower, more preferably 80°C or lower, and further preferably 70°C or lower.
  • the lower limit of the boiling point of the poorly water-soluble organic solvent is preferably 30°C or higher, more preferably 40°C or higher.
  • the poorly water-soluble organic solvent is not particularly limited, and examples thereof include a chloroprene monomer (2-chloro-1,3-butadiene), a halogen-based organic solvent such as methylene chloride, chloroform and carbon tetrachloride, and benzene. At least one kind or two or more kinds selected from the group consisting of can be used.
  • the poorly water-soluble organic solvent having a specific gravity at 20° C. of 0.8 or more and a boiling point of 95° C. or less can be appropriately selected according to the type of elastomer.
  • the elastomer include chloroprene rubber (CR), styrene-butadiene rubber (SBR), acrylic rubber (ACM), styrene-butadiene-styrene triblock copolymer (SBS) and styrene-chloroprene-styrene triblock copolymer (
  • the poorly water-soluble organic solvent is preferably a chloroprene monomer (2-chloro-1,3-butadiene), a halogen-based organic solvent such as methylene chloride, chloroform, carbon tetrachloride and benzene.
  • the poorly water-soluble organic solvent is the chloroprene rubber (CR), styrene-isoprene-styrene triblock copolymer (SIS) and styrene-chloroprene-styrene triblock copolymer (SCS), the poorly water-soluble organic solvent is The chloroprene monomer is more preferable.
  • the elastomer is, for example, nitrile rubber (NBR) and epichlorohydrin rubber (ECO)
  • the poorly water-soluble organic solvent is preferably a halogen-based organic solvent such as chloroprene monomer, methylene chloride, chloroform and carbon tetrachloride.
  • the sparingly water-soluble organic solvent is preferably benzene.
  • the water-insoluble organic solvent is preferably a halogen-based organic solvent, Chloroprene monomers are more preferred.
  • the elastomer solution used in the production method I can be obtained by an elastomer solution preparation step of dissolving the elastomer in the poorly water-soluble organic solvent.
  • the method for dissolving the elastomer in the poorly water-soluble organic solvent is not particularly limited, and for example, the poorly water-soluble organic solvent and the elastomer may be stirred using a stirrer.
  • the temperature at this time is not particularly limited as long as it can dissolve the elastomer, but may be, for example, room temperature, and more specifically, 5 to 40° C. or 10 to 30° C.
  • a polymerization terminator or the like may be appropriately added to the poorly water-soluble organic solvent or the elastomer solution in order to prevent the polymerization reaction from occurring.
  • the type of the polymerization terminator is not particularly limited, and examples thereof include amine compounds such as phenothiazine and thiodiphenylamine; 4-tert-butylcatechol, 2,2′-methylene (bis-4-methyl-6-tert-butylphenol). 1) or 2 or more selected from the group consisting of phenolic compounds such as ). Of these, a phenolic compound is preferable, and 4-tert-butylcatechol is more preferable.
  • the content of the elastomer in the elastomer solution is not particularly limited, but is preferably 5 to 50 parts by mass and more preferably 10 to 40 parts by mass in 100 parts by mass of the elastomer solution.
  • the elastomer solution is an elastomer solution in which an elastomer and a surfactant having an HLB of 8.0 or less are dissolved in a poorly water-soluble organic solvent having a specific gravity at 20° C. of 0.8 or more and a boiling point of 95° C. or less.
  • a surfactant having an HLB of 8.0 or less is dissolved in the poorly water-soluble organic solvent.
  • the elastomer solution is an elastomer solution in which an elastomer and a surfactant having an HLB of 8.0 or less are dissolved in a poorly water-soluble organic solvent having a specific gravity at 20° C. of 0.8 or more and a boiling point of 95° C. or less.
  • the HLB of the above-mentioned surfactant is preferably 8.0 or less, more preferably 7.0 or less, further preferably 6.0 or less, and particularly preferably 5.0 or less.
  • the surfactant is not particularly limited, and examples thereof include sucrose fatty acid ester; sorbitan monostearate, sorbitan monopalmitate, sorbitan monobehenate, sorbitan monomontanate, and other sorbitan fatty acid ester surfactants; glycerin monolaurate. Rate, glycerin monopalmitate, glycerin monostearate, diglycerin distearate, triglycerin monostearate, glycerin fatty acid ester-based surfactants such as tetraglycerin monomontanate, and the like, selected from the group consisting of these. It is at least one kind. Among the above-mentioned surfactants, nonionic surfactants are preferable.
  • the surfactant having an HLB of 8.0 or less is preferably sorbitan monopalmitate (Span 40, HLB: 6.7), sorbitan monostearate (Span 60, HLB: 4.7), sorbitan tristearate (Span 65, HLB: 2.1), sorbitan monooleate (Span80, HLB: 4.3), sorbitan sesquioaleate (Span83, HLB: 3.7), sorbitan trioleate (Span85, HLB: 1.8), and Sorbitan fatty acid ester system such as sorbitan isostearate (Span120, HLB: 4.7); glycerol monostearate (MS-60, HLB: 3.5), glycerol monostearate (MS-50, HLB: 2.8) ), glycerol monooleate (MO-60, HLB: 2.8), and other glycerin fatty acid ester-based compounds; and the like.
  • more preferable is at least one selected from the group consisting of sorbit
  • the surfactants may be used alone or in combination of two or more.
  • the term “surfactant having an HLB of 8.0 or less” means that the HLB of each surfactant is 8.0 or less. It does not mean that the average value of HLB of the activator is 8.0 or less.
  • the content of the surfactant in the elastomer solution is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 5 parts by mass in 100 parts by mass of the elastomer solution.
  • the method of dissolving the surfactant in the poorly water-soluble organic solvent is not particularly limited, and for example, after stirring the poorly water-soluble organic solvent and the surfactant with a stirring device, the elastomer is added. And stir further.
  • the polyvinyl alcohol having a saponification degree of 60 to 97 mol% used in the production method I has a lower saponification degree of preferably 70 mol% or more, more preferably 75 mol% or more, still more preferably 80 mol% or more. is there.
  • the upper limit of the saponification degree of the polyvinyl alcohol is preferably 95 mol% or less, more preferably 90 mol% or less.
  • the degree of saponification of polyvinyl alcohol of less than 60 mol% or more than 97 mol% is also applicable, but when the polyvinyl alcohol is used alone, when water in which polyvinyl alcohol is dissolved and an elastomer solution are stirred, It cannot be stably emulsified, and it is difficult to stably finely disperse the elastomer solution in water.
  • the polyvinyl alcohol having a saponification degree of 60 to 97 mol% may be used alone or in combination of two or more kinds.
  • the "polyvinyl alcohol having a saponification degree of 60 to 97 mol%" means that the saponification degree of each polyvinyl alcohol is 60 to 97 mol. %, and does not mean that the average saponification degree of two or more polyvinyl alcohols is 60 to 97 mol %.
  • polyvinyl alcohol having a saponification degree of 20 to 59 mol% and/or carboxy-modified polyvinyl acetate is used together, the aqueous phase inside the fine droplets is more stabilized, and the internal aqueous phase when the poorly water-soluble organic solvent evaporates Withdrawal is suppressed more effectively.
  • the generation of elastomer particles having no voids inside is suppressed, so that it is possible to increase the yield of elastomer particles having voids inside.
  • the polyvinyl alcohol having a saponification degree of 20 to 59 mol% has a lower saponification degree of preferably 25 mol% or more, more preferably 30 mol% or more, and further preferably 35 mol% or more.
  • the upper limit is preferably 50 mol% or less, more preferably 45 mol% or less.
  • the polyvinyl alcohol having a saponification degree of 20 to 59 mol% may be used alone or in combination of two or more kinds.
  • the "polyvinyl alcohol having a saponification degree of 20 to 59 mol%" means that the saponification degree of each polyvinyl alcohol is 20 to 59 mol. %, and does not mean that the average saponification degree of two or more polyvinyl alcohols is 20 to 59 mol %.
  • Carboxy-modified polyvinyl acetate is a copolymer of vinyl acetate and unsaturated carboxylic acid.
  • the unsaturated carboxylic acid is at least one selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, maleic acid monoester, fumaric acid monoester and itaconic acid monoester.
  • Examples of commercially available carboxy-modified polyvinyl acetate include DENKA ASR CH-09 (manufactured by DENKA CORPORATION).
  • the carboxy-modified polyvinyl acetate may be used alone or in combination of two or more kinds.
  • the method in which the water in which the polyvinyl alcohol is dissolved and the elastomer solution are mixed and then stirred to obtain a dispersion liquid in which the elastomer solution is finely dispersed in the water as fine droplets having an aqueous phase inside is It is not particularly limited.
  • water in which polyvinyl alcohol is dissolved and the elastomer solution may be placed in a reaction vessel and stirred using a stirrer. At the time of stirring, the reaction vessel may be cooled in order to suppress the temperature increase due to shearing heat generation.
  • the cooling temperature at this time is not particularly limited, but examples thereof include 20 to 0° C., 10 to 0° C., and 4 to 0° C.
  • the number average particle diameter of the fine droplets in the dispersion is preferably adjusted to 10.0 ⁇ m or less by adjusting the rotation speed of the stirring device.
  • the content of water in which polyvinyl alcohol is dissolved is preferably 50 to 300 parts by mass, more preferably 50 to 200 parts by mass, relative to 100 parts by mass of the elastomer solution.
  • the content of polyvinyl alcohol having a saponification degree of 60 to 97 mol% is preferably 5 to 30 parts by mass, more preferably 5 to 25 parts by mass, based on 100 parts by mass of the elastomer solution. It is more preferably about 20 to 20 parts by mass.
  • the total content of polyvinyl alcohol having a saponification degree of 20 to 59 mol% and/or carboxy-modified polyvinyl acetate is 0.1 to 10 parts by mass with respect to 100 parts by mass of the elastomer solution. Part by weight is preferred, 0.5 to 10 parts by weight is more preferred, and 0.5 to 5 parts by weight is even more preferred.
  • a step of evaporating a soluble organic solvent under normal pressure or under reduced pressure to generate elastomer particles having one or more aqueous phases inside.
  • the temperature for evaporating is not particularly limited, but its upper limit is preferably 50° C. or lower, more preferably 40° C. or lower, and its lower limit is preferably 20° C. or higher, more preferably 30° C. or higher.
  • the depressurizing condition is not particularly limited, but the upper limit is preferably 100 mmHg or less, more preferably 80 mmHg or less, and the lower limit is preferably 20 mmHg or more, more preferably 40 mmHg or more.
  • the elastomer solution is finely dispersed as fine droplets having an aqueous phase inside.
  • the poorly water-soluble organic solvent in the elastomer solution forming the fine droplets evaporates and disappears.
  • the structure of the elastomer forming the fine droplets is fixed and the elastomer particles are generated.
  • the immobilization the aqueous phase (internal aqueous phase) inside the fine droplets is confined in the voids inside the elastomer particles.
  • the latex containing the elastomer particles is subjected to drying, whereby the aqueous phase remaining inside the elastomer particles is removed, and the portions where the aqueous phase is removed become voids.
  • the internal aqueous phase is fixed inside the elastomer particles to form a void structure, and can therefore be said to be a “void nucleus”.
  • the internal water phase is unstable, when the sparingly water-soluble organic solvent evaporates in the solvent evaporation process, the internal water phase separates from the fine droplets, and elastomer particles without void nuclei inside can be generated. Therefore, the yield of the elastomer particles having voids inside may decrease when the latex is dried.
  • the production method II comprises water and an elastomer solution in which an elastomer and a surfactant having an HLB of 8.0 or less are dissolved in a poorly water-soluble organic solvent having a specific gravity of 0.8 or more at 20° C. and a boiling point of 95° C. or less. Is mixed and stirred, and then a method for producing a latex is provided, which comprises a step of adding water in which polyvinyl alcohol having a saponification degree of 60 to 97 mol% is dissolved and stirring.
  • the production method II is not particularly limited as long as it includes the above steps, but the following production method is preferable: Water (A), An elastomer solution in which an elastomer and a surfactant having an HLB of 8.0 or less are dissolved in a poorly water-soluble organic solvent having a specific gravity at 20°C of 0.8 or more and a boiling point of 95°C or less, Are mixed and stirred to obtain a dispersion liquid (a) in which water (A) is finely dispersed in the elastomer solution, Water (B) in which polyvinyl alcohol having a saponification degree of 60 to 97 mol% is dissolved is added to the dispersion (a) and stirred, and the dispersion (a) is added to the water (B).
  • a method for producing a latex which comprises a step of obtaining a finely dispersed dispersion liquid (b).
  • the above production method II is more preferably the following production method: An elastomer solution preparation step of obtaining an elastomer solution by dissolving an elastomer and a surfactant having an HLB of 8.0 or less in a poorly water-soluble organic solvent; A first dispersion liquid preparation step in which the elastomer solution and water (A) are mixed and stirred to obtain a dispersion liquid (a) in which the water (A) is finely dispersed in the elastomer solution; Water (B) in which polyvinyl alcohol having a saponification degree of 60 to 97 mol% is dissolved is added to the dispersion liquid (a) and stirred, and the dispersion liquid (a) is added to the water (B). A second dispersion liquid producing step for obtaining a finely dispersed dispersion liquid (b); A method for producing a latex, comprising:
  • the above dispersion liquid (b) is a W/O/W type emulsion, and is a dispersion liquid in which the elastomer solution is finely dispersed in water (B) as fine droplets having an aqueous phase inside.
  • the production method II uses a specific polyvinyl alcohol and a specific poorly water-soluble organic solvent to obtain an aqueous phase (internal aqueous phase) inside the fine droplets in the dispersion (b) (W/O/W type emulsion). Can be stabilized, and thus a stable W/O/W type emulsion can be formed.
  • polyvinyl alcohol having a saponification degree of 20 to 59 mol% and/or carboxy-modified polyvinyl acetate is used in combination, the aqueous phase inside the fine droplets is stabilized and the internal water phase when the sparingly water-soluble organic solvent evaporates Withdrawal is suppressed.
  • the generation of elastomer particles having no voids inside is suppressed, so that it is possible to increase the yield of elastomer particles having voids inside.
  • the HLB of the surfactant used in Production Method II is 8.0 or less, preferably 7.0 or less, more preferably 6.0 or less, and further preferably 5.0 or less. When the HLB is more than 8.0, it is difficult to form a stable W/O/W type emulsion.
  • the elastomer solution used in the production method II can be obtained by an elastomer solution preparation step in which an elastomer and a surfactant having an HLB of 8.0 or less are dissolved in the poorly water-soluble organic solvent to obtain an elastomer solution.
  • the method of dissolving the elastomer and the surfactant in the poorly water-soluble organic solvent is not particularly limited, for example, after stirring the poorly water-soluble organic solvent and the surfactant using a stirring device, if the elastomer is added and further stirred Good.
  • the content of the elastomer in the elastomer solution is preferably 5 to 50 parts by mass and more preferably 10 to 40 parts by mass in 100 parts by mass of the elastomer solution.
  • the content of the surfactant in the elastomer solution is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 5 parts by mass in 100 parts by mass of the elastomer solution.
  • the method of obtaining the dispersion liquid (a) in which the water (A) is finely dispersed in the elastomer solution after mixing and stirring the water (A) and the elastomer solution is not particularly limited.
  • the dispersion liquid (a) can be obtained by placing water (A) and the elastomer solution in a reaction container and stirring the mixture using a stirring device. At the time of stirring, the reaction vessel may be cooled in order to suppress the temperature increase due to shearing heat generation.
  • the number average particle diameter of the fine droplets in the dispersion liquid (a) is preferably adjusted to 7.0 ⁇ m or less by adjusting the rotation speed of the stirring device.
  • the cooling temperature at this time is not particularly limited, but examples thereof include 20 to 0° C., 10 to 0° C., and 4 to 0° C.
  • the content of water (A) is preferably 10 to 100 parts by mass, and more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the elastomer solution.
  • Water (B) in which polyvinyl alcohol having a saponification degree of 60 to 97 mol% is dissolved is added to the dispersion liquid (a) and stirred, and the dispersion liquid (a) is added to the water (B).
  • the method for obtaining the finely dispersed dispersion liquid (b) is not particularly limited as long as the elastomer solution can be finely dispersed in water (B) as fine particle droplets having an aqueous phase therein.
  • the water (B) may be added to the dispersion liquid (a) and stirred using a stirrer, and cooling may be performed during stirring in order to suppress a temperature increase due to shear heat generation.
  • the number average particle diameter of the fine droplets in the dispersion liquid (b) is preferably adjusted to 10.0 ⁇ m or less by adjusting the rotation speed of the stirring device.
  • Manufacturing method II is one in which at least one is obtained by evaporating the poorly water-soluble organic solvent in the dispersion obtained by the above-mentioned steps, that is, the poorly water-soluble organic solvent in the dispersion (b) under normal pressure or reduced pressure. It is preferable to include the step (solvent evaporation step) of producing the elastomer particles having the aqueous phase. The details of the solvent evaporation step are the same as those described in the above manufacturing method I, and thus the description thereof is omitted here.
  • the aqueous phase inside the fine droplets is stabilized and This makes it possible to improve the yield of elastomer particles having voids.
  • the reason why the stabilization of the aqueous phase inside the fine droplets contributes to the improvement of the yield is as described in the above-mentioned production method I.
  • the latex according to one embodiment of the present invention is a dispersion liquid (latex) obtained by the above-mentioned method for producing latex (Production Method I or Production Method II).
  • the latex of the present embodiment is preferably a latex obtained by a solvent evaporation step after the sparingly water-soluble organic solvent has been evaporated.
  • the latex after the sparingly water-soluble organic solvent has been evaporated preferably has at least one aqueous phase therein, and has an saponification degree of 60 and the elastomer particles having the aqueous phase forming voids. And a water in which about 97 mol% of polyvinyl alcohol is dissolved. More preferably, the latex further contains a surfactant having an HLB of 8.0 or less. More preferably, the latex further contains at least one of polyvinyl alcohol having a saponification degree of 20 to 59 mol% and carboxy-modified polyvinyl acetate. In the latex, an aqueous phase that forms voids when dried exists inside the elastomer particles.
  • Elastomer particles contained in the latex of the present embodiment has an aqueous phase inside which forms voids by drying, and since it is composed of an elastomer that is a soft material, it has the basic characteristics of void structure. It has a certain heat insulating property (low thermal conductivity) and flexibility which is a basic characteristic of an elastomer. Therefore, the latex of the present embodiment exhibits excellent heat insulating properties, breaking strength and breaking elongation when formed into a film.
  • the cast film produced according to the following production conditions using the latex of the present embodiment has a thermal conductivity of 0.100 W/mk or less, a breaking strength of 3.5 MPa or more, and a breaking elongation of 180%. That is all.
  • the thermal conductivity can be measured using a rapid thermal conductivity meter QTM-500 (manufactured by Kyoto Electronics Manufacturing Co., Ltd.).
  • the breaking strength and breaking elongation can be measured based on Japanese Industrial Standard JIS K6251.
  • the latex of this embodiment can be used for applications such as water-based adhesives, water-based paints, water-based coating agents, and linings, but is suitable for water-based adhesives and water-based paints.
  • the method for producing an aqueous adhesive and an aqueous paint using the above latex is not particularly limited as long as the above latex is blended. That is, the water-based adhesive and water-based coating material using the above latex can be manufactured by a conventional method using a known machine or device.
  • the elastomer particles according to one embodiment of the present invention are elastomer particles having one or more voids inside.
  • the elastomer particles of the present embodiment can be obtained by drying the latex after evaporating the poorly water-soluble organic solvent.
  • the method of drying is not particularly limited, and water may be evaporated by drying the latex under reduced pressure at room temperature.
  • the number average particle size of the elastomer particles of the present embodiment is preferably 0.05 to 10.0 ⁇ m, more preferably 0.1 to 5.0 ⁇ m. Further, in the elastomer particles of the present embodiment, the diameter of the voids inside is preferably 10 to 1000 nm, more preferably 50 to 500 nm. The number average particle diameter of the elastomer particles and the diameter of the voids can be measured by a transmission electron microscope.
  • the "number average particle diameter" here is a value calculated by image analysis using a scanning electron microscope (SEM) photograph, and is a value obtained by observing 100 particles and averaging them. Microscopic observation can be performed, for example, by pre-treating particles to be measured and using a field emission scanning electron microscope (SU6600/manufactured by Hitachi High-Technologies Corporation) at an acceleration voltage of 5 kV.
  • SEM scanning electron microscope
  • the pretreatment of the elastomer particles to be observed by SEM is as follows.
  • (I) 0.5 ml of pure water is put into a 6 ml screw tube bottle (manufactured by AS ONE), and 2 drops of the elastomer particle dispersion liquid is dropped therein with a dropper and mixed.
  • (Ii) One drop of the liquid mixed in (i) is placed on the collodion film-attached mesh, and vapor fixation is performed for 1 hour using a 2% OsO 4 aqueous solution.
  • (Iii) After air-drying at room temperature, an OsO 4 coat (coat thickness 7 nm) is applied.
  • the diameter of the voids of the elastomer particles can be measured by observation with a scanning electron microscope (SEM), like the number average particle diameter described above.
  • Example 1 ⁇ Preparation of elastomer solution>
  • a 200 mL glass bottle 76 g of chloroprene monomer (specific gravity at 20° C.: 0.96, boiling point: 59° C.) to which 4-tert-butylcatechol was added, and 24 g of chloroprene rubber (manufactured by DENKA CORPORATION, trade name: A-30) And were added, and the mixture was stirred at room temperature for 12 hours to dissolve the chloroprene rubber.
  • the room temperature in this example is 20°C.
  • AHG-160D manufactured by As One Co., Ltd.
  • Example 2 ⁇ Preparation of elastomer solution>
  • chloroprene monomer added with 4-tert-butylcatechol, 1 g of Span80 (sorbitan monooleate) (NOF Corporation, trade name: Nonion OP-80R, HLB: 4.3)
  • Span80 sorbitan monooleate
  • HLB 4.3
  • Example 2 After that, in the same procedure as in Example 1, an aqueous polyvinyl alcohol solution was prepared, a dispersion liquid was obtained, and a solvent evaporation step was performed, and then a cast film was prepared.
  • Example 3 In preparation of the elastomer solution, except that Span 80 (sorbitan monooleate) was replaced by Span 85 (sorbitan trioleate) (NOF Corporation, trade name: Nonion OP-85R, HLB: 1.8). A cast film was produced in the same procedure as in Example 2.
  • Example 4 After preparing an elastomer solution and a polyvinyl alcohol aqueous solution by the same procedure as in Example 2, a dispersion was prepared by the following procedure.
  • Example 5 In the preparation of the elastomer solution, a dispersion liquid (b) was obtained in the same procedure as in Example 4 except that Span 85 (sorbitan trioleate) was used instead of Span 80 (sorbitan monooleate), and the solvent evaporation step was performed. After that, a cast film was produced.
  • Span 85 sorbitan trioleate
  • Span 80 sorbitan monooleate
  • Example 6 In the preparation of the polyvinyl alcohol aqueous solution, in addition to 85 g of pure water and 15 g of polyvinyl alcohol (PVA 3-88), polyvinyl alcohol (manufactured by Kuraray Co., Ltd., trade name: PVA LM-10, saponification degree: 40 mol%) ) A dispersion liquid (b) was obtained in the same procedure as in Example 5 except that 2.5 g was used, and a solvent evaporation step was performed, and then a cast film was produced.
  • PVA 3-88 polyvinyl alcohol
  • PVA LM-10 saponification degree: 40 mol%
  • Example 7 In the preparation of an aqueous polyvinyl alcohol solution, in addition to 85 g of pure water and 15 g of polyvinyl alcohol (PVA 3-88), carboxylic acid-modified polyvinyl acetate (manufactured by DENKA CORPORATION, trade name: DENKA ASR CH-09) 1 Dispersion liquid (b) was obtained in the same procedure as in Example 5 except that 0.0 g was used, and a solvent evaporation step was carried out to produce a cast film.
  • Example 8 Example 2 was repeated except that glycerol monostearate (manufactured by Kao Corporation, trade name: Rheodor MS-60, HLB: 3.5) was used in place of Span 80 (sorbitan monooleate) in the preparation of the elastomer solution. A cast film was produced by the same procedure.
  • glycerol monostearate manufactured by Kao Corporation, trade name: Rheodor MS-60, HLB: 3.5
  • Span 80 sorbitan monooleate
  • Example 9 In the preparation of the elastomer solution, Span 20 (sorbitan monolaurate) (NOF Corporation, trade name: Nonion LP-20R, HLB: 8.6) was used instead of Span 80 (sorbitan monooleate). A cast film was produced in the same procedure as in Example 2.
  • Example 10 In the preparation of the polyvinyl alcohol aqueous solution, in addition to 85 g of pure water and 15 g of polyvinyl alcohol (PVA 3-88), polyvinyl alcohol (manufactured by Kuraray Co., Ltd., trade name: PVA LM-10, saponification degree: 40 mol%) ) A cast film was produced in the same procedure as in Example 1 except that 2.5 g was used.
  • Example 11 In the preparation of an aqueous polyvinyl alcohol solution, in addition to 85 g of pure water and 15 g of polyvinyl alcohol (PVA 3-88), carboxylic acid-modified polyvinyl acetate (manufactured by DENKA CORPORATION, trade name: DENKA ASR CH-09) 1 A cast film was produced by the same procedure as in Example 1 except that 0.0 g was used.
  • Example 12 In the preparation of the elastomer solution, methylene chloride (specific gravity at 20°C: 1.33, boiling point: 40°C) was used instead of the chloroprene monomer, and nitrile rubber (manufactured by Nippon Zeon Co., Ltd., trade name: Nipol1043) was used instead of chloroprene rubber. A cast film was produced in the same procedure as in Example 3 except that was used.
  • Example 13 In the preparation of the elastomer solution, the same procedure as in Example 1 was performed except that styrene-isoprene-styrene triblock copolymer (SIS) (manufactured by Zeon Corporation, trade name: Quintac3421) was used instead of chloroprene rubber. A cast film was produced.
  • SIS styrene-isoprene-styrene triblock copolymer
  • Example 14 In the preparation of the polyvinyl alcohol aqueous solution, in addition to 85 g of pure water and 15 g of polyvinyl alcohol (PVA 3-88), polyvinyl alcohol (manufactured by Kuraray Co., Ltd., trade name: PVA LM-10, saponification degree: 40 mol%) ) A cast film was produced in the same procedure as in Example 3 except that 2.5 g was used.
  • Example 15 In the preparation of an aqueous polyvinyl alcohol solution, in addition to 85 g of pure water and 15 g of polyvinyl alcohol (PVA 3-88), carboxylic acid-modified polyvinyl acetate (manufactured by DENKA CORPORATION, trade name: DENKA ASR CH-09) 1 A cast film was produced by the same procedure as in Example 3 except that 0.0 g was used.
  • Example 2 A cast film was produced in the same procedure as in Example 1 except that an aqueous solution was produced using Tween 20 (trade name: Nonion LT-221, HLB: 16.7, manufactured by NOF CORPORATION) instead of polyvinyl alcohol. ..
  • Example 3 Example 1 except that in the preparation of the polyvinyl alcohol aqueous solution, the amount of pure water was changed from 85 g to 96 g and 4 g of polyvinyl alcohol (PVA LM-10) was used instead of 15 g of polyvinyl alcohol (PVA 3-88). A cast film was produced by the same procedure as in.
  • breaking strength and breaking elongation A tensile test was performed based on JIS K 6251, and the breaking strength (MPa) and breaking elongation (%) of the cast film were measured. The breaking strength was 3.5 MPa or more, and the breaking elongation was 180% or more.
  • the thermal conductivity (W/mk) of the cast film was measured using a rapid thermal conductivity meter QTM-500 (manufactured by Kyoto Electronics Manufacturing Co., Ltd.).
  • Example 1 to 15 it was confirmed that the yield of elastomer particles having one or more voids inside was high. It was also confirmed that the cast films of Examples 1 to 15 had low thermal conductivity and excellent heat insulating properties, and also had good breaking strength and breaking elongation. Specifically, the cast films of Examples 1 to 15 had a thermal conductivity of 0.100 W/mk or less, a breaking strength of 3.5 MPa or more, and a breaking elongation of 180% or more.
  • the number average particle diameter of these elastomer particles of Examples 1 to 15 obtained in the ⁇ solvent evaporation step (production of elastomer particles)> was 0.1 to 5 when measured with a transmission electron microscope. It was in the range of 0.0 ⁇ m and the diameter of the voids inside these was in the range of 50 to 500 nm.
  • Comparative Example 1 using polyvinyl alcohol having a saponification degree of more than 97 mol %, Comparative Example 2 using Tween 20 instead of polyvinyl alcohol, and Comparative Example 3 using polyvinyl alcohol having a saponification degree of less than 60 mol %, The emulsion could not be stably emulsified and the elastomer particles could not be produced.
  • Comparative Example 4 using a poorly water-soluble organic solvent having a specific gravity at 20° C. of less than 0.8
  • Comparative Example 5 using a poorly water-soluble organic solvent having a boiling point over 95° C., an elastomer having one or more voids inside was very low.

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Abstract

A method for producing a latex that comprises a step wherein a water in which a polyvinyl alcohol having a saponification degree of 60-97% by mole is dissolved and an elastomer solution which is obtained by dissolving an elastomer into a poorly water-soluble organic solvent that has a specific gravity at 20°C of 0.8 or more and a boiling point of 95°C or less are mixed with each other and stirred.

Description

ラテックスの製造方法及びラテックスMethod for producing latex and latex
 本発明は、ラテックスの製造方法及びラテックスに関する。より詳しくは、内部に1つ以上の水相を有し、乾燥させることで該水相が空隙を形成するエラストマー粒子を生成するためのラテックスの製造方法、及び、内部に1つ以上の水相を有し、乾燥させることで該水相が空隙を形成するエラストマー粒子を含有するラテックスに関する。 The present invention relates to a latex manufacturing method and a latex. More specifically, a method for producing a latex having one or more water phases inside and producing an elastomer particle in which the water phase forms voids by drying, and one or more water phases inside And a latex containing elastomer particles whose aqueous phase forms voids upon drying.
 内部に空隙を有する粒子は、軽量化(低比重化)、断熱性や遮音性といった基本特性を有し、低誘電損失、低電気伝導、反射・散乱異常、耐衝撃性、剛性改善、風合付与などの観点でも特異な性質を発現することが知られている。このような理由から、内部に空隙を有する粒子は、従来、各種成形体や壁紙、塗料、建材、シーリング剤、粘着剤、靴底、合成皮革、タイヤ、紙、セメント、タイル、FRP及びキャパシタなどの極めて広範な分野で利用されている。 Particles with voids inside have basic properties such as weight reduction (low specific gravity), heat insulation and sound insulation, and low dielectric loss, low electrical conduction, reflection/scattering abnormality, impact resistance, rigidity improvement, texture It is known that a unique property is also expressed from the viewpoint of application. For these reasons, particles having voids in the interior have hitherto been used in various molded articles, wallpaper, paints, building materials, sealing agents, adhesives, shoe soles, synthetic leather, tires, paper, cement, tiles, FRP, capacitors, etc. Is used in an extremely wide range of fields.
 内部に空隙を有する粒子としては、例えば、無水ケイ酸で表面処理された微粒子酸化チタンからなる中空顆粒がある(特許文献1)。また、中空のシリカ系微粒子(特許文献2、3)や、球状重合体微粒子の表面に金属酸化物からなる被覆層を形成した後に重合体を除去して作製した金属酸化物の中空粒子も提案されている(特許文献4)。更に、カーボンナノチューブにホウ素酸化物を高温で反応させて得られるフラーレン状窒化ホウ素の中空微粒子も提案されている(特許文献5)。しかしながら、これらの粒子は、常温環境下において柔軟性が乏しく、柔軟性が要求される製品分野には適さない場合がある。 The particles having voids inside are, for example, hollow granules made of fine particle titanium oxide surface-treated with silicic acid anhydride (Patent Document 1). Also proposed are hollow silica-based fine particles (Patent Documents 2 and 3) and hollow particles of metal oxide produced by removing a polymer after forming a coating layer made of a metal oxide on the surface of spherical polymer fine particles. (Patent Document 4). Furthermore, hollow fine particles of fullerene-like boron nitride obtained by reacting carbon nanotubes with boron oxide at high temperature have also been proposed (Patent Document 5). However, these particles have poor flexibility in a room temperature environment and may not be suitable for a product field requiring flexibility.
 そこで、内部に空隙を有しつつ常温環境下において柔軟性を備える粒子を、エラストマーを用いて製造する技術が研究されている。例えば、ポリスチレンブロックとポリオレフィンブロックを含むスチレン系熱可塑性エラストマーからなり、かつ空隙率が10~95%である中空マイクロカプセルが提案されている(特許文献6)。また、ガラス転移点が-100~0℃であるエラストマーからなり、少なくとも1つの空隙を有するエラストマー粒子も提案されている(特許文献7)。 Therefore, research is being conducted on a technology for producing particles that have flexibility inside a room temperature environment while having voids inside by using an elastomer. For example, there has been proposed a hollow microcapsule composed of a styrene-based thermoplastic elastomer containing a polystyrene block and a polyolefin block and having a porosity of 10 to 95% (Patent Document 6). Further, an elastomer particle having an glass transition point of −100 to 0° C. and having at least one void has been proposed (Patent Document 7).
特開2014-58441号公報JP, 2014-58441, A 特開2013-121911号公報JP, 2013-121911, A 特開2014-58683号公報JP, 2014-58683, A 特開2000-34582号公報Japanese Patent Laid-Open No. 2000-34582 特開2001-294409号公報JP, 2001-294409, A 特開2009-207973号公報JP, 2009-207973, A 国際公開第2016/031845号International Publication No. 2016/031845
 このような特性を備えるエラストマー粒子は、従来の柔軟性に欠ける中空粒子とは異なる分野でも利用されることが見込まれ、需要の拡大が期待されている。このため、内部に空隙を有するエラストマー粒子をより効率的に製造可能な技術が求められている。 Demand for elastomer particles with such properties is expected to grow, as they are expected to be used in fields other than conventional hollow particles that lack flexibility. Therefore, there is a demand for a technique capable of more efficiently producing elastomer particles having voids inside.
 そこで、本発明は、内部に1つ以上の水相を有し、乾燥させることで該水相が空隙を形成するエラストマー粒子の収率を向上させることが可能なラテックスの製造方法を提供することを主目的とする。 Therefore, the present invention provides a method for producing a latex, which has one or more water phases inside and can improve the yield of elastomer particles in which the water phase forms voids by drying. The main purpose is.
 すなわち、本発明は、
 ケン化度が60~97モル%のポリビニルアルコールが溶解されている水と、
 20℃における比重が0.8以上、沸点が95℃以下である水難溶性有機溶剤にエラストマーが溶解されているエラストマー溶液と、
 を混合して撹拌する工程を含む、ラテックスの製造方法を提供する。
 前記製造方法において、前記水難溶性有機溶剤にHLBが8.0以下の界面活性剤が溶解されていてもよい。
 また、本発明は、
 水と、
 20℃における比重が0.8以上、沸点が95℃以下である水難溶性有機溶剤にエラストマー及びHLBが8.0以下の界面活性剤が溶解されているエラストマー溶液と、
 を混合して撹拌した後、
 ケン化度が60~97モル%のポリビニルアルコールが溶解されている水を添加して撹拌する工程を含む、ラテックスの製造方法を提供する。
 前記HLBが8.0以下の界面活性剤は、ソルビタンモノオレアート、ソルビタントリオレアート及びグリセロールモノステアレートからなる群から選択される少なくとも1種であってもよい。
 前記エラストマー溶液及び前記ケン化度が60~97モル%のポリビニルアルコールが溶解されている水の少なくとも一方に、ケン化度が20~59モル%のポリビニルアルコール及びカルボキシ変性のポリ酢酸ビニルのうち少なくとも1種が溶解されていてもよい。
 前記ポリ酢酸ビニルは、アクリル酸、メタクリル酸、マレイン酸、フマル酸、クロトン酸、イタコン酸、マレイン酸モノエステル、フマル酸モノエステル及びイタコン酸モノエステルからなる群から選択される少なくとも1種と、酢酸ビニルと、の共重合体であってもよい。
 前記エラストマーは、クロロプレンゴム、ニトリルゴム又はスチレン系ブロック共重合体であってもよい。
 前記水難溶性有機溶剤は、ハロゲン系有機溶剤であってもよい。
That is, the present invention is
Water in which polyvinyl alcohol having a saponification degree of 60 to 97 mol% is dissolved,
An elastomer solution in which an elastomer is dissolved in a poorly water-soluble organic solvent having a specific gravity at 20°C of 0.8 or more and a boiling point of 95°C or less,
There is provided a method for producing a latex, which comprises the step of mixing and stirring.
In the manufacturing method, a surfactant having an HLB of 8.0 or less may be dissolved in the poorly water-soluble organic solvent.
Further, the present invention is
water and,
An elastomer solution in which an elastomer and a surfactant having an HLB of 8.0 or less are dissolved in a poorly water-soluble organic solvent having a specific gravity at 20°C of 0.8 or more and a boiling point of 95°C or less,
After mixing and stirring,
Provided is a method for producing a latex, which comprises a step of adding water in which polyvinyl alcohol having a saponification degree of 60 to 97 mol% is dissolved and stirring the mixture.
The surfactant having an HLB of 8.0 or less may be at least one selected from the group consisting of sorbitan monooleate, sorbitan trioleate and glycerol monostearate.
At least one of polyvinyl alcohol having a saponification degree of 20 to 59 mol% and carboxy-modified polyvinyl acetate in at least one of the water in which the elastomer solution and the polyvinyl alcohol having a saponification degree of 60 to 97 mol% are dissolved. One kind may be dissolved.
The polyvinyl acetate is at least one selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, maleic acid monoester, fumaric acid monoester and itaconic acid monoester, It may be a copolymer with vinyl acetate.
The elastomer may be chloroprene rubber, nitrile rubber, or styrene block copolymer.
The poorly water-soluble organic solvent may be a halogen-based organic solvent.
 また、本発明は、
 内部に1つ以上の水相を有し、乾燥させることで該水相が空隙を形成するエラストマー粒子と、
 ケン化度が60~97モル%のポリビニルアルコールが溶解されている水と、を含有するラテックスを提供する。
 前記ラテックスは、HLBが8.0以下の界面活性剤を含有してもよい。
 前記ラテックスは、ケン化度が20~59モル%のポリビニルアルコール及びカルボキシ変性のポリ酢酸ビニルのうち少なくとも1種を含有してもよい。
 前記ラテックスを用いて下記作製条件に準じて作製されたキャストフィルムの熱伝導率が0.100W/mk以下、破断強度が3.5MPa以上、破断伸びが180%以上であってもよい。
 作製条件:
 前記ラテックスを水平に設置したガラス板上へ流し、3日間室温乾燥させて厚さ0.5mmのフィルム膜を形成した後、室温で1日間真空乾燥して水分を蒸散させ、縦100mm、横50mmに成形して、キャストフィルムを作製する。
 前記ラテックスは、水系接着剤用又は水系塗料用であってもよい。
 また、本発明は、前記ラテックスを用いてなる、水系接着剤又は水系塗料を提供する。
Further, the present invention is
Elastomer particles having one or more aqueous phases therein, and the aqueous phases forming voids when dried,
A latex containing water in which polyvinyl alcohol having a saponification degree of 60 to 97 mol% is dissolved is provided.
The latex may contain a surfactant having an HLB of 8.0 or less.
The latex may contain at least one of polyvinyl alcohol having a saponification degree of 20 to 59 mol% and carboxy-modified polyvinyl acetate.
A cast film produced using the above latex according to the following production conditions may have a thermal conductivity of 0.100 W/mk or less, a breaking strength of 3.5 MPa or more, and a breaking elongation of 180% or more.
Manufacturing conditions:
The latex is poured on a glass plate placed horizontally and dried at room temperature for 3 days to form a film film having a thickness of 0.5 mm, and then vacuum dried at room temperature for 1 day to evaporate water, 100 mm in length, 50 mm in width. And molded into a cast film.
The latex may be for water-based adhesives or water-based paints.
The present invention also provides a water-based adhesive or water-based coating material using the latex.
 本発明によれば、内部に1つ以上の水相を有し、乾燥させることで該水相が空隙を形成するエラストマー粒子の収率を向上させることが可能なラテックスの製造方法が提供されうる。 INDUSTRIAL APPLICABILITY According to the present invention, there can be provided a method for producing a latex that has one or more aqueous phases inside and can improve the yield of elastomer particles in which the aqueous phase forms voids when dried. ..
 以下、本発明を実施するための形態について説明する。なお、以下に説明する実施形態は、本発明の実施形態の一例を示したものであり、これにより本発明の範囲が狭く解釈されることはない。なお、各数値範囲の上限値と下限値は、所望により、任意に組み合わせることができる。 Hereinafter, modes for carrying out the present invention will be described. It should be noted that the embodiment described below is an example of the embodiment of the present invention, and the scope of the present invention is not narrowly interpreted by this. The upper limit value and the lower limit value of each numerical range can be arbitrarily combined as desired.
<1.ラテックスの製造方法>
 本発明の一実施形態に係るラテックスの製造方法は、内部に1つ以上の空隙を有するエラストマー粒子を生成するためのラテックスを製造する方法である。また、本実施形態に係るラテックスの製造方法は、内部に1つ以上の水相を有し、乾燥させることで該水相が空隙を形成するエラストマー粒子を含有するラテックスを製造する方法でもありうる。なお、内部に1つ以上の水相を有し、乾燥させることで該水相が空隙を形成するエラストマー粒子には、内部に1つの水相を有し、乾燥させることで該水相が1つの空隙を形成する単核のエラストマー粒子と、内部に複数の水相を有し、乾燥させることで該水相が複数の空隙を形成する多中空のエラストマー粒子と、の両方が含まれる。
<1. Latex production method>
A method for producing a latex according to an embodiment of the present invention is a method for producing a latex for producing an elastomer particle having one or more voids inside. Further, the method for producing a latex according to the present embodiment may also be a method for producing a latex containing elastomer particles having one or more water phases inside and drying the water phase to form voids. .. It should be noted that the elastomer particles having one or more water phase inside and forming a void in the water phase when dried have one water phase inside and are dried to have a water phase of 1 Both a mononuclear elastomer particle forming one void and a multi-hollow elastomer particle having a plurality of aqueous phases therein and the aqueous phase forming a plurality of voids when dried are included.
 本実施形態の製造方法は、後述する製造方法Iと製造方法IIとに大別される。製造方法I又は製造方法IIから得られるラテックスは、どちらも、内部に1つ以上の水相を有し、乾燥させることで該水相が空隙を形成するエラストマー粒子を収率よく生成するために好適に用いられる。以下、製造方法I及び製造方法IIについて詳細に説明する。 The manufacturing method of this embodiment is roughly classified into a manufacturing method I and a manufacturing method II described later. In order to produce elastomer particles in which the latex obtained from the production method I or the production method II has one or more water phases inside and the water phase forms voids when dried, the yield is high. It is preferably used. Hereinafter, the manufacturing method I and the manufacturing method II will be described in detail.
(1)製造方法I
 製造方法Iは、ケン化度が60~97モル%のポリビニルアルコールが溶解されている水と、20℃における比重が0.8以上、沸点が95℃以下である水難溶性有機溶剤にエラストマーが溶解されているエラストマー溶液と、を混合して撹拌する工程を含む、ラテックスの製造方法である。
(1) Manufacturing method I
In the production method I, the elastomer is dissolved in water in which polyvinyl alcohol having a saponification degree of 60 to 97 mol% is dissolved, and a poorly water-soluble organic solvent having a specific gravity at 20°C of 0.8 or more and a boiling point of 95°C or less. Is a method for producing a latex, which comprises a step of mixing the above-mentioned elastomer solution and stirring.
 上記水と上記エラストマー溶液とを混合して撹拌する工程は、好ましくは、上記水と上記エラストマー溶液とを混合して撹拌し、上記エラストマー溶液を内部に水相を有する微粒液滴として上記水中に微分散させた分散液を得る工程である。「微粒液滴」とは、数平均粒子径が10.0μm以下の液滴をいう。 The step of mixing and stirring the water and the elastomer solution is preferably mixing and stirring the water and the elastomer solution, and the elastomer solution in the water as fine droplets having an aqueous phase inside. This is a step of obtaining a finely dispersed dispersion liquid. The “fine droplet” means a droplet having a number average particle diameter of 10.0 μm or less.
 製造方法Iは、上記のような撹拌を行う工程を含むものであれば特に限定されないが、好ましくは、以下の製造方法である:
 20℃における比重が0.8以上、沸点が95℃以下である水難溶性有機溶剤にエラストマーを溶解させてエラストマー溶液を得るエラストマー溶液作製工程と、
 ケン化度が60~97モル%のポリビニルアルコールが溶解されている水と、上記エラストマー溶液と、を混合して撹拌し、上記エラストマー溶液を内部に水相を有する微粒液滴として上記水中に微分散させた分散液を得る分散液作製工程と、
 を含む、ラテックスの製造方法。
The production method I is not particularly limited as long as it includes the step of performing stirring as described above, but the following production method is preferable:
An elastomer solution preparation step of obtaining an elastomer solution by dissolving the elastomer in a poorly water-soluble organic solvent having a specific gravity at 20°C of 0.8 or more and a boiling point of 95°C or less;
Water in which polyvinyl alcohol having a saponification degree of 60 to 97 mol% is dissolved and the above-mentioned elastomer solution are mixed and stirred, and the above-mentioned elastomer solution is finely dispersed in the above-mentioned water as fine droplets having an aqueous phase therein. A dispersion liquid preparation step of obtaining a dispersed dispersion liquid,
A method for producing a latex, comprising:
 上記分散液は、エラストマー溶液が内部に水相を有する微粒液滴として水中に微分散された、W/O/W型エマルジョンである。製造方法Iは、特定のポリビニルアルコールと特定の水難溶性有機溶剤とを用いることで、分散液(W/O/W型エマルジョン)中の微粒液滴内部の水相(内部水相)を安定化させることができ、ひいては、安定なW/O/W型エマルジョンを形成することができる。 The dispersion liquid is a W/O/W type emulsion in which the elastomer solution is finely dispersed in water as fine droplets having an aqueous phase inside. The production method I stabilizes the aqueous phase (internal aqueous phase) inside the fine droplets in the dispersion (W/O/W type emulsion) by using a specific polyvinyl alcohol and a specific poorly water-soluble organic solvent. It is possible to form a stable W/O/W type emulsion.
 詳細は後述するが、上記分散液に含まれる水難溶性有機溶剤を蒸散させることで、分散液中の微粒液滴は、エラストマー粒子となる。微粒液滴内部の水相(内部水相)は、エラストマー粒子の内部で固定化された後、乾燥に供されることで空隙構造を形成する「空隙核」であり、内部水相の安定性は、内部に空隙を有するエラストマー粒子の収率に影響を及ぼす。つまり、内部水相を安定化させることで、水難溶性有機溶剤が蒸散する際の内部水相の離脱が抑制され、その結果、乾燥に供した際に内部に空隙を有しないエラストマー粒子の発生が抑えられるため、内部に空隙を有するエラストマー粒子の収率を上げることが可能となる。 Details will be described later, but by evaporating the poorly water-soluble organic solvent contained in the dispersion, the fine droplets in the dispersion become elastomer particles. The stability of the internal aqueous phase is the “aqueous core” that forms the void structure when the aqueous phase (internal aqueous phase) inside the fine droplets is fixed inside the elastomer particles and then dried. Influences the yield of elastomer particles having voids inside. That is, by stabilizing the internal water phase, the separation of the internal water phase at the time of evaporation of the poorly water-soluble organic solvent is suppressed, as a result, the generation of elastomer particles having no voids when subjected to drying Since it is suppressed, it is possible to increase the yield of the elastomer particles having voids inside.
 上記エラストマーとしては、合成ゴム及び/又は熱可塑性エラストマーが好ましい。合成ゴムは、好ましくは、クロロプレンゴム(CR)、スチレン-ブタジエンゴム(SBR)、アクリルゴム(ACM)、ニトリルゴム(NBR)、エピクロルヒドリンゴム(ECO)、ブタジエンゴム(BR)、エチレン-プロピレン-ジエンゴム(EPDM)、天然ゴム(NR)及びイソプレンゴム(IR)である。熱可塑性エラストマーは、好ましくは、スチレン系ブロック共重合体である。 As the above elastomer, synthetic rubber and/or thermoplastic elastomer is preferable. The synthetic rubber is preferably chloroprene rubber (CR), styrene-butadiene rubber (SBR), acrylic rubber (ACM), nitrile rubber (NBR), epichlorohydrin rubber (ECO), butadiene rubber (BR), ethylene-propylene-diene rubber. (EPDM), natural rubber (NR) and isoprene rubber (IR). The thermoplastic elastomer is preferably a styrene block copolymer.
 「スチレン系ブロック共重合体」とは、スチレンと、スチレンと共重合可能な単量体と、のブロック共重合体を意味する。スチレンと共重合可能な単量体としては、例えば、イソプレン、ブタジエン、クロロプレンなどが挙げられる。スチレン系ブロック共重合体としては、例えば、スチレン-イソプレン-スチレントリブロック共重合体(SIS)、スチレン-ブタジエン-スチレントリブロック共重合体(SBS)、スチレン-エチレンブチレン-スチレントリブロック共重合体(SEBS)、スチレン-エチレンプロピレン-スチレントリブロック共重合体(SEPS)、スチレン-クロロプレン-スチレントリブロック共重合体(SCS)などが挙げられる。 “Styrene-based block copolymer” means a block copolymer of styrene and a monomer copolymerizable with styrene. Examples of the monomer copolymerizable with styrene include isoprene, butadiene, chloroprene and the like. Examples of the styrene block copolymer include styrene-isoprene-styrene triblock copolymer (SIS), styrene-butadiene-styrene triblock copolymer (SBS), styrene-ethylenebutylene-styrene triblock copolymer. (SEBS), styrene-ethylene propylene-styrene triblock copolymer (SEPS), styrene-chloroprene-styrene triblock copolymer (SCS) and the like.
 得られるエラストマー粒子の熱伝導率、破断強度及び破断伸びを向上させる観点から、エラストマーとしては、クロロプレンゴム、ニトリルゴム及びスチレン系ブロック共重合体がより好ましく、クロロプレンゴムがさらに好ましい。これらのエラストマーは、単独で用いられてもよく、2種以上が併用されてもよい。 From the viewpoint of improving the thermal conductivity, breaking strength and breaking elongation of the obtained elastomer particles, the elastomer is more preferably chloroprene rubber, nitrile rubber or styrene block copolymer, and even more preferably chloroprene rubber. These elastomers may be used alone or in combination of two or more.
 上記水難溶性有機溶剤は、20℃における比重が0.8以上であり、より好ましくは0.9以上であり、またその上限値は、特に限定されないが、好ましくは1.8以下であり、好ましくは1.6以下である。20℃における比重が0.8未満であると、ポリビニルアルコールが溶解されている水とエラストマー溶液とを撹拌する際に、エラストマー溶液が浮いてきてしまい、水中にエラストマー溶液を安定的に微分散させることが難しい。 The water-insoluble organic solvent has a specific gravity at 20° C. of 0.8 or more, more preferably 0.9 or more, and its upper limit is not particularly limited, but preferably 1.8 or less, and preferably Is 1.6 or less. If the specific gravity at 20° C. is less than 0.8, the elastomer solution will float when the water in which the polyvinyl alcohol is dissolved and the elastomer solution are stirred, and the elastomer solution will be stably finely dispersed in water. Difficult to do.
 上記水難溶性有機溶剤は、沸点の上限が95℃以下であり、好ましくは90℃以下、より好ましくは80℃以下、さらに好ましくは70℃以下である。また、上記水難溶性有機溶剤は、沸点の下限が好ましくは30℃以上であり、より好ましくは40℃以上である。本実施形態の製造方法により得られるラテックスからエラストマー粒子を生成する際には水難溶性有機溶剤を蒸散させる必要があるが、水難溶性有機溶剤の沸点が95℃超であると、水難溶性有機溶剤よりも先に水が蒸散してしまい、内部に空隙を有するエラストマー粒子の収率が低下するおそれがある。 The upper limit of the boiling point of the poorly water-soluble organic solvent is 95°C or lower, preferably 90°C or lower, more preferably 80°C or lower, and further preferably 70°C or lower. The lower limit of the boiling point of the poorly water-soluble organic solvent is preferably 30°C or higher, more preferably 40°C or higher. When producing elastomer particles from the latex obtained by the production method of the present embodiment, it is necessary to evaporate the poorly water-soluble organic solvent, but when the boiling point of the poorly water-soluble organic solvent is higher than 95° C., it is better than the poorly water-soluble organic solvent. However, water may evaporate first, and the yield of elastomer particles having voids inside may decrease.
 上記水難溶性有機溶剤として、特に限定されないが、例えば、クロロプレンモノマー(2-クロロ-1,3-ブタジエン)、塩化メチレン、クロロホルム、四塩化炭素などのハロゲン系有機溶剤及びベンゼンなどが挙げられ、これらからなる群から選択される少なくとも1種又は2種以上を使用することができる。 The poorly water-soluble organic solvent is not particularly limited, and examples thereof include a chloroprene monomer (2-chloro-1,3-butadiene), a halogen-based organic solvent such as methylene chloride, chloroform and carbon tetrachloride, and benzene. At least one kind or two or more kinds selected from the group consisting of can be used.
 20℃における比重が0.8以上であり、且つ、沸点が95℃以下である水難溶性有機溶剤は、エラストマーの種類に応じて適宜選択されうる。
 エラストマーが、例えば、クロロプレンゴム(CR)、スチレン-ブタジエンゴム(SBR)、アクリルゴム(ACM)、スチレン-ブタジエン-スチレントリブロック共重合体(SBS)及びスチレン-クロロプレン-スチレントリブロック共重合体(SCS)の少なくともいずれかの場合、水難溶性有機溶剤は、クロロプレンモノマー(2-クロロ-1,3-ブタジエン)、塩化メチレン、クロロホルム、四塩化炭素などのハロゲン系有機溶剤及びベンゼンが好ましい。
 エラストマーが、例えば、クロロプレンゴム(CR)、スチレン-イソプレン-スチレントリブロック共重合体(SIS)及びスチレン-クロロプレン-スチレントリブロック共重合体(SCS)の少なくともいずれかの場合、水難溶性有機溶剤は、クロロプレンモノマーがより好ましい。エラストマーが、例えば、ニトリルゴム(NBR)及びエピクロルヒドリンゴム(ECO)の場合、水難溶性有機溶剤は、クロロプレンモノマー、塩化メチレン、クロロホルム、四塩化炭素などのハロゲン系有機溶剤が好ましい。
 エラストマーが、例えば、ブタジエンゴム(BR)、エチレン-プロピレン-ジエンゴム(EPDM)、天然ゴム(NR)及びイソプレンゴム(IR)の場合、水難溶性有機溶剤は、ベンゼンが好ましい。
 得られるエラストマー粒子の熱伝導率、破断強度及び破断伸びを向上させる観点から、エラストマーとしてクロロプレンゴム、ニトリルゴム又はスチレン系ブロック共重合体を用いる場合、水難溶性有機溶剤はハロゲン系有機溶剤が好ましく、クロロプレンモノマーがより好ましい。
The poorly water-soluble organic solvent having a specific gravity at 20° C. of 0.8 or more and a boiling point of 95° C. or less can be appropriately selected according to the type of elastomer.
Examples of the elastomer include chloroprene rubber (CR), styrene-butadiene rubber (SBR), acrylic rubber (ACM), styrene-butadiene-styrene triblock copolymer (SBS) and styrene-chloroprene-styrene triblock copolymer ( In at least one of SCS), the poorly water-soluble organic solvent is preferably a chloroprene monomer (2-chloro-1,3-butadiene), a halogen-based organic solvent such as methylene chloride, chloroform, carbon tetrachloride and benzene.
When the elastomer is, for example, at least one of chloroprene rubber (CR), styrene-isoprene-styrene triblock copolymer (SIS) and styrene-chloroprene-styrene triblock copolymer (SCS), the poorly water-soluble organic solvent is The chloroprene monomer is more preferable. When the elastomer is, for example, nitrile rubber (NBR) and epichlorohydrin rubber (ECO), the poorly water-soluble organic solvent is preferably a halogen-based organic solvent such as chloroprene monomer, methylene chloride, chloroform and carbon tetrachloride.
When the elastomer is, for example, butadiene rubber (BR), ethylene-propylene-diene rubber (EPDM), natural rubber (NR) and isoprene rubber (IR), the sparingly water-soluble organic solvent is preferably benzene.
From the viewpoint of improving the thermal conductivity of the obtained elastomer particles, the breaking strength and the breaking elongation, when using chloroprene rubber as the elastomer, nitrile rubber or a styrene block copolymer, the water-insoluble organic solvent is preferably a halogen-based organic solvent, Chloroprene monomers are more preferred.
 製造方法Iで用いられるエラストマー溶液は、上記水難溶性有機溶剤に上記エラストマーを溶解するエラストマー溶液作製工程により得られうる。水難溶性有機溶剤にエラストマーを溶解する方法は特に限定されず、例えば撹拌装置を用いて水難溶性有機溶剤とエラストマーとを撹拌すればよい。このときの温度は、エラストマーを溶解できる温度であれば特に限定されないが、例えば室温で行ってもよく、より具体的には5~40℃や10~30℃で行ってもよい。 The elastomer solution used in the production method I can be obtained by an elastomer solution preparation step of dissolving the elastomer in the poorly water-soluble organic solvent. The method for dissolving the elastomer in the poorly water-soluble organic solvent is not particularly limited, and for example, the poorly water-soluble organic solvent and the elastomer may be stirred using a stirrer. The temperature at this time is not particularly limited as long as it can dissolve the elastomer, but may be, for example, room temperature, and more specifically, 5 to 40° C. or 10 to 30° C.
 水難溶性有機溶剤又はエラストマー溶液に、重合反応が起こらないようにするために、重合停止剤などを適宜添加してもよい。当該重合停止剤の種類は、特に限定されず、例えば、フェノチアジン、チオジフェニルアミン等のアミン系化合物;4-tert-ブチルカテコール、2,2’-メチレン(ビス-4-メチル-6-tert-ブチルフェノール)等のフェノール系化合物などからなる群から選択される1種又は2種以上を用いることができる。このうち、フェノール系化合物が好ましく、より好ましくは4-tert-ブチルカテコールである。 A polymerization terminator or the like may be appropriately added to the poorly water-soluble organic solvent or the elastomer solution in order to prevent the polymerization reaction from occurring. The type of the polymerization terminator is not particularly limited, and examples thereof include amine compounds such as phenothiazine and thiodiphenylamine; 4-tert-butylcatechol, 2,2′-methylene (bis-4-methyl-6-tert-butylphenol). 1) or 2 or more selected from the group consisting of phenolic compounds such as ). Of these, a phenolic compound is preferable, and 4-tert-butylcatechol is more preferable.
 エラストマー溶液中のエラストマーの含有量は、特に限定されないが、エラストマー溶液100質量部中5~50質量部が好ましく、10~40質量部がより好ましい。 The content of the elastomer in the elastomer solution is not particularly limited, but is preferably 5 to 50 parts by mass and more preferably 10 to 40 parts by mass in 100 parts by mass of the elastomer solution.
 製造方法Iにおいて、上記水難溶性有機溶剤には、HLBが8.0以下の界面活性剤が溶解されていることが好ましい。すなわち、上記エラストマー溶液は、20℃における比重が0.8以上、沸点が95℃以下である水難溶性有機溶剤に、エラストマー及びHLBが8.0以下の界面活性剤が溶解されているエラストマー溶液であることが好ましい。 In the production method I, it is preferable that a surfactant having an HLB of 8.0 or less is dissolved in the poorly water-soluble organic solvent. That is, the elastomer solution is an elastomer solution in which an elastomer and a surfactant having an HLB of 8.0 or less are dissolved in a poorly water-soluble organic solvent having a specific gravity at 20° C. of 0.8 or more and a boiling point of 95° C. or less. Preferably.
 上記界面活性剤のHLBは、好ましくは8.0以下であり、より好ましくは7.0以下、さらに好ましくは6.0以下、特に好ましくは5.0以下である。HLBが8.0以下の界面活性剤を用いることで、分散液中の内部水相の安定性がより向上し、水難溶性有機溶剤の蒸散時における内部水相の離脱が抑制されるため、内部に空隙を有するエラストマー粒子の収率をさらに上げることが可能である。 The HLB of the above-mentioned surfactant is preferably 8.0 or less, more preferably 7.0 or less, further preferably 6.0 or less, and particularly preferably 5.0 or less. By using a surfactant having an HLB of 8.0 or less, the stability of the internal aqueous phase in the dispersion liquid is further improved, and the internal aqueous phase is prevented from being desorbed during evaporation of the poorly water-soluble organic solvent. It is possible to further increase the yield of elastomer particles having voids.
 上記界面活性剤として、特に限定されないが、例えば、ショ糖脂肪酸エステル;ソルビタンモノステアレート、ソルビタンモノパルミテート、ソルビタンモノベヘネート、ソルビタンモノモンタネートなどのソルビタン脂肪酸エステル系界面活性剤;グリセリンモノラウレート、グリセリンモノパルミテート、グリセリンモノステアレート、ジグリセリンジステアレート、トリグリセリンモノステアレート、テトラグリセリンモノモンタネートなどのグリセリン脂肪酸エステル系界面活性剤などが挙げられ、これらからなる群から選択される少なくとも1種である。
 上記界面活性剤のうち、ノニオン性界面活性剤が好ましい。
The surfactant is not particularly limited, and examples thereof include sucrose fatty acid ester; sorbitan monostearate, sorbitan monopalmitate, sorbitan monobehenate, sorbitan monomontanate, and other sorbitan fatty acid ester surfactants; glycerin monolaurate. Rate, glycerin monopalmitate, glycerin monostearate, diglycerin distearate, triglycerin monostearate, glycerin fatty acid ester-based surfactants such as tetraglycerin monomontanate, and the like, selected from the group consisting of these. It is at least one kind.
Among the above-mentioned surfactants, nonionic surfactants are preferable.
 HLBが8.0以下の界面活性剤は、好ましくは、ソルビタンモノパルミテート(Span40、HLB:6.7)、ソルビタンモノステアレート(Span60、HLB:4.7)、ソルビタントリステアレート(Span65、HLB:2.1)、ソルビタンモノオレアート(Span80、HLB:4.3)、ソルビタンセスキオアレアート(Span83、HLB:3.7)、ソルビタントリオレアート(Span85、HLB:1.8)、及びソルビタンイソステアレート(Span120、HLB:4.7)などのソルビタン脂肪酸エステル系;グリセロールモノステアレート(MS-60、HLB:3.5)、グリセロールモノステアレート(MS-50、HLB:2.8)、グリセロールモノオレエート(MO-60、HLB:2.8)などのグリセリン脂肪酸エステル系;などからなる群から選択される少なくとも1種である。これらの中でも、より好ましくは、ソルビタンモノオレアート、ソルビタントリオレアート及びグリセロールモノステアレートからなる群から選択される少なくとも1種である。 The surfactant having an HLB of 8.0 or less is preferably sorbitan monopalmitate (Span 40, HLB: 6.7), sorbitan monostearate (Span 60, HLB: 4.7), sorbitan tristearate (Span 65, HLB: 2.1), sorbitan monooleate (Span80, HLB: 4.3), sorbitan sesquioaleate (Span83, HLB: 3.7), sorbitan trioleate (Span85, HLB: 1.8), and Sorbitan fatty acid ester system such as sorbitan isostearate (Span120, HLB: 4.7); glycerol monostearate (MS-60, HLB: 3.5), glycerol monostearate (MS-50, HLB: 2.8) ), glycerol monooleate (MO-60, HLB: 2.8), and other glycerin fatty acid ester-based compounds; and the like. Among these, more preferable is at least one selected from the group consisting of sorbitan monooleate, sorbitan trioleate and glycerol monostearate.
 界面活性剤は、単独で用いられてもよく、2種以上が併用されてもよい。2種以上の界面活性を併用する場合、「HLBが8.0以下の界面活性剤」とは、それぞれの界面活性剤のHLBが8.0以下であることを意味し、2種以上の界面活性剤のHLBの平均値が8.0以下であることを意味するものではない。 The surfactants may be used alone or in combination of two or more. When two or more kinds of surface active agents are used in combination, the term “surfactant having an HLB of 8.0 or less” means that the HLB of each surfactant is 8.0 or less. It does not mean that the average value of HLB of the activator is 8.0 or less.
 界面活性剤を用いる場合、エラストマー溶液中の界面活性剤の含有量は、エラストマー溶液100質量部中0.01~5質量部が好ましく、0.1~5質量部がより好ましい。上述したエラストマー溶液作製工程において、水難溶性有機溶剤に界面活性剤を溶解する方法は特に限定されず、例えば、水難溶性有機溶剤と界面活性剤とを撹拌装置を用いて撹拌した後、エラストマーを添加して更に撹拌すればよい。 When a surfactant is used, the content of the surfactant in the elastomer solution is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 5 parts by mass in 100 parts by mass of the elastomer solution. In the elastomer solution preparation step described above, the method of dissolving the surfactant in the poorly water-soluble organic solvent is not particularly limited, and for example, after stirring the poorly water-soluble organic solvent and the surfactant with a stirring device, the elastomer is added. And stir further.
 製造方法Iで用いられるケン化度が60~97モル%のポリビニルアルコールは、ケン化度の下限が、好ましくは70モル%以上、より好ましくは75モル%以上、さらに好ましくは80モル%以上である。また、上記ポリビニルアルコールは、ケン化度の上限が、好ましくは95モル%以下、より好ましくは90モル%以下である。ポリビニルアルコールのケン化度が60モル%未満又は97モル%超も適用可能であるが、該ポリビニルアルコールを単独で使用すると、ポリビニルアルコールが溶解されている水とエラストマー溶液とを撹拌した際に、安定的に乳化できず、水中にエラストマー溶液を安定的に微分散させることが困難である。 The polyvinyl alcohol having a saponification degree of 60 to 97 mol% used in the production method I has a lower saponification degree of preferably 70 mol% or more, more preferably 75 mol% or more, still more preferably 80 mol% or more. is there. The upper limit of the saponification degree of the polyvinyl alcohol is preferably 95 mol% or less, more preferably 90 mol% or less. The degree of saponification of polyvinyl alcohol of less than 60 mol% or more than 97 mol% is also applicable, but when the polyvinyl alcohol is used alone, when water in which polyvinyl alcohol is dissolved and an elastomer solution are stirred, It cannot be stably emulsified, and it is difficult to stably finely disperse the elastomer solution in water.
 ケン化度が60~97モル%のポリビニルアルコールは、単独で用いられてもよく、2種以上が併用されてもよい。ケン化度が60~97モル%のポリビニルアルコールを2種以上併用する場合、「ケン化度が60~97モル%のポリビニルアルコール」とは、それぞれのポリビニルアルコールのケン化度が60~97モル%であることを意味し、2種以上のポリビニルアルコールのケン化度の平均値が60~97モル%であることを意味するものではない。 The polyvinyl alcohol having a saponification degree of 60 to 97 mol% may be used alone or in combination of two or more kinds. When two or more polyvinyl alcohols having a saponification degree of 60 to 97 mol% are used in combination, the "polyvinyl alcohol having a saponification degree of 60 to 97 mol%" means that the saponification degree of each polyvinyl alcohol is 60 to 97 mol. %, and does not mean that the average saponification degree of two or more polyvinyl alcohols is 60 to 97 mol %.
 エラストマー溶液及びケン化度が60~97モル%のポリビニルアルコールが溶解されている水のうち少なくとも一方には、さらに、ケン化度が20~59モル%のポリビニルアルコール及びカルボキシ変性のポリ酢酸ビニルのうち少なくとも1種が溶解されていることが好ましい。ケン化度が20~59モル%のポリビニルアルコール及び/又はカルボキシ変性のポリ酢酸ビニルを併用すると、微粒液滴内部の水相はより安定化され、水難溶性有機溶剤が蒸散する際の内部水相の離脱がより効果的に抑制される。その結果、ラテックスを乾燥に供した際に内部に空隙を有しないエラストマー粒子の発生が抑えられるため、内部に空隙を有するエラストマー粒子の収率を上げることが可能となる。 At least one of the elastomer solution and water in which polyvinyl alcohol having a saponification degree of 60 to 97 mol% is dissolved, polyvinyl alcohol having a saponification degree of 20 to 59 mol% and carboxy-modified polyvinyl acetate are further added. It is preferable that at least one of them is dissolved. When polyvinyl alcohol having a saponification degree of 20 to 59 mol% and/or carboxy-modified polyvinyl acetate is used together, the aqueous phase inside the fine droplets is more stabilized, and the internal aqueous phase when the poorly water-soluble organic solvent evaporates Withdrawal is suppressed more effectively. As a result, when the latex is dried, the generation of elastomer particles having no voids inside is suppressed, so that it is possible to increase the yield of elastomer particles having voids inside.
 ケン化度が20~59モル%のポリビニルアルコールは、ケン化度の下限が、好ましくは25モル%以上、より好ましくは30モル%以上、さらに好ましくは35モル%以上であり、ケン化度の上限が、好ましくは50モル%以下、より好ましくは45モル%以下である。 The polyvinyl alcohol having a saponification degree of 20 to 59 mol% has a lower saponification degree of preferably 25 mol% or more, more preferably 30 mol% or more, and further preferably 35 mol% or more. The upper limit is preferably 50 mol% or less, more preferably 45 mol% or less.
 ケン化度が20~59モル%のポリビニルアルコールは、単独で用いられてもよく、2種以上が併用されてもよい。ケン化度が20~59モル%のポリビニルアルコールを2種以上併用する場合、「ケン化度が20~59モル%のポリビニルアルコール」とは、それぞれのポリビニルアルコールのケン化度が20~59モル%であることを意味し、2種以上のポリビニルアルコールのケン化度の平均値が20~59モル%であることを意味するものではない。 The polyvinyl alcohol having a saponification degree of 20 to 59 mol% may be used alone or in combination of two or more kinds. When two or more kinds of polyvinyl alcohol having a saponification degree of 20 to 59 mol% are used in combination, the "polyvinyl alcohol having a saponification degree of 20 to 59 mol%" means that the saponification degree of each polyvinyl alcohol is 20 to 59 mol. %, and does not mean that the average saponification degree of two or more polyvinyl alcohols is 20 to 59 mol %.
 カルボキシ変性のポリ酢酸ビニルとは、酢酸ビニルと不飽和カルボン酸との共重合体である。不飽和カルボン酸としては、アクリル酸、メタクリル酸、マレイン酸、フマル酸、クロトン酸、イタコン酸、マレイン酸モノエステル、フマル酸モノエステル及びイタコン酸モノエステルからなる群から選択される少なくとも1種であることが好ましい。カルボキシ変性のポリ酢酸ビニルの市販品としては、例えば、デンカASR CH-09(デンカ株式会社製)などがある。カルボキシ変性のポリ酢酸ビニルは、単独で用いられてもよく、2種以上が併用されてもよい。 Carboxy-modified polyvinyl acetate is a copolymer of vinyl acetate and unsaturated carboxylic acid. The unsaturated carboxylic acid is at least one selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, maleic acid monoester, fumaric acid monoester and itaconic acid monoester. Preferably. Examples of commercially available carboxy-modified polyvinyl acetate include DENKA ASR CH-09 (manufactured by DENKA CORPORATION). The carboxy-modified polyvinyl acetate may be used alone or in combination of two or more kinds.
 上記ポリビニルアルコールが溶解されている水と、上記エラストマー溶液と、を混合した後に撹拌し、上記エラストマー溶液を内部に水相を有する微粒液滴として上記水中に微分散させた分散液を得る方法は、特に限定されない。例えば、ポリビニルアルコールが溶解されている水と、エラストマー溶液と、を反応容器に入れて撹拌装置を用いて撹拌すればよい。撹拌時、せん断発熱による温度上昇を抑制するために反応容器を冷却してもよい。このときの冷却温度は、特に限定されないが、例えば、20~0℃、10~0℃や4~0℃などが挙げられる。分散液中の微粒液滴の数平均粒子径は、撹拌装置の回転数を調整するなどにより、10.0μm以下に調整することが好ましい。 The method in which the water in which the polyvinyl alcohol is dissolved and the elastomer solution are mixed and then stirred to obtain a dispersion liquid in which the elastomer solution is finely dispersed in the water as fine droplets having an aqueous phase inside is It is not particularly limited. For example, water in which polyvinyl alcohol is dissolved and the elastomer solution may be placed in a reaction vessel and stirred using a stirrer. At the time of stirring, the reaction vessel may be cooled in order to suppress the temperature increase due to shearing heat generation. The cooling temperature at this time is not particularly limited, but examples thereof include 20 to 0° C., 10 to 0° C., and 4 to 0° C. The number average particle diameter of the fine droplets in the dispersion is preferably adjusted to 10.0 μm or less by adjusting the rotation speed of the stirring device.
 上記分散液において、ポリビニルアルコールが溶解されている水の含有量は、エラストマー溶液100質量部に対して50~300質量部が好ましく、50~200質量部がより好ましい。また、上記分散液において、ケン化度が60~97モル%のポリビニルアルコールの含有量は、エラストマー溶液100質量部に対して5~30質量部が好ましく、5~25質量部がより好ましく、5~20質量部がさらに好ましい。また、上記分散液において、ケン化度が20~59モル%のポリビニルアルコール及び/又はカルボキシ変性のポリ酢酸ビニルの含有量は、合計で、エラストマー溶液100質量部に対して0.1~10質量部が好ましく、0.5~10質量部がより好ましく、0.5~5質量部がさらに好ましい。 In the dispersion liquid, the content of water in which polyvinyl alcohol is dissolved is preferably 50 to 300 parts by mass, more preferably 50 to 200 parts by mass, relative to 100 parts by mass of the elastomer solution. In the above dispersion, the content of polyvinyl alcohol having a saponification degree of 60 to 97 mol% is preferably 5 to 30 parts by mass, more preferably 5 to 25 parts by mass, based on 100 parts by mass of the elastomer solution. It is more preferably about 20 to 20 parts by mass. In the above dispersion, the total content of polyvinyl alcohol having a saponification degree of 20 to 59 mol% and/or carboxy-modified polyvinyl acetate is 0.1 to 10 parts by mass with respect to 100 parts by mass of the elastomer solution. Part by weight is preferred, 0.5 to 10 parts by weight is more preferred, and 0.5 to 5 parts by weight is even more preferred.
 製造方法Iは、ケン化度が60~97モル%のポリビニルアルコールが溶解されている水と、エラストマー溶液と、を混合し撹拌して分散液を得る工程に加えて、当該分散液中の水難溶性有機溶剤を常圧下又は減圧下で蒸散させて、内部に1つ以上の水相を有するエラストマー粒子を生成させる工程(溶剤蒸散工程)を含むことが好ましい。蒸散させるときの温度は、特に限定されないが、その上限は好ましくは50℃以下、より好ましくは40℃以下であり、また、その下限は好ましくは20℃以上、より好ましくは30℃以上である。また、減圧条件は、特に限定されないが、その上限は好ましくは100mmHg以下、より好ましくは80mmHg以下であり、また、その下限は好ましくは20mmHg以上、より好ましくは40mmHg以上である。 In the production method I, water in which polyvinyl alcohol having a saponification degree of 60 to 97 mol% is dissolved and an elastomer solution are mixed and stirred to obtain a dispersion liquid. It is preferable to include a step (solvent evaporation step) of evaporating a soluble organic solvent under normal pressure or under reduced pressure to generate elastomer particles having one or more aqueous phases inside. The temperature for evaporating is not particularly limited, but its upper limit is preferably 50° C. or lower, more preferably 40° C. or lower, and its lower limit is preferably 20° C. or higher, more preferably 30° C. or higher. The depressurizing condition is not particularly limited, but the upper limit is preferably 100 mmHg or less, more preferably 80 mmHg or less, and the lower limit is preferably 20 mmHg or more, more preferably 40 mmHg or more.
 前述のとおり、上記分散液内では、エラストマー溶液が内部に水相を有する微粒液滴として微分散されている。溶剤蒸散工程を行うことで、微粒液滴を構成するエラストマー溶液中の水難溶性有機溶剤が蒸散して消失する。その結果、微粒液滴を構成するエラストマーの構造が固定化され、エラストマー粒子が生成される。また、上記固定化により、微粒液滴内部の水相(内部水相)は、エラストマー粒子の内部の空隙に閉じ込められる。その後、エラストマー粒子を含有するラテックスが乾燥に供されることで、エラストマー粒子の内部に残存した水相が抜けて、水相が抜けた部分が空隙となる。このように、内部水相は、エラストマー粒子の内部で固定化されて空隙構造を形成することから「空隙核」であるともいえる。 As described above, in the above dispersion liquid, the elastomer solution is finely dispersed as fine droplets having an aqueous phase inside. By performing the solvent evaporation step, the poorly water-soluble organic solvent in the elastomer solution forming the fine droplets evaporates and disappears. As a result, the structure of the elastomer forming the fine droplets is fixed and the elastomer particles are generated. Further, by the immobilization, the aqueous phase (internal aqueous phase) inside the fine droplets is confined in the voids inside the elastomer particles. Then, the latex containing the elastomer particles is subjected to drying, whereby the aqueous phase remaining inside the elastomer particles is removed, and the portions where the aqueous phase is removed become voids. In this way, the internal aqueous phase is fixed inside the elastomer particles to form a void structure, and can therefore be said to be a “void nucleus”.
 内部水相が不安定であると、溶剤蒸散工程において水難溶性有機溶剤が蒸散する際に、内部水相が微粒液滴から離脱して、内部に空隙核を有しないエラストマー粒子が生成される可能性が高まるため、ラテックスを乾燥に供した際に内部に空隙を有するエラストマー粒子の収率が低下するおそれがある。しかしながら、製造方法Iでは、特定の水難溶性有機溶剤及び特定のポリビニルアルコールを用いることで、内部水相を安定化させることが可能であるため、内部水相の離脱が抑制されて、内部水相は安定した空隙核を形成する。その結果、内部に空隙を有しないエラストマー粒子の発生が抑えられて、内部に空隙を有するエラストマー粒子の収率を上げることが可能となる。 When the internal water phase is unstable, when the sparingly water-soluble organic solvent evaporates in the solvent evaporation process, the internal water phase separates from the fine droplets, and elastomer particles without void nuclei inside can be generated. Therefore, the yield of the elastomer particles having voids inside may decrease when the latex is dried. However, in the production method I, it is possible to stabilize the internal aqueous phase by using the specific poorly water-soluble organic solvent and the specific polyvinyl alcohol, so that the internal aqueous phase is prevented from being released and the internal aqueous phase is suppressed. Form stable void nuclei. As a result, generation of elastomer particles having no voids inside is suppressed, and the yield of elastomer particles having voids inside can be increased.
 以上が製造方法Iに関する説明である。次に、製造方法IIについて説明する。 The above is a description of manufacturing method I. Next, the manufacturing method II will be described.
(2)製造方法II
 製造方法IIは、水と、20℃における比重が0.8以上、沸点が95℃以下である水難溶性有機溶剤にエラストマー及びHLBが8.0以下の界面活性剤が溶解されているエラストマー溶液と、を混合して撹拌した後、ケン化度が60~97モル%のポリビニルアルコールが溶解されている水を添加して撹拌する工程を含む、ラテックスの製造方法である。
(2) Manufacturing method II
The production method II comprises water and an elastomer solution in which an elastomer and a surfactant having an HLB of 8.0 or less are dissolved in a poorly water-soluble organic solvent having a specific gravity of 0.8 or more at 20° C. and a boiling point of 95° C. or less. Is mixed and stirred, and then a method for producing a latex is provided, which comprises a step of adding water in which polyvinyl alcohol having a saponification degree of 60 to 97 mol% is dissolved and stirring.
 上記製造方法IIは、上記工程を含むものであれば特に限定されないが、好ましくは、以下の製造方法である:
 水(A)と、
 20℃における比重が0.8以上、沸点が95℃以下である水難溶性有機溶剤にエラストマー及びHLBが8.0以下の界面活性剤が溶解されているエラストマー溶液と、
 を混合して撹拌し、上記エラストマー溶液中に水(A)を微分散させた分散液(a)を得た後、
 上記分散液(a)に、ケン化度が60~97モル%のポリビニルアルコールが溶解されている水(B)を添加して撹拌し、上記分散液(a)を上記水(B)中に微分散させた分散液(b)を得る工程を含む、ラテックスの製造方法。
The production method II is not particularly limited as long as it includes the above steps, but the following production method is preferable:
Water (A),
An elastomer solution in which an elastomer and a surfactant having an HLB of 8.0 or less are dissolved in a poorly water-soluble organic solvent having a specific gravity at 20°C of 0.8 or more and a boiling point of 95°C or less,
Are mixed and stirred to obtain a dispersion liquid (a) in which water (A) is finely dispersed in the elastomer solution,
Water (B) in which polyvinyl alcohol having a saponification degree of 60 to 97 mol% is dissolved is added to the dispersion (a) and stirred, and the dispersion (a) is added to the water (B). A method for producing a latex, which comprises a step of obtaining a finely dispersed dispersion liquid (b).
 上記製造方法IIは、より好ましくは、以下の製造方法である:
 水難溶性有機溶剤にエラストマー及びHLBが8.0以下の界面活性剤を溶解させてエラストマー溶液を得るエラストマー溶液作製工程と、
 上記エラストマー溶液と、水(A)と、を混合して撹拌し、上記エラストマー溶液中に上記水(A)を微分散させた分散液(a)を得る第1分散液作製工程と、
 上記分散液(a)に、ケン化度が60~97モル%のポリビニルアルコールが溶解されている水(B)を添加して撹拌し、上記水(B)中に上記分散液(a)を微分散させた分散液(b)を得る第2分散液作製工程と、
 を含む、ラテックスの製造方法。
The above production method II is more preferably the following production method:
An elastomer solution preparation step of obtaining an elastomer solution by dissolving an elastomer and a surfactant having an HLB of 8.0 or less in a poorly water-soluble organic solvent;
A first dispersion liquid preparation step in which the elastomer solution and water (A) are mixed and stirred to obtain a dispersion liquid (a) in which the water (A) is finely dispersed in the elastomer solution;
Water (B) in which polyvinyl alcohol having a saponification degree of 60 to 97 mol% is dissolved is added to the dispersion liquid (a) and stirred, and the dispersion liquid (a) is added to the water (B). A second dispersion liquid producing step for obtaining a finely dispersed dispersion liquid (b);
A method for producing a latex, comprising:
 上記分散液(b)は、W/O/W型エマルジョンであり、エラストマー溶液が内部に水相を有する微粒液滴として水(B)中に微分散された分散液である。製造方法IIは、特定のポリビニルアルコールと特定の水難溶性有機溶剤とを用いることで、分散液(b)(W/O/W型エマルジョン)中の微粒液滴内部の水相(内部水相)を安定化させることができ、ひいては、安定なW/O/W型エマルジョンを形成することができる。上記製造方法Iで述べたとおり、内部水相を安定化させることにより、内部に空隙を有しないエラストマー粒子の発生が抑えられて、内部に空隙を有するエラストマー粒子の収率を上げることが可能となる。 The above dispersion liquid (b) is a W/O/W type emulsion, and is a dispersion liquid in which the elastomer solution is finely dispersed in water (B) as fine droplets having an aqueous phase inside. The production method II uses a specific polyvinyl alcohol and a specific poorly water-soluble organic solvent to obtain an aqueous phase (internal aqueous phase) inside the fine droplets in the dispersion (b) (W/O/W type emulsion). Can be stabilized, and thus a stable W/O/W type emulsion can be formed. As described in the above-mentioned production method I, by stabilizing the internal aqueous phase, generation of elastomer particles having no voids inside can be suppressed, and the yield of elastomer particles having voids inside can be increased. Become.
 製造方法IIで用いられるエラストマー、水難溶性有機溶剤及びケン化度が60~97モル%のポリビニルアルコールの詳細は、上記製造方法Iで説明したとおりであるため、ここでは説明を省略する。 Details of the elastomer, the poorly water-soluble organic solvent, and the polyvinyl alcohol having a saponification degree of 60 to 97 mol% used in the production method II are the same as those described in the production method I, and therefore the description thereof is omitted here.
 エラストマー溶液及びケン化度が60~97モル%のポリビニルアルコールが溶解されている水のうち少なくとも一方には、さらに、ケン化度が20~59モル%のポリビニルアルコール及びカルボキシ変性のポリ酢酸ビニルのうち少なくとも1種が溶解されていることが好ましい。ケン化度が20~59モル%のポリビニルアルコール及び/又はカルボキシ変性のポリ酢酸ビニルを併用すると、微粒液滴内部の水相は安定化され、水難溶性有機溶剤が蒸散する際の内部水相の離脱が抑制される。その結果、ラテックスを乾燥に供した際に内部に空隙を有しないエラストマー粒子の発生が抑えられるため、内部に空隙を有するエラストマー粒子の収率を上げることが可能となる。 At least one of the elastomer solution and water in which polyvinyl alcohol having a saponification degree of 60 to 97 mol% is dissolved, polyvinyl alcohol having a saponification degree of 20 to 59 mol% and carboxy-modified polyvinyl acetate are further added. It is preferable that at least one of them is dissolved. When polyvinyl alcohol having a saponification degree of 20 to 59 mol% and/or carboxy-modified polyvinyl acetate is used in combination, the aqueous phase inside the fine droplets is stabilized and the internal water phase when the sparingly water-soluble organic solvent evaporates Withdrawal is suppressed. As a result, when the latex is dried, the generation of elastomer particles having no voids inside is suppressed, so that it is possible to increase the yield of elastomer particles having voids inside.
 製造方法IIで用いられるケン化度が20~59モル%のポリビニルアルコール及びカルボキシ変性のポリ酢酸ビニルの詳細は、上記製造方法Iで説明したとおりであるため、ここでは説明を省略する。 Details of the polyvinyl alcohol having a saponification degree of 20 to 59 mol% and the carboxy-modified polyvinyl acetate used in the production method II are the same as those described in the production method I, and therefore the description thereof is omitted here.
 製造方法IIで用いられる界面活性剤のHLBは、8.0以下であり、好ましくは7.0以下、より好ましくは6.0以下、さらに好ましくは5.0以下である。HLBが8.0超であると、安定なW/O/W型エマルジョンを形成することが困難である。 The HLB of the surfactant used in Production Method II is 8.0 or less, preferably 7.0 or less, more preferably 6.0 or less, and further preferably 5.0 or less. When the HLB is more than 8.0, it is difficult to form a stable W/O/W type emulsion.
 HLBが8.0以下の界面活性剤の詳細は、上記製造方法Iで説明したとおりであるため、ここでは説明を省略する。 The details of the surfactant having an HLB of 8.0 or less are the same as those described in the above manufacturing method I, and thus the description thereof is omitted here.
 製造方法IIで用いられるエラストマー溶液は、上記水難溶性有機溶剤にエラストマー及びHLBが8.0以下の界面活性剤を溶解させてエラストマー溶液を得るエラストマー溶液作製工程により得られうる。水難溶性有機溶剤にエラストマー及び界面活性剤を溶解する方法は特に限定されないが、例えば、水難溶性有機溶剤と界面活性剤とを撹拌装置を用いて撹拌した後、エラストマーを添加して更に撹拌すればよい。 The elastomer solution used in the production method II can be obtained by an elastomer solution preparation step in which an elastomer and a surfactant having an HLB of 8.0 or less are dissolved in the poorly water-soluble organic solvent to obtain an elastomer solution. The method of dissolving the elastomer and the surfactant in the poorly water-soluble organic solvent is not particularly limited, for example, after stirring the poorly water-soluble organic solvent and the surfactant using a stirring device, if the elastomer is added and further stirred Good.
 製造方法IIにおいて、エラストマー溶液中のエラストマーの含有量は、エラストマー溶液100質量部中5~50質量部が好ましく、10~40質量部がより好ましい。また、エラストマー溶液中の界面活性剤の含有量は、エラストマー溶液100質量部中0.01~5質量部が好ましく、0.1~5質量部がより好ましい。 In the production method II, the content of the elastomer in the elastomer solution is preferably 5 to 50 parts by mass and more preferably 10 to 40 parts by mass in 100 parts by mass of the elastomer solution. Further, the content of the surfactant in the elastomer solution is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 5 parts by mass in 100 parts by mass of the elastomer solution.
 上記水(A)と、上記エラストマー溶液と、を混合して撹拌した後、上記エラストマー溶液中に水(A)を微分散させた分散液(a)を得る方法は、特に限定されない。例えば、水(A)と、エラストマー溶液と、を反応容器に入れて撹拌装置を用いて撹拌することで、分散液(a)を得ることができる。撹拌時、せん断発熱による温度上昇を抑制するために反応容器を冷却してもよい。分散液(a)中の微粒液滴の数平均粒子径は、撹拌装置の回転数を調整するなどにより、7.0μm以下に調整することが好ましい。このときの冷却温度は、特に限定されないが、例えば、20~0℃、10~0℃や4~0℃などが挙げられる。 The method of obtaining the dispersion liquid (a) in which the water (A) is finely dispersed in the elastomer solution after mixing and stirring the water (A) and the elastomer solution is not particularly limited. For example, the dispersion liquid (a) can be obtained by placing water (A) and the elastomer solution in a reaction container and stirring the mixture using a stirring device. At the time of stirring, the reaction vessel may be cooled in order to suppress the temperature increase due to shearing heat generation. The number average particle diameter of the fine droplets in the dispersion liquid (a) is preferably adjusted to 7.0 μm or less by adjusting the rotation speed of the stirring device. The cooling temperature at this time is not particularly limited, but examples thereof include 20 to 0° C., 10 to 0° C., and 4 to 0° C.
 上記分散液(a)において、水(A)の含有量は、エラストマー溶液100質量部に対して10~100質量部が好ましく、10~50質量部がより好ましい。 In the dispersion liquid (a), the content of water (A) is preferably 10 to 100 parts by mass, and more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the elastomer solution.
 上記分散液(a)に、ケン化度が60~97モル%のポリビニルアルコールが溶解されている水(B)を添加して撹拌し、上記水(B)中に上記分散液(a)を微分散させた分散液(b)を得る方法は、上記エラストマー溶液を内部に水相を有する微粒液滴として水(B)中に微分散させることが可能であれば、特に限定されない。例えば、上記分散液(a)に上記水(B)を添加して撹拌装置を用いて撹拌すればよく、せん断発熱による温度上昇を抑制するために撹拌中に冷却してもよい。分散液(b)中の微粒液滴の数平均粒子径は、撹拌装置の回転数を調整するなどにより、10.0μm以下に調整することが好ましい。 Water (B) in which polyvinyl alcohol having a saponification degree of 60 to 97 mol% is dissolved is added to the dispersion liquid (a) and stirred, and the dispersion liquid (a) is added to the water (B). The method for obtaining the finely dispersed dispersion liquid (b) is not particularly limited as long as the elastomer solution can be finely dispersed in water (B) as fine particle droplets having an aqueous phase therein. For example, the water (B) may be added to the dispersion liquid (a) and stirred using a stirrer, and cooling may be performed during stirring in order to suppress a temperature increase due to shear heat generation. The number average particle diameter of the fine droplets in the dispersion liquid (b) is preferably adjusted to 10.0 μm or less by adjusting the rotation speed of the stirring device.
 製造方法IIは、上述した工程により得られる分散液中の水難溶性有機溶剤、すなわち上記分散液(b)中の水難溶性有機溶剤を、常圧下又は減圧下で蒸散させて、内部に1つ以上の水相を有するエラストマー粒子を生成させる工程(溶剤蒸散工程)を含むことが好ましい。溶剤蒸散工程の詳細は、上記製造方法Iで説明したとおりであるため、ここでは説明を省略する。 Manufacturing method II is one in which at least one is obtained by evaporating the poorly water-soluble organic solvent in the dispersion obtained by the above-mentioned steps, that is, the poorly water-soluble organic solvent in the dispersion (b) under normal pressure or reduced pressure. It is preferable to include the step (solvent evaporation step) of producing the elastomer particles having the aqueous phase. The details of the solvent evaporation step are the same as those described in the above manufacturing method I, and thus the description thereof is omitted here.
 以上詳述した製造方法I及び製造方法IIでは、特定の界面活性剤、特定の水難溶性有機溶剤及び特定のポリビニルアルコールを用いることで、微粒液滴内部の水相を安定化させて、内部に空隙を有するエラストマー粒子の収率向上を可能としている。微粒液滴内部の水相の安定化が収率向上に寄与する理由は、上記製造方法Iで述べたとおりである。 In the production method I and the production method II described in detail above, by using a specific surfactant, a specific poorly water-soluble organic solvent and a specific polyvinyl alcohol, the aqueous phase inside the fine droplets is stabilized and This makes it possible to improve the yield of elastomer particles having voids. The reason why the stabilization of the aqueous phase inside the fine droplets contributes to the improvement of the yield is as described in the above-mentioned production method I.
<2.ラテックス>
 本発明の一実施形態に係るラテックスは、上記ラテックスの製造方法(製造方法I又は製造方法II)により得られる分散液(ラテックス)である。本実施形態のラテックスは、好ましくは、溶剤蒸散工程を経て得られる、水難溶性有機溶剤が蒸散された後のラテックスである。
<2. Latex>
The latex according to one embodiment of the present invention is a dispersion liquid (latex) obtained by the above-mentioned method for producing latex (Production Method I or Production Method II). The latex of the present embodiment is preferably a latex obtained by a solvent evaporation step after the sparingly water-soluble organic solvent has been evaporated.
 水難溶性有機溶剤が蒸散された後のラテックスとは、好ましくは、内部に1つ以上の水相を有し、乾燥させることで該水相が空隙を形成するエラストマー粒子と、ケン化度が60~97モル%のポリビニルアルコールが溶解されている水と、を含有するラテックスである。より好ましくは、ラテックスは、HLBが8.0以下の界面活性剤をさらに含有する。さらに好ましくは、ラテックスは、ケン化度が20~59モル%のポリビニルアルコール及びカルボキシ変性のポリ酢酸ビニルのうち少なくとも1種をさらに含有する。ラテックス中において、エラストマー粒子の内部には乾燥により空隙を形成する水相が存在している。 The latex after the sparingly water-soluble organic solvent has been evaporated preferably has at least one aqueous phase therein, and has an saponification degree of 60 and the elastomer particles having the aqueous phase forming voids. And a water in which about 97 mol% of polyvinyl alcohol is dissolved. More preferably, the latex further contains a surfactant having an HLB of 8.0 or less. More preferably, the latex further contains at least one of polyvinyl alcohol having a saponification degree of 20 to 59 mol% and carboxy-modified polyvinyl acetate. In the latex, an aqueous phase that forms voids when dried exists inside the elastomer particles.
 本実施形態のラテックスに含有されるエラストマー粒子は、内部に乾燥により空隙を形成する水相を有しており、且つ、軟質材料であるエラストマーにより構成されていることから、空隙構造の基本特性である断熱性(低熱伝導率)と、エラストマーの基本特性である柔軟性と、を兼ね備える。このため、本実施形態のラテックスは、フィルム状に形成した際に、優れた断熱性、破断強度及び破断伸びを示す。 Elastomer particles contained in the latex of the present embodiment has an aqueous phase inside which forms voids by drying, and since it is composed of an elastomer that is a soft material, it has the basic characteristics of void structure. It has a certain heat insulating property (low thermal conductivity) and flexibility which is a basic characteristic of an elastomer. Therefore, the latex of the present embodiment exhibits excellent heat insulating properties, breaking strength and breaking elongation when formed into a film.
 具体的には、本実施形態のラテックスを用いて下記作製条件に準じて作製されたキャストフィルムは、熱伝導率が0.100W/mk以下、破断強度が3.5MPa以上、破断伸びが180%以上である。
 作製条件:
 上記ラテックスを水平に設置したガラス板上へ流し、3日間室温乾燥させて厚さ0.5mmのフィルム膜を形成した後、室温で1日間真空乾燥して水分を蒸散させ、縦100mm、横50mmに成形して、キャストフィルムを作製する。
Specifically, the cast film produced according to the following production conditions using the latex of the present embodiment has a thermal conductivity of 0.100 W/mk or less, a breaking strength of 3.5 MPa or more, and a breaking elongation of 180%. That is all.
Manufacturing conditions:
The above latex is poured onto a glass plate placed horizontally and dried at room temperature for 3 days to form a film film having a thickness of 0.5 mm, and then vacuum dried at room temperature for 1 day to evaporate water, 100 mm in length, 50 mm in width. And molded into a cast film.
 熱伝導率は、迅速熱伝導率計QTM-500(京都電子工業株式会社製)を用いて測定することができる。破断強度及び破断伸びは、日本工業規格のJIS K6251に基づいて測定することができる。 The thermal conductivity can be measured using a rapid thermal conductivity meter QTM-500 (manufactured by Kyoto Electronics Manufacturing Co., Ltd.). The breaking strength and breaking elongation can be measured based on Japanese Industrial Standard JIS K6251.
 本実施形態のラテックスは、水系接着剤、水系塗料、水系コーティング剤、ライニングなどの用途に用いられうるが、水系接着剤及び水系塗料の用途に好適である。上記ラテックスを用いてなる水系接着剤及び水系塗料の製造方法は、上記ラテックスを配合しさえすればよく、特に限定されない。すなわち、上記ラテックスを用いた水系接着剤及び水系塗料は、公知の機械や装置を用いて常法に従って製造することができる。 The latex of this embodiment can be used for applications such as water-based adhesives, water-based paints, water-based coating agents, and linings, but is suitable for water-based adhesives and water-based paints. The method for producing an aqueous adhesive and an aqueous paint using the above latex is not particularly limited as long as the above latex is blended. That is, the water-based adhesive and water-based coating material using the above latex can be manufactured by a conventional method using a known machine or device.
<3.エラストマー粒子>
 本発明の一実施形態に係るエラストマー粒子は、内部に1つ以上の空隙を有するエラストマー粒子である。本実施形態のエラストマー粒子は、水難溶性有機溶剤を蒸散させた後の上記ラテックスを乾燥させることで得られうる。乾燥の方法は特に限定されず、ラテックスを常温で減圧乾燥することにより水を蒸散すればよい。
<3. Elastomer particles>
The elastomer particles according to one embodiment of the present invention are elastomer particles having one or more voids inside. The elastomer particles of the present embodiment can be obtained by drying the latex after evaporating the poorly water-soluble organic solvent. The method of drying is not particularly limited, and water may be evaporated by drying the latex under reduced pressure at room temperature.
 本実施形態のエラストマー粒子は、数平均粒子径が、好ましくは0.05~10.0μmであり、より好ましくは0.1~5.0μmである。また、本実施形態のエラストマー粒子は、内部の空隙の直径が、好ましくは10~1000nmであり、より好ましくは50~500nmである。エラストマー粒子の数平均粒子径及び空隙の直径は、透過型電子顕微鏡により測定することができる。 The number average particle size of the elastomer particles of the present embodiment is preferably 0.05 to 10.0 μm, more preferably 0.1 to 5.0 μm. Further, in the elastomer particles of the present embodiment, the diameter of the voids inside is preferably 10 to 1000 nm, more preferably 50 to 500 nm. The number average particle diameter of the elastomer particles and the diameter of the voids can be measured by a transmission electron microscope.
 ここでいう「数平均粒子径」は、走査型電子顕微鏡(SEM)写真を用いて、画像解析により算出した値であり、100個の粒子を観察し、平均した値である。顕微鏡観察は、例えば、測定する粒子を前処理して、例えば電界放出形走査電子顕微鏡(SU6600/株式会社日立ハイテクノロジーズ製)を用いて、加速電圧5kVにて行うことができる。 The "number average particle diameter" here is a value calculated by image analysis using a scanning electron microscope (SEM) photograph, and is a value obtained by observing 100 particles and averaging them. Microscopic observation can be performed, for example, by pre-treating particles to be measured and using a field emission scanning electron microscope (SU6600/manufactured by Hitachi High-Technologies Corporation) at an acceleration voltage of 5 kV.
 SEM観察するエラストマー粒子の前処理は、以下のとおりである。
(i)6mlのスクリュー管瓶(アズワン製)に純水0.5mlを入れ、ここにエラストマー粒子分散液をスポイトで2滴滴下し、混合する。
(ii)コロジオン膜貼り付けメッシュ上に、(i)で混合した液を1滴乗せて、2%OsO水溶液を用いて1時間蒸気固定を行う。
(iii)室温で風乾後、OsO4コート(コート厚7nm)をする。
The pretreatment of the elastomer particles to be observed by SEM is as follows.
(I) 0.5 ml of pure water is put into a 6 ml screw tube bottle (manufactured by AS ONE), and 2 drops of the elastomer particle dispersion liquid is dropped therein with a dropper and mixed.
(Ii) One drop of the liquid mixed in (i) is placed on the collodion film-attached mesh, and vapor fixation is performed for 1 hour using a 2% OsO 4 aqueous solution.
(Iii) After air-drying at room temperature, an OsO 4 coat (coat thickness 7 nm) is applied.
 また、エラストマー粒子の空隙の直径は、前述した数平均粒子径と同様に、走査型電子顕微鏡(SEM)観察により測定することができる。 Also, the diameter of the voids of the elastomer particles can be measured by observation with a scanning electron microscope (SEM), like the number average particle diameter described above.
 以下、実施例に基づいて本発明を更に詳細に説明する。なお、以下に説明する実施例は、本発明の代表的な実施例の一例を示したものであり、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail based on examples. The embodiments described below are examples of typical embodiments of the present invention, and the present invention is not limited to the following embodiments.
[実施例1]
<エラストマー溶液の作製>
 200mLのガラス瓶に、4-tert-ブチルカテコールを添加したクロロプレンモノマー(20℃の比重:0.96、沸点:59℃)76gと、クロロプレンゴム(デンカ株式会社製、商品名:A-30)24gと、を入れ、室温で12時間攪拌し、クロロプレンゴムを溶解した。なお、本実施例での室温は20℃である。
[Example 1]
<Preparation of elastomer solution>
In a 200 mL glass bottle, 76 g of chloroprene monomer (specific gravity at 20° C.: 0.96, boiling point: 59° C.) to which 4-tert-butylcatechol was added, and 24 g of chloroprene rubber (manufactured by DENKA CORPORATION, trade name: A-30) And were added, and the mixture was stirred at room temperature for 12 hours to dissolve the chloroprene rubber. The room temperature in this example is 20°C.
<ポリビニルアルコール水溶液の作製>
 200mLビーカーに、純水85gと、ポリビニルアルコール(PVA)(株式会社クラレ製、商品名:PVA 3-88、ケン化度:88モル%)15gと、を入れ、60℃で2時間攪拌し、ポリビニルアルコールを溶解した。
<Preparation of polyvinyl alcohol aqueous solution>
In a 200 mL beaker, 85 g of pure water and 15 g of polyvinyl alcohol (PVA) (manufactured by Kuraray Co., Ltd., trade name: PVA 3-88, saponification degree: 88 mol%) were placed and stirred at 60° C. for 2 hours, Polyvinyl alcohol was dissolved.
<分散液の作製>
 ビーカーに、上述のエラストマー溶液100gとポリビニルアルコール水溶液100gを入れ、氷浴で冷却しながらホモジナイザーAHG-160D(アズワン株式会社製)を用いて12000rpmで攪拌し、分散液を得た。
<Preparation of dispersion>
100 g of the above-mentioned elastomer solution and 100 g of an aqueous polyvinyl alcohol solution were placed in a beaker and stirred at 12000 rpm using a homogenizer AHG-160D (manufactured by As One Co., Ltd.) while cooling with an ice bath to obtain a dispersion liquid.
<溶剤蒸散工程(エラストマー粒子の生成)>
 上記分散液を500mLナスフラスコへ移し、消泡剤を加え、エバポレーターにて35℃、60mmhgの条件で30分間減圧乾燥することで、水難溶性有機溶剤を蒸散させた。これにより、内部に水相を有するエラストマー粒子(クロロプレンゴム微粒子)が水に分散した分散液を得た。
<Solvent evaporation process (elastomer particle generation)>
The dispersion was transferred to a 500 mL eggplant-shaped flask, an antifoaming agent was added, and the mixture was dried under reduced pressure for 30 minutes under an evaporator at 35° C. and 60 mmhg to evaporate the poorly water-soluble organic solvent. As a result, a dispersion liquid was obtained in which the elastomer particles (chloroprene rubber fine particles) having an aqueous phase inside were dispersed in water.
<キャストフィルムの作製>
 エラストマー粒子が水に分散した分散液を水平に設置したガラス板上へ流し、3日間室温乾燥させて厚さ0.5mmのフィルム膜を形成した後、室温で1日間真空乾燥して水分を蒸散させ、縦100mm、横50mmに成形して、キャストフィルムを作製した。
<Production of cast film>
The dispersion in which the elastomer particles are dispersed in water is poured onto a horizontally placed glass plate and dried at room temperature for 3 days to form a film film having a thickness of 0.5 mm, and then vacuum dried at room temperature for 1 day to evaporate water. Then, it was molded into a length of 100 mm and a width of 50 mm to produce a cast film.
[実施例2]
<エラストマー溶液の作製>
 200mLのガラス瓶に、4-tert-ブチルカテコールを添加したクロロプレンモノマー75gと、Span80(ソルビタンモノオレアート)(日油株式会社製、商品名:ノニオンOP-80R、HLB:4.3)1gと、を入れ、密封して室温で10分間攪拌した。その後、クロロプレンゴム24gを加え、室温で12時間攪拌し、クロロプレンゴムを溶解した。
[Example 2]
<Preparation of elastomer solution>
In a 200 mL glass bottle, 75 g of chloroprene monomer added with 4-tert-butylcatechol, 1 g of Span80 (sorbitan monooleate) (NOF Corporation, trade name: Nonion OP-80R, HLB: 4.3), , Sealed and stirred at room temperature for 10 minutes. Then, 24 g of chloroprene rubber was added and stirred at room temperature for 12 hours to dissolve the chloroprene rubber.
 その後、実施例1と同様の手順で、ポリビニルアルコール水溶液を作製し、分散液を得て、溶剤蒸散工程を行った後にキャストフィルムを作製した。 After that, in the same procedure as in Example 1, an aqueous polyvinyl alcohol solution was prepared, a dispersion liquid was obtained, and a solvent evaporation step was performed, and then a cast film was prepared.
[実施例3]
 エラストマー溶液の作製において、Span80(ソルビタンモノオレアート)の代わりにSpan85(ソルビタントリオレアート)(日油株式会社製、商品名:ノニオンOP-85R、HLB:1.8)を用いた以外は、実施例2と同様の手順でキャストフィルムを作製した。
[Example 3]
In preparation of the elastomer solution, except that Span 80 (sorbitan monooleate) was replaced by Span 85 (sorbitan trioleate) (NOF Corporation, trade name: Nonion OP-85R, HLB: 1.8). A cast film was produced in the same procedure as in Example 2.
[実施例4]
 実施例2と同様の手順で、エラストマー溶液とポリビニルアルコール水溶液とを作製した後、以下の手順で分散液を作製した。
[Example 4]
After preparing an elastomer solution and a polyvinyl alcohol aqueous solution by the same procedure as in Example 2, a dispersion was prepared by the following procedure.
<分散液の作製>
(第1分散液作製工程)
 300mLビーカーに、エラストマー溶液100gと純水25gを入れ、氷浴で冷却しながらホモジナイザーAHG-160Dを用いて12000rpmで攪拌し、分散液(a)を作製した。なお、本実施例での氷浴は0℃である。
(第2分散液作製工程)
 次いで、分散液(a)にポリビニルアルコール水溶液100gを加え、氷浴で冷却しながらホモジナイザーAHG-160Dを用いて12000rpmで攪拌し、分散液(b)を作製した。
<Preparation of dispersion>
(First dispersion liquid preparation step)
100 g of the elastomer solution and 25 g of pure water were placed in a 300 mL beaker and stirred at 12000 rpm using a homogenizer AHG-160D while cooling with an ice bath to prepare a dispersion liquid (a). The ice bath in this example is 0°C.
(Second dispersion liquid preparation step)
Next, 100 g of an aqueous polyvinyl alcohol solution was added to the dispersion liquid (a) and stirred at 12000 rpm using a homogenizer AHG-160D while cooling with an ice bath to prepare a dispersion liquid (b).
 上記分散液(b)を用いて、実施例1と同様の手順で溶剤蒸散工程を行った後にキャストフィルムを作製した。 Using the above dispersion liquid (b), a solvent evaporation process was performed in the same procedure as in Example 1, and then a cast film was produced.
[実施例5]
 エラストマー溶液の作製において、Span80(ソルビタンモノオレアート)の代わりにSpan85(ソルビタントリオレアート)を用いた以外は、実施例4と同様の手順で分散液(b)を得て、溶剤蒸散工程を行った後キャストフィルムを作製した。
[Example 5]
In the preparation of the elastomer solution, a dispersion liquid (b) was obtained in the same procedure as in Example 4 except that Span 85 (sorbitan trioleate) was used instead of Span 80 (sorbitan monooleate), and the solvent evaporation step was performed. After that, a cast film was produced.
[実施例6]
 ポリビニルアルコール水溶液の作製において、純水85gと、ポリビニルアルコール(PVA 3-88)15gと、に加えて、ポリビニルアルコール(クラレ株式会社製、商品名:PVA LM-10、ケン化度:40モル%)2.5gを用いた以外は、実施例5と同様の手順で分散液(b)を得て、溶剤蒸散工程を行った後キャストフィルムを作製した。
[Example 6]
In the preparation of the polyvinyl alcohol aqueous solution, in addition to 85 g of pure water and 15 g of polyvinyl alcohol (PVA 3-88), polyvinyl alcohol (manufactured by Kuraray Co., Ltd., trade name: PVA LM-10, saponification degree: 40 mol%) ) A dispersion liquid (b) was obtained in the same procedure as in Example 5 except that 2.5 g was used, and a solvent evaporation step was performed, and then a cast film was produced.
[実施例7]
 ポリビニルアルコール水溶液の作製において、純水85gと、ポリビニルアルコール(PVA 3-88)15gと、に加えて、カルボン酸変性のポリ酢酸ビニル(デンカ株式会社製、商品名:デンカASR CH-09)1.0gを用いた以外は、実施例5と同様の手順で分散液(b)を得て、溶剤蒸散工程を行った後キャストフィルムを作製した。
[Example 7]
In the preparation of an aqueous polyvinyl alcohol solution, in addition to 85 g of pure water and 15 g of polyvinyl alcohol (PVA 3-88), carboxylic acid-modified polyvinyl acetate (manufactured by DENKA CORPORATION, trade name: DENKA ASR CH-09) 1 Dispersion liquid (b) was obtained in the same procedure as in Example 5 except that 0.0 g was used, and a solvent evaporation step was carried out to produce a cast film.
[実施例8]
 エラストマー溶液の作製において、Span80(ソルビタンモノオレアート)の代わりにグリセロールモノステアレート(花王株式会社製、商品名:レオドールMS-60、HLB:3.5)を用いた以外は、実施例2と同様の手順でキャストフィルムを作製した。
[Example 8]
Example 2 was repeated except that glycerol monostearate (manufactured by Kao Corporation, trade name: Rheodor MS-60, HLB: 3.5) was used in place of Span 80 (sorbitan monooleate) in the preparation of the elastomer solution. A cast film was produced by the same procedure.
[実施例9]
 エラストマー溶液の作製において、Span80(ソルビタンモノオレアート)の代わりにSpan20(ソルビタンモノラウレート)(日油株式会社製、商品名:ノニオンLP-20R、HLB:8.6)を用いた以外は、実施例2と同様の手順でキャストフィルムを作製した。
[Example 9]
In the preparation of the elastomer solution, Span 20 (sorbitan monolaurate) (NOF Corporation, trade name: Nonion LP-20R, HLB: 8.6) was used instead of Span 80 (sorbitan monooleate). A cast film was produced in the same procedure as in Example 2.
[実施例10]
 ポリビニルアルコール水溶液の作製において、純水85gと、ポリビニルアルコール(PVA 3-88)15gと、に加えて、ポリビニルアルコール(クラレ株式会社製、商品名:PVA LM-10、ケン化度:40モル%)2.5gを用いた以外は、実施例1と同様の手順でキャストフィルムを作製した。
[Example 10]
In the preparation of the polyvinyl alcohol aqueous solution, in addition to 85 g of pure water and 15 g of polyvinyl alcohol (PVA 3-88), polyvinyl alcohol (manufactured by Kuraray Co., Ltd., trade name: PVA LM-10, saponification degree: 40 mol%) ) A cast film was produced in the same procedure as in Example 1 except that 2.5 g was used.
[実施例11]
 ポリビニルアルコール水溶液の作製において、純水85gと、ポリビニルアルコール(PVA 3-88)15gと、に加えて、カルボン酸変性のポリ酢酸ビニル(デンカ株式会社製、商品名:デンカASR CH-09)1.0gを用いた以外は、実施例1と同様の手順でキャストフィルムを作製した。
[Example 11]
In the preparation of an aqueous polyvinyl alcohol solution, in addition to 85 g of pure water and 15 g of polyvinyl alcohol (PVA 3-88), carboxylic acid-modified polyvinyl acetate (manufactured by DENKA CORPORATION, trade name: DENKA ASR CH-09) 1 A cast film was produced by the same procedure as in Example 1 except that 0.0 g was used.
[実施例12]
 エラストマー溶液の作製において、クロロプレンモノマーの代わりに塩化メチレン(20℃の比重:1.33、沸点:40℃)を用い、クロロプレンゴムの代わりにニトリルゴム(日本ゼオン株式会社製、商品名:Nipol1043)を用いた以外は、実施例3と同様の手順でキャストフィルムを作製した。
[Example 12]
In the preparation of the elastomer solution, methylene chloride (specific gravity at 20°C: 1.33, boiling point: 40°C) was used instead of the chloroprene monomer, and nitrile rubber (manufactured by Nippon Zeon Co., Ltd., trade name: Nipol1043) was used instead of chloroprene rubber. A cast film was produced in the same procedure as in Example 3 except that was used.
[実施例13]
 エラストマー溶液の作製において、クロロプレンゴムの代わりにスチレン-イソプレン-スチレントリブロック共重合体(SIS)(日本ゼオン株式会社製、商品名:Quintac3421)を用いた以外は、実施例1と同様の手順でキャストフィルムを作製した。
[Example 13]
In the preparation of the elastomer solution, the same procedure as in Example 1 was performed except that styrene-isoprene-styrene triblock copolymer (SIS) (manufactured by Zeon Corporation, trade name: Quintac3421) was used instead of chloroprene rubber. A cast film was produced.
[実施例14]
 ポリビニルアルコール水溶液の作製において、純水85gと、ポリビニルアルコール(PVA 3-88)15gと、に加えて、ポリビニルアルコール(クラレ株式会社製、商品名:PVA LM-10、ケン化度:40モル%)2.5gを用いた以外は、実施例3と同様の手順でキャストフィルムを作製した。
[Example 14]
In the preparation of the polyvinyl alcohol aqueous solution, in addition to 85 g of pure water and 15 g of polyvinyl alcohol (PVA 3-88), polyvinyl alcohol (manufactured by Kuraray Co., Ltd., trade name: PVA LM-10, saponification degree: 40 mol%) ) A cast film was produced in the same procedure as in Example 3 except that 2.5 g was used.
[実施例15]
 ポリビニルアルコール水溶液の作製において、純水85gと、ポリビニルアルコール(PVA 3-88)15gと、に加えて、カルボン酸変性のポリ酢酸ビニル(デンカ株式会社製、商品名:デンカASR CH-09)1.0gを用いた以外は、実施例3と同様の手順でキャストフィルムを作製した。
[Example 15]
In the preparation of an aqueous polyvinyl alcohol solution, in addition to 85 g of pure water and 15 g of polyvinyl alcohol (PVA 3-88), carboxylic acid-modified polyvinyl acetate (manufactured by DENKA CORPORATION, trade name: DENKA ASR CH-09) 1 A cast film was produced by the same procedure as in Example 3 except that 0.0 g was used.
[比較例1]
 ポリビニルアルコール水溶液の作製において、ポリビニルアルコール(PVA 3-88)の代わりに、ポリビニルアルコール(株式会社クラレ製、商品名:PVA 3-98、ケン化度:98モル%)を用いた以外は、実施例1と同様の手順でキャストフィルムを作製した。
[Comparative Example 1]
In the preparation of the polyvinyl alcohol aqueous solution, except that polyvinyl alcohol (manufactured by Kuraray Co., Ltd., trade name: PVA 3-98, saponification degree: 98 mol%) was used instead of polyvinyl alcohol (PVA 3-88). A cast film was produced in the same procedure as in Example 1.
[比較例2]
 ポリビニルアルコールの代わりにTween20(日油株式会社製、商品名:ノニオンLT-221、HLB:16.7)を用いて水溶液を作製した以外は、実施例1と同様の手順でキャストフィルムを作製した。
[Comparative example 2]
A cast film was produced in the same procedure as in Example 1 except that an aqueous solution was produced using Tween 20 (trade name: Nonion LT-221, HLB: 16.7, manufactured by NOF CORPORATION) instead of polyvinyl alcohol. ..
[比較例3]
 ポリビニルアルコール水溶液の作製において、純水の量を85gから96gに変更し、ポリビニルアルコール(PVA 3-88)15gの代わりに、ポリビニルアルコール(PVA LM-10)4gを用いた以外は、実施例1と同様の手順でキャストフィルムを作製した。
[Comparative Example 3]
Example 1 except that in the preparation of the polyvinyl alcohol aqueous solution, the amount of pure water was changed from 85 g to 96 g and 4 g of polyvinyl alcohol (PVA LM-10) was used instead of 15 g of polyvinyl alcohol (PVA 3-88). A cast film was produced by the same procedure as in.
[比較例4]
 エラストマー溶液の作製において、クロロプレンモノマーの代わりにシクロヘキサン(20℃の比重:0.78、沸点:81℃)を使用し、クロロプレンゴムの代わりにエチレン-プロピレン-ジエンゴム(三井化学株式会社製、商品名:三井EPT4045)を使用した以外は、実施例1と同様の手順でキャストフィルムを作製した。
[Comparative Example 4]
In the preparation of the elastomer solution, cyclohexane (specific gravity at 20° C.: 0.78, boiling point: 81° C.) was used instead of the chloroprene monomer, and ethylene-propylene-diene rubber (trade name, manufactured by Mitsui Chemicals, Inc.) was used instead of chloroprene rubber. : A cast film was produced in the same procedure as in Example 1 except that Mitsui EPT4045) was used.
[比較例5]
 エラストマー溶液の作製において、クロロプレンモノマーの代わりにトルエン(20℃の比重:0.87、沸点:110℃)を用いた以外は、実施例1と同様の手順でキャストフィルムを作製した。
[Comparative Example 5]
In the production of the elastomer solution, a cast film was produced in the same procedure as in Example 1 except that toluene (specific gravity at 20°C: 0.87, boiling point: 110°C) was used instead of the chloroprene monomer.
<破断強度及び破断伸びの測定>
 JIS K 6251に基づいて引張試験を行い、キャストフィルムの破断強度(MPa)及び破断伸び(%)を測定した。破断強度は3.5MPa以上を合格とし、破断伸びは180%以上を合格とした。
<Measurement of breaking strength and breaking elongation>
A tensile test was performed based on JIS K 6251, and the breaking strength (MPa) and breaking elongation (%) of the cast film were measured. The breaking strength was 3.5 MPa or more, and the breaking elongation was 180% or more.
<熱伝導率の測定>
 迅速熱伝導率計QTM-500(京都電子工業株式会社製)を用いて、キャストフィルムの熱伝導率(W/mk)を測定した。
<Measurement of thermal conductivity>
The thermal conductivity (W/mk) of the cast film was measured using a rapid thermal conductivity meter QTM-500 (manufactured by Kyoto Electronics Manufacturing Co., Ltd.).
<中空粒子率の算出>
 各実施例及び比較例の手順で得られた分散液0.1mlを純水50mlに添加して、TEM用コロジオン膜貼付メッシュ上に滴下した。その後、室温で30分間2%OsO水溶液の蒸気にさらし、風乾後、透過型顕微鏡にて粒子の観察を行った。透過型電子顕微鏡で得られた画像中の粒子を無作為に200個選出し、空隙を1つ以上有する粒子を計数することで比率を算出した。
<Calculation of hollow particle ratio>
0.1 ml of the dispersion liquid obtained by the procedure of each Example and Comparative Example was added to 50 ml of pure water, and the solution was dropped on the mesh for attaching a collodion film for TEM. Then, it was exposed to the vapor of 2% OsO 4 aqueous solution for 30 minutes at room temperature, air-dried, and then the particles were observed with a transmission microscope. The ratio was calculated by randomly selecting 200 particles in the image obtained by a transmission electron microscope and counting the particles having one or more voids.
 実施例及び比較例の結果を下記表1~3に示す。なお、表1~3において、各成分の配合量は、エラストマー溶液を100質量部とした場合の量であり、単位は「質量部」である。 The results of Examples and Comparative Examples are shown in Tables 1 to 3 below. In Tables 1 to 3, the blending amount of each component is the amount when the elastomer solution is 100 parts by mass, and the unit is "parts by mass".
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
 実施例1~15では、内部に1つ以上の空隙を有するエラストマー粒子の収率が高いことが確認された。また、実施例1~15のキャストフィルムは、熱伝導率が低く断熱性に優れていること、また、破断強度及び破断伸びが良好であることが確認された。具体的には、実施例1~15のキャストフィルムは、熱伝導率が0.100W/mk以下、破断強度が3.5MPa以上、破断伸びが180%以上であった。
 また、<溶剤蒸散工程(エラストマー粒子の生成)>において得られた、実施例1~15の各エラストマー粒子を透過型電子顕微鏡にて測定したところ、これらの数平均粒子径は0.1~5.0μmの範囲内にあり、これらの内部の空隙の直径は50~500nmの範囲内にあった。
In Examples 1 to 15, it was confirmed that the yield of elastomer particles having one or more voids inside was high. It was also confirmed that the cast films of Examples 1 to 15 had low thermal conductivity and excellent heat insulating properties, and also had good breaking strength and breaking elongation. Specifically, the cast films of Examples 1 to 15 had a thermal conductivity of 0.100 W/mk or less, a breaking strength of 3.5 MPa or more, and a breaking elongation of 180% or more.
The number average particle diameter of these elastomer particles of Examples 1 to 15 obtained in the <solvent evaporation step (production of elastomer particles)> was 0.1 to 5 when measured with a transmission electron microscope. It was in the range of 0.0 μm and the diameter of the voids inside these was in the range of 50 to 500 nm.
 ケン化度が97モル%超のポリビニルアルコールを使用した比較例1、ポリビニルアルコールの代わりにTween20を使用した比較例2、ケン化度が60モル%未満のポリビニルアルコールを用いた比較例3では、安定に乳化できず、エラストマー粒子を生成することができなかった。20℃における比重が0.8未満の水難溶性有機溶剤を用いた比較例4と、沸点が95℃超の水難溶性有機溶剤を用いた比較例5では、内部に1つ以上の空隙を有するエラストマーの収率が極めて低かった。 In Comparative Example 1 using polyvinyl alcohol having a saponification degree of more than 97 mol %, Comparative Example 2 using Tween 20 instead of polyvinyl alcohol, and Comparative Example 3 using polyvinyl alcohol having a saponification degree of less than 60 mol %, The emulsion could not be stably emulsified and the elastomer particles could not be produced. In Comparative Example 4 using a poorly water-soluble organic solvent having a specific gravity at 20° C. of less than 0.8 and Comparative Example 5 using a poorly water-soluble organic solvent having a boiling point over 95° C., an elastomer having one or more voids inside Was very low.

Claims (14)

  1.  ケン化度が60~97モル%のポリビニルアルコールが溶解されている水と、
     20℃における比重が0.8以上、沸点が95℃以下である水難溶性有機溶剤にエラストマーが溶解されているエラストマー溶液と、
     を混合して撹拌する工程を含む、ラテックスの製造方法。
    Water in which polyvinyl alcohol having a saponification degree of 60 to 97 mol% is dissolved,
    An elastomer solution in which an elastomer is dissolved in a poorly water-soluble organic solvent having a specific gravity at 20°C of 0.8 or more and a boiling point of 95°C or less,
    A method for producing latex, which comprises the step of mixing and stirring.
  2.  前記水難溶性有機溶剤にHLBが8.0以下の界面活性剤が溶解されている、請求項1に記載のラテックスの製造方法。 The method for producing a latex according to claim 1, wherein a surfactant having an HLB of 8.0 or less is dissolved in the poorly water-soluble organic solvent.
  3.  水と、
     20℃における比重が0.8以上、沸点が95℃以下である水難溶性有機溶剤にエラストマー及びHLBが8.0以下の界面活性剤が溶解されているエラストマー溶液と、
     を混合して撹拌した後、
     ケン化度が60~97モル%のポリビニルアルコールが溶解されている水を添加して撹拌する工程を含む、ラテックスの製造方法。
    water and,
    An elastomer solution in which an elastomer and a surfactant having an HLB of 8.0 or less are dissolved in a poorly water-soluble organic solvent having a specific gravity at 20°C of 0.8 or more and a boiling point of 95°C or less,
    After mixing and stirring,
    A method for producing a latex, which comprises a step of adding water in which polyvinyl alcohol having a saponification degree of 60 to 97 mol% is dissolved and stirring the mixture.
  4.  前記HLBが8.0以下の界面活性剤は、ソルビタンモノオレアート、ソルビタントリオレアート及びグリセロールモノステアレートからなる群から選択される少なくとも1種である、請求項2又は3に記載のラテックスの製造方法。 The production of a latex according to claim 2 or 3, wherein the surfactant having an HLB of 8.0 or less is at least one selected from the group consisting of sorbitan monooleate, sorbitan trioleate and glycerol monostearate. Method.
  5.  前記エラストマー溶液及び前記ケン化度が60~97モル%のポリビニルアルコールが溶解されている水のうち少なくとも一方に、ケン化度が20~59モル%のポリビニルアルコール及びカルボキシ変性のポリ酢酸ビニルのうち少なくとも1種が溶解されている、請求項1~4のいずれか一項に記載のラテックスの製造方法。 At least one of water in which the elastomer solution and the polyvinyl alcohol having a saponification degree of 60 to 97 mol% are dissolved in polyvinyl alcohol having a saponification degree of 20 to 59 mol% and carboxy-modified polyvinyl acetate The method for producing a latex according to any one of claims 1 to 4, wherein at least one kind is dissolved.
  6.  前記ポリ酢酸ビニルは、アクリル酸、メタクリル酸、マレイン酸、フマル酸、クロトン酸、イタコン酸、マレイン酸モノエステル、フマル酸モノエステル及びイタコン酸モノエステルからなる群から選択される少なくとも1種と、酢酸ビニルと、の共重合体である、請求項5に記載のラテックスの製造方法。 The polyvinyl acetate is at least one selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, maleic acid monoester, fumaric acid monoester and itaconic acid monoester, The method for producing a latex according to claim 5, which is a copolymer with vinyl acetate.
  7.  前記エラストマーは、クロロプレンゴム、ニトリルゴム又はスチレン系ブロック共重合体である、請求項1~6のいずれか一項に記載のラテックスの製造方法。 The method for producing a latex according to any one of claims 1 to 6, wherein the elastomer is chloroprene rubber, nitrile rubber or styrene block copolymer.
  8.  前記水難溶性有機溶剤は、ハロゲン系有機溶剤である、請求項7に記載のラテックスの製造方法。 The method for producing a latex according to claim 7, wherein the poorly water-soluble organic solvent is a halogen-based organic solvent.
  9.  内部に1つ以上の水相を有し、乾燥させることで該水相が空隙を形成するエラストマー粒子と、
     ケン化度が60~97モル%のポリビニルアルコールが溶解されている水と、を含有するラテックス。
    Elastomer particles having one or more aqueous phases therein, and the aqueous phases forming voids when dried,
    A latex containing water in which polyvinyl alcohol having a saponification degree of 60 to 97 mol% is dissolved.
  10.  HLBが8.0以下の界面活性剤を含有する、請求項9に記載のラテックス。 The latex according to claim 9, wherein the HLB contains a surfactant having a pH of 8.0 or less.
  11.  ケン化度が20~59モル%のポリビニルアルコール及びカルボキシ変性のポリ酢酸ビニルのうち少なくとも1種を含有する、請求項9又は10に記載のラテックス。 The latex according to claim 9 or 10, containing at least one of polyvinyl alcohol having a saponification degree of 20 to 59 mol% and carboxy-modified polyvinyl acetate.
  12.  下記作製条件に準じて作製されたキャストフィルムの熱伝導率が0.100W/mk以下、破断強度が3.5MPa以上、破断伸びが180%以上である、請求項9~11のいずれか一項に記載のラテックス。
     作製条件:
     ラテックスを水平に設置したガラス板上へ流し、3日間室温乾燥させて厚さ0.5mmのフィルム膜を形成した後、室温で1日間真空乾燥して水分を蒸散させ、縦100mm、横50mmに成形して、キャストフィルムを作製する。
    The cast film produced according to the following production conditions has a thermal conductivity of 0.100 W/mk or less, a breaking strength of 3.5 MPa or more, and a breaking elongation of 180% or more. Latex described in.
    Manufacturing conditions:
    The latex is poured on a glass plate placed horizontally and dried at room temperature for 3 days to form a film having a thickness of 0.5 mm, and then vacuum dried at room temperature for 1 day to evaporate the water content to 100 mm in length and 50 mm in width. Mold to form a cast film.
  13.  水系接着剤用又は水系塗料用である、請求項9~12のいずれか一項に記載のラテックス。 The latex according to any one of claims 9 to 12, which is for water-based adhesive or water-based paint.
  14.  請求項9~13のいずれか一項に記載のラテックスを用いてなる、水系接着剤又は水系塗料。 A water-based adhesive or water-based coating material, which comprises the latex according to any one of claims 9 to 13.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111808556A (en) * 2020-07-17 2020-10-23 江苏兴达文具集团有限公司 White latex and preparation method thereof
WO2023190065A1 (en) * 2022-03-30 2023-10-05 デンカ株式会社 Chloroprene-based latex composition, chloroprene-based latex composition production method, and aqueous adhesive agent

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4112626B1 (en) * 1962-03-19 1966-07-18
WO2002043698A1 (en) * 2000-11-29 2002-06-06 Taisho Pharmaceutical Co.,Ltd. W/o/w composite emulsion
WO2016031845A1 (en) * 2014-08-29 2016-03-03 国立大学法人山形大学 Elastomer particles, production method therefor, elastomer composition, elastomer particle dispersion liquid, and molded body

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4112626B1 (en) * 1962-03-19 1966-07-18
WO2002043698A1 (en) * 2000-11-29 2002-06-06 Taisho Pharmaceutical Co.,Ltd. W/o/w composite emulsion
WO2016031845A1 (en) * 2014-08-29 2016-03-03 国立大学法人山形大学 Elastomer particles, production method therefor, elastomer composition, elastomer particle dispersion liquid, and molded body

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111808556A (en) * 2020-07-17 2020-10-23 江苏兴达文具集团有限公司 White latex and preparation method thereof
WO2023190065A1 (en) * 2022-03-30 2023-10-05 デンカ株式会社 Chloroprene-based latex composition, chloroprene-based latex composition production method, and aqueous adhesive agent

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