WO2019189662A1 - Particules de résine thermoplastique expansibles, particules pré-expansées de résine thermoplastique et mousse de résine thermoplastique - Google Patents

Particules de résine thermoplastique expansibles, particules pré-expansées de résine thermoplastique et mousse de résine thermoplastique Download PDF

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Publication number
WO2019189662A1
WO2019189662A1 PCT/JP2019/013794 JP2019013794W WO2019189662A1 WO 2019189662 A1 WO2019189662 A1 WO 2019189662A1 JP 2019013794 W JP2019013794 W JP 2019013794W WO 2019189662 A1 WO2019189662 A1 WO 2019189662A1
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WIPO (PCT)
Prior art keywords
thermoplastic resin
hydroxyethyl
hydroxyalkylamine
salt
resin particles
Prior art date
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Ceased
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PCT/JP2019/013794
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English (en)
Japanese (ja)
Inventor
賢明 南田
充宏 田村
大原　洋一
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Kaneka Corp
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Kaneka Corp
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Priority to JP2020511034A priority Critical patent/JP7250768B2/ja
Publication of WO2019189662A1 publication Critical patent/WO2019189662A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/36—Feeding the material to be shaped
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/224—Surface treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent

Definitions

  • the present invention relates to expandable thermoplastic resin particles, thermoplastic resin pre-expanded particles, and thermoplastic resin foam.
  • the present invention relates to low-charge amount expandable polystyrene resin particles, polystyrene resin pre-expanded particles, and polystyrene resin foam.
  • Expandable thermoplastic resin particles are relatively inexpensive, can be foam-molded with steam and the like without using a special method, and have a high buffering effect and a high heat insulation effect, so they are socially useful materials. .
  • Expandable thermoplastic resin particles can be obtained by, for example, adding a foaming agent (that is, easily volatile aliphatic hydrocarbons such as butane, pentane, etc.) to polystyrene resin particles in an aqueous suspension. Manufactured by the impregnation method. The expandable polystyrene resin particles thus manufactured are used as a raw material for manufacturing a polystyrene resin foam.
  • a foaming agent that is, easily volatile aliphatic hydrocarbons such as butane, pentane, etc.
  • the obtained polystyrene resin foam is used in a wide range of applications such as fish boxes, agricultural boxes, food containers, cushioning materials for home appliances, and insulation materials for building materials.
  • the foamable thermoplastic resin particles and the thermoplastic resin pre-foamed particles move in the pipe while being transported or dried by, for example, pneumatic transportation.
  • the expandable polystyrene resin particles containing the polystyrene resin and the polystyrene resin pre-expanded particles have a high electrical insulating property, and thus are easily charged by friction. Therefore, there is a possibility of igniting and exploding hydrocarbons as the foaming agent due to electrostatic discharge derived from charging.
  • thermoplastic resin foam when used as a cushioning material for home appliances and precision parts, a low-charge amount cushioning material (thermoplastic resin foam) is used from the viewpoint of preventing dust and the like on precision parts. It is requested.
  • Patent Document 3 discloses a foaming property characterized in that a hydroxyalkylamine compound having an aliphatic hydrocarbon group having 13 to 20 carbon atoms and having a hydroxyl group in the side chain is attached to the particle surface.
  • Styrenic resin particles corresponding to expandable polystyrene resin particles
  • low charge amount of expandable styrene resin particles (expandable polystyrene resin) Equivalent to particles
  • pre-expanded particles and methods for producing foams
  • Patent Documents 1 to 4 have a tendency that it is difficult to efficiently exhibit antistatic performance.
  • One embodiment of the present invention has been made in view of the above situation, and the purpose thereof is an expandable thermoplastic resin particle, a thermoplastic resin pre-expanded particle, which can efficiently obtain an antistatic effect, And providing a thermoplastic resin foam.
  • the inventors of the present invention have intensively studied for the purpose of improving the drawbacks of the prior art, and as a result, completed the present invention.
  • one embodiment of the present invention includes the following configuration.
  • One embodiment of the present invention is an expandable thermoplastic resin particle comprising thermoplastic resin particles and a foaming agent, which comprises N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A), N—
  • the foamed thermoplastic resin particle surface is coated with the hydroxyethyl-N-2-hydroxyalkylamine salt B (B), and the N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A) is an N-hydroxyethyl-N-2-hydroxyalkylamine salt B, wherein the alkyl group has 8 to 12 carbon atoms, has one amino group and two hydroxyl groups in the molecule.
  • the total amount of the ruamine salt A (A) and the N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B) is based on 100 parts by weight of the expandable thermoplastic resin particles.
  • the present invention relates to expandable thermoplastic resin particles, characterized in that the amount is 0.005 to 0.075 parts by weight.
  • One embodiment of the present invention is a pre-foamed thermoplastic resin particle obtained by foaming foamable thermoplastic resin particles containing thermoplastic resin particles and a foaming agent, and comprising N-hydroxyethyl-N-2-hydroxyalkyl
  • the surface of the thermoplastic resin pre-foamed particles is coated with an amine salt A (A) and an N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B), and the N-hydroxyethyl -N-2-hydroxyalkylamine salt A (A) has 8 to 12 carbon atoms in the alkyl group, and has one amino group and two hydroxyl groups in the molecule.
  • -N-2-hydroxyalkylamine salt B (B) has an alkyl group with 14 carbon atoms, and has one amino group and two hydroxyl groups in the molecule. Wherein, it relates to a thermoplastic resin pre-expanded particles.
  • thermoplastic resin foam formed by foaming and molding foamable thermoplastic resin particles containing thermoplastic resin particles and a foaming agent, and comprising N-hydroxyethyl-N-2-
  • the surface of the thermoplastic resin foam is coated with the salt A (A) of hydroxyalkylamine and the salt B (B) of N-hydroxyethyl-N-2-hydroxyalkylamine, and the N-hydroxy
  • the salt A (A) of ethyl-N-2-hydroxyalkylamine has an alkyl group having 8 to 12 carbon atoms, has one amino group and two hydroxyl groups in the molecule
  • the N-hydroxy Ethyl-N-2-hydroxyalkylamine salt B (B) is characterized in that the alkyl group has 14 carbon atoms and has one amino group and two hydroxyl groups in the molecule.
  • One embodiment of the present invention is a method for producing expandable thermoplastic resin particles, the method comprising contacting a thermoplastic resin particle with a foaming agent and impregnating the thermoplastic resin particle with the foaming agent; and N-hydroxy An aqueous solution containing an ethyl-N-2-hydroxyalkylamine salt A (A) and an N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B) is added to the foamable thermoplastic resin particles.
  • the N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A) has an alkyl group having 8 to 12 carbon atoms, and one amino group in the molecule.
  • One embodiment of the present invention is a process for producing thermoplastic resin pre-expanded particles, the step of foaming expandable thermoplastic resin particles, and a salt A (A of N-hydroxyethyl-N-2-hydroxyalkylamine) And an aqueous solution containing N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B) on the surface of the thermoplastic resin pre-expanded particles, and the N-hydroxy
  • the salt A (A) of ethyl-N-2-hydroxyalkylamine has an alkyl group having 8 to 12 carbon atoms, has one amino group and two hydroxyl groups in the molecule
  • the N-hydroxy Ethyl-N-2-hydroxyalkylamine salt B (B) is characterized in that the alkyl group has 14 carbon atoms and has one amino group and two hydroxyl groups in the molecule.
  • One embodiment of the present invention is a method for producing a thermoplastic resin foam, the step of molding thermoplastic resin pre-expanded particles, and a salt A (A) of N-hydroxyethyl-N-2-hydroxyalkylamine And an aqueous solution containing N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B) on the surface of the thermoplastic resin foam, the N-hydroxyethyl-
  • the salt A (A) of N-2-hydroxyalkylamine has an alkyl group having 8 to 12 carbon atoms, one amino group and two hydroxyl groups in the molecule, and the N-hydroxyethyl-
  • the salt B (B) of N-2-hydroxyalkylamine is characterized in that the alkyl group has 14 carbon atoms and has one amino group and two hydroxyl groups in the molecule.
  • expandable thermoplastic resin particles (expandable polystyrene resin particles) and thermoplastic resin pre-expanded particles that can effectively obtain an antistatic effect by combining two hydroxyalkylamines. And a thermoplastic resin foam can be obtained.
  • a to B representing a numerical range is intended to be “A or more (including A and greater than A) and B or less (including B and less than B)”.
  • a structural unit a structural unit derived from X 1 monomer, a structural unit derived from X 2 monomer, ..., and X n monomer (n is And an integer of 2 or more) is also referred to as “X 1 / X 2 /... / X n copolymer”.
  • the X 1 / X 2 /... / X n copolymer is not particularly limited unless otherwise specified, and may be a random copolymer or a block copolymer. It may be a graft copolymer.
  • One embodiment of the present invention relates to a foamable thermoplastic resin particle, a thermoplastic resin pre-foamed particle, and a thermoplastic resin foam characterized by coating a surface with a specific amount of a combination of two kinds of hydroxyalkylamine salts. Is the body. Furthermore, one embodiment of the present invention is characterized in that when two kinds of hydroxyalkylamine salts are added, the two kinds of hydroxyalkylamine salts are applied in an aqueous solution to be applied immediately. Low charge amount expandable thermoplastic resin particles, thermoplastic resin pre-expanded particles, and thermoplastic resin foam.
  • the “salt of two types of hydroxyalkylamine” may be referred to as “antistatic agent”.
  • the two hydroxyalkylamine salts are intended as N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A) and N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B). . Therefore, hereinafter, “N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A)” and “N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B)” are referred to as “charged”. "Inhibitor”. In the following, N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A) and N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B) are simply referred to as (A) and Sometimes referred to as (B).
  • the thermoplastic resin pre-foamed particles and the thermoplastic resin foam may be referred to as pre-foamed particles and foam, respectively.
  • the expandable thermoplastic resin particles according to an embodiment of the present invention are expandable thermoplastic resin particles containing thermoplastic resin particles and a foaming agent, and are N-hydroxyethyl-N-2-hydroxyalkylamine salts.
  • the foamable thermoplastic resin particle surface is coated with A (A) and N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B), and the N-hydroxyethyl-N—
  • the salt A (A) of 2-hydroxyalkylamine has an alkyl group having 8 to 12 carbon atoms, has one amino group and two hydroxyl groups in the molecule, and the N-hydroxyethyl-N—
  • the salt B (B) of 2-hydroxyalkylamine has an alkyl group with 14 carbon atoms, has one amino group and two hydroxyl groups in the molecule, and the N-hydroxyethyl -N-2-hydroxyalkylamine salt A (A) and the total amount of N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B) adhered to the foaming thermoplasticity
  • the amount is 0.005 to 0.075 parts by weight with respect to 100 parts by weight of the resin particles.
  • the low-charge amount foamable thermoplastic resin particle can be obtained.
  • the low charge amount of the expandable thermoplastic resin particles means that the expandable thermoplastic resin particles have an antistatic effect.
  • the expandable thermoplastic resin particles according to an embodiment of the present invention can provide pre-expanded particles and a foam having a low charge amount, that is, having an antistatic effect.
  • thermoplastic resin constituting the expandable thermoplastic resin particles according to the embodiment of the present invention
  • thermoplastic resin examples include styrene homopolymer, styrene / ethylene copolymer, styrene / butadiene copolymer, and styrene / acrylonitrile copolymer.
  • examples thereof include styrene / acrylic acid ester copolymers, acrylic acid ester homopolymers, acrylic acid ester / acrylic acid ester copolymers, ethylene homopolymers, and propylene homopolymers.
  • thermoplastic resins can be used alone or in combination of two or more.
  • the base resin constituting the foamable thermoplastic resin particles is preferably obtained by copolymerizing a styrene monomer and an acrylate monomer.
  • the “base resin” intends a resin constituting 50% by weight or more out of 100% by weight of the foamable thermoplastic resin particles.
  • styrenic monomer constituting the expandable thermoplastic resin particles in one embodiment of the present invention examples include styrene derivatives such as styrene, ⁇ -methylstyrene, paramethylstyrene, t-butylstyrene, and chlorostyrene. Can be mentioned.
  • styrene monomers can be used alone or in combination of two or more.
  • acrylic ester monomer constituting the expandable thermoplastic resin particle in one embodiment of the present invention examples include acrylic acid and methacrylic acid such as methyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, and cetyl methacrylate. Of the ester.
  • acrylate monomers can be used alone or in combination of two or more.
  • the acrylate monomer is also a component copolymerizable with the styrene monomer.
  • various components that can be copolymerized with styrene monomers include various monomers such as acrylonitrile, dimethyl fumarate, and ethyl fumarate, divinylbenzene, and alkylene glycol dimethacrylate. And bifunctional monomers. One or more components that can be copolymerized with these styrenic monomers may be used for copolymerization.
  • the styrene monomer and the acrylate monomer constituting the expandable thermoplastic resin particle in one embodiment of the present invention respectively constitute the expandable thermoplastic resin particle in one embodiment of the present invention.
  • foaming agent examples include known ones such as (i) aliphatic hydrocarbons such as propane, isobutane, normal butane, isopentane, normal pentane, neopentane, and the like ( ii) Volatile foaming agents such as hydrofluorocarbons such as difluoroethane and tetrafluoroethane having zero ozone depletion coefficient, (iii) Inorganic gases such as air, nitrogen and carbon dioxide, (iv) Water and the like. These foaming agents may be used alone or in combination of two or more. Of these foaming agents, butane is preferred because of its good foaming power.
  • aliphatic hydrocarbons such as propane, isobutane, normal butane, isopentane, normal pentane, neopentane, and the like
  • Volatile foaming agents such as hydrofluorocarbons such as difluoroethane and tetrafluoroethane having zero
  • the foamable thermoplastic resin particles can be made into prefoamed particles by blowing steam and the like and heating. Further, the pre-expanded particles are filled into a mold, and steam or the like is blown into the foamed product by heating and foaming.
  • the antistatic agent has an alkyl group of N-hydroxyethyl-N-2-hydroxyalkylamine having 8 to 12 carbon atoms and includes one amino group and two hydroxyl groups in the molecule.
  • the alkyl group has 8 or more carbon atoms
  • the adhesive force between the antistatic agent and the foamable thermoplastic resin can be maintained, and the foamable thermoplastic resin particles can be charged while foaming and molding the foamable thermoplastic resin particles. It is difficult for the inhibitor to flow, and the antistatic performance of the foam is improved.
  • the alkyl group has 14 or less carbon atoms, it does not precipitate particularly when the antistatic agent is made into an aqueous solution, so that it can be uniformly applied to the surface of the foamable thermoplastic resin particles, and the antistatic performance is improved.
  • the antistatic agent of one embodiment of the present invention is not particularly limited as long as it is a commonly used hydroxyalkylamine.
  • Antistatic agents include, for example, commonly used N-hydroxyethyl-N-2-hydroxyhexadecylamine, N, N-bis (hydroxyethyl) dodecylamine, N, N-bis (hydroxyethyl) tetradecylamine, N, N-bis (hydroxyethyl) hexadecylamine, N, N-bis (hydroxyethyl) octadecylamine, N-hydroxyethyl-N-2-hydroxytetradecylamine, N-hydroxyethyl-N-2-hydroxyhexadecylamine, N-hydroxyethyl-N-2-hydroxyoctadecylamine, N-hydroxypropyl-N-2-hydroxytetradecylamine, N-hydroxybutyl-N-2- Hydroxytetradecylamine, N-hydroxypentyl-N-2-hy Roxytetradecylamine, N-hydroxypenty
  • the antistatic agent of one embodiment of the present invention also includes glycerin, polyethylene glycol, polypropylene glycol, fatty acid monoglyceride, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester and the like that are generally used.
  • glycerin polyethylene glycol, polypropylene glycol, fatty acid monoglyceride, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester and the like that are generally used.
  • One of these antistatic agents may be used alone, or two or more thereof may be used in combination.
  • the adhesion amount of the antistatic agent is 0.005 parts by weight to 0.075 parts by weight with respect to 100 parts by weight of the expandable thermoplastic resin particles. Further, since the charge amount can be stably reduced, the adhesion of the antistatic agent is preferably 0.005 to 0.060 parts by weight with respect to 100 parts by weight of the expandable thermoplastic resin particles. is there.
  • the adhesion amount of the antistatic agent is (a) 0.005 parts by weight or more with respect to 100 parts by weight of the expandable thermoplastic resin particles, good antistatic performance can be obtained, and (b) 0.075 weights.
  • the amount is less than or equal to a part, a blocking phenomenon in which particles are coalesced during preliminary foaming does not occur, and thus good productivity can be maintained.
  • the “antistatic agent adhesion amount” intends the total amount of the antistatic agent adhering to the surface of the foamable thermoplastic resin particles.
  • the “adhesion amount of the antistatic agent” refers to the N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A) and N-hydroxyethyl-N— with respect to the expandable thermoplastic resin particles.
  • the total amount of adhesion of 2-hydroxyalkylamine salt B (B) is intended.
  • the adhesion amount of the antistatic agent in one embodiment of the present invention is preferably 0.005 parts by weight to 0.075 parts by weight, and 0.005 parts by weight to 0.060 parts by weight with respect to 100 parts by weight of the pre-expanded particles. Is more preferable.
  • the adhesion amount of the antistatic agent in one embodiment of the present invention is preferably 0.005 parts by weight to 0.075 parts by weight, and 0.005 parts by weight to 0.060 parts by weight with respect to 100 parts by weight of the foam. More preferred. This configuration has an advantage that good antistatic performance can be obtained.
  • the “adhesion amount of the antistatic agent” intends the total amount of the antistatic agent adhering to the surface of the pre-expanded particles or the foam.
  • the “adhesion amount of the antistatic agent” refers to N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A) and N-hydroxyethyl-N— The total amount of adhesion of 2-hydroxyalkylamine salt B (B) is intended.
  • the blending ratio of the N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B) in the antistatic agent is 99 or less, it does not precipitate particularly when it is made into an aqueous solution.
  • the antistatic performance is improved. Further, when the blending ratio of the N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A) in the antistatic agent is 50 or less, the adhesion between the antistatic agent and the foamable thermoplastic resin is maintained. The antistatic agent does not easily flow from the foamable thermoplastic resin particles during foaming and molding of the foamable thermoplastic resin particles, and the antistatic performance of the foam is improved.
  • a general method can be selected as a method for applying the antistatic agent in one embodiment of the present invention.
  • the method of applying the antistatic agent includes two kinds of N-hydroxyethyl-N-2-hydroxyalkylamine salts (that is, (A) on the surface of the expandable thermoplastic resin particles. And (B)) are not particularly limited as long as they exist together.
  • the antistatic agent may be prepared by previously mixing two types of N-hydroxyethyl-N-2-hydroxyalkylamine salts and then applying the mixture to the surface of the foamable thermoplastic resin particles.
  • the antistatic agent is obtained by individually coating each of the N-hydroxyethyl-N-2-hydroxyalkylamine salts on the surface of the expandable thermoplastic resin particles and mixing on the surface of the expandable thermoplastic resin particles. Also good.
  • a method of preparing an aqueous solution of the antistatic agent and applying the aqueous solution to the surface of the expandable thermoplastic resin particles is preferable.
  • the antistatic agent in the form of an aqueous solution, (a) the antistatic agent can be uniformly attached to the surface of the foamable thermoplastic resin particles, so even if the amount of the antistatic agent applied is small The antistatic effect can be efficiently obtained, and (b) since water is contained, the immediate effect of the effect of the antistatic agent can be obtained.
  • a method for preparing (adjusting) an aqueous solution of an antistatic agent is a method in which the salt A (A) and / or B (B) of N-hydroxyethyl-N-2-hydroxyalkylamine is dissolved.
  • the dissolution method is not particularly limited.
  • the N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A) and / or B (B) is dissolved in a solvent such as water, or the N-hydroxy Examples thereof include a method of dissolving a solvent such as water in ethyl-N-2-hydroxyalkylamine salt A (A) and / or B (B).
  • the aqueous solution of the antistatic agent may contain a solvent other than water as long as it contains water.
  • the solvent used in the aqueous solution of the antistatic agent is not particularly limited as long as it is a commonly used solvent. Specific examples include ethanol, propanol, isopropanol, butanol, isobutanol, and tertiary butanol. As for these solvents, only one kind of solvent may be used in combination with water, or two or more kinds of solvents may be used in combination with water. When the aqueous solution of the antistatic agent contains a solvent, the solubility of the antistatic agent can be increased.
  • case A an aqueous solution containing the N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A) and an aqueous solution containing the N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B) And the two aqueous solutions may be applied to the surface of the expandable thermoplastic resin particles, respectively.
  • an aqueous solution containing the N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A) and the N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B) is used.
  • the aqueous solution may be prepared and applied to the surface of the expandable thermoplastic resin particles.
  • the salt A (A) of the N-hydroxyethyl-N-2-hydroxyalkylamine and the N-hydroxyethyl-N-2-hydroxyalkylamine It is preferable to prepare an aqueous solution containing the salt B (B) and apply the aqueous solution to the surface of the expandable thermoplastic resin particles.
  • the method of applying the antistatic agent in one embodiment of the present invention is not limited to the method of applying the antistatic agent in the state of an aqueous solution.
  • the method for applying the antistatic agent to the surface of the foamable thermoplastic resin particles is not particularly limited, and may be a known method.
  • the method include (i) a method of spraying an aqueous solution of an antistatic agent on a dehydrated foamable thermoplastic resin particle using a spray nozzle in a pipe, and (ii) a method of charging the dehydrated foamable thermoplastic resin particle.
  • Examples thereof include a method in which an aqueous solution of an inhibitor is dropped and mixed with a mixer, and (iii) a method in which an antistatic agent is added and mixed when the foaming thermoplastic resin particles are mixed with an external additive using a blender or the like.
  • the timing of adding the antistatic agent is not particularly limited as long as it can be applied to the surface of the foamable thermoplastic resin.
  • As the timing for example, after dehydrating the foamable thermoplastic resin particles, while the foamable thermoplastic resin particles are being sent, before adding the additive to the foamable thermoplastic resin particles, or For example, after adhesion.
  • the concentration of the aqueous solution of the antistatic agent when applied to the surface of the foamable thermoplastic resin is preferably 3% by weight to 25% by weight with respect to 100 parts by weight of the aqueous solution.
  • the concentration of the aqueous solution of the antistatic agent is more preferably 4% by weight to 10% by weight.
  • the antistatic agent in the aqueous solution does not precipitate, so that the nozzle spraying the aqueous solution is clogged.
  • the aqueous solution can be uniformly applied to the surface of the expandable thermoplastic resin particles.
  • the “concentration of the aqueous solution of the antistatic agent” refers to “the salt A (A) of the N-hydroxyethyl-N-2-hydroxyalkylamine and the N-hydroxyethyl-N-2-hydroxyalkylamine in the aqueous solution”. It can also be said that “the concentration of the salt B (B)”. That is, in one embodiment of the present invention, the N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A) and the N-hydroxyethyl-N-2-hydroxy in an aqueous solution of the antistatic agent It can be said that the concentration of the alkylamine salt B (B) is preferably 3 to 25% by weight, more preferably 4 to 10% by weight.
  • an aqueous solution containing the salt A (A) and an aqueous solution containing the salt B (B) are prepared separately, and each of these two aqueous solutions is treated with an object (for example, a foamable thermoplastic resin).
  • an object for example, a foamable thermoplastic resin.
  • the aqueous solution when an aqueous solution containing the salt A (A) and the salt B (B) is prepared, and the aqueous solution is applied to the surface of an object (for example, expandable thermoplastic resin particles), the aqueous solution
  • concentrations of the salt A (A) and the salt B (B) are the total concentration of the salt A (A) and the salt B (B) in the aqueous solution.
  • the mixer for mixing the antistatic agent after dehydrating and drying the foamable thermoplastic resin particles is not particularly limited, and any mixer that can apply uniformly can be used.
  • a super mixer a riboblender, a V-type blender, a Nauta mixer, a Henschel mixer, a Redige mixer, a universal mixer, an apex mixer, and the like.
  • the antistatic agent may be applied to the pre-expanded particles or may be applied to the foam.
  • the method of applying the antistatic agent to the pre-expanded particles and the foam is obtained by applying two kinds of the N-hydroxyethyl-N-2-hydroxyalkylamine salts ((A) and (N) on the surface of the pre-expanded particles and the foam.
  • the various aspects related to the application of the antistatic agent to the expandable thermoplastic resin particles described above can be appropriately used as the various aspects related to the application of the antistatic agent to the pre-expanded particles and the foam.
  • plasticizers, nucleating agents, flame retardants, flame retardant aids, external additives, etc. as additives that can be added do not impair the effects of the present invention It may be used in a range.
  • plasticizer used in one embodiment of the present invention examples include diisobutyl adipate, dioctyl adipate, dibutyl sebacate, glycerin tristearate, glycerin tricaprylate, coconut oil, palm oil, and rapeseed oil.
  • plasticizers when the foam is used in the medical field or the packaging material field in direct contact with food, edible oil is preferable, and palm oil, palm oil, and rapeseed oil are more preferable.
  • a plasticizer may be added in a polymerization step of thermoplastic resin particles, a step of impregnating a foaming agent, or the like.
  • nucleating agent used in one embodiment of the present invention examples include methyl methacrylate copolymer, polyethylene wax, talc, fatty acid bisamide, ethylene-vinyl acetate copolymer resin, and the like.
  • fatty acid bisamide examples include methylene bisstearyl amide, ethylene bisstearyl amide, hexamethylene bispalmitic acid amide, ethylene bisoleic acid amide and the like.
  • flame retardant and flame retardant aid used in one embodiment of the present invention known and conventional ones can be used.
  • the flame retardant include, for example, (i) halogenated aliphatic hydrocarbon compounds such as hexabromocyclododecane, tetrabromobutane, hexabromocyclohexane, (ii) tetrabromobisphenol A, tetrabromobisphenol F, Brominated phenols such as 2,4,6-tribromophenol, (iii) tetrabromobisphenol A-bis (2,3-dibromopropyl ether), tetrabromobisphenol A-bis (2,3-dibromo-2- Brominated phenol derivatives such as methylpropyl ether), tetrabromobisphenol A-diglycidyl ether, 2,2-bis [4 '(2 ", 3" -dibromoalkoxy) -3', 5'-dibromophenyl] -propane (Iv) a bromine,
  • the brominated styrene / butadiene block copolymer is a block copolymer including a structural unit derived from a styrene monomer and a structural unit derived from a butadiene monomer as a structural unit, and is derived from a styrene monomer.
  • a copolymer in which at least one of the structural units is brominated is intended.
  • Brominated random styrene / butadiene copolymers, brominated styrene / butadiene graft copolymers and brominated butadiene / vinyl aromatic hydrocarbon copolymers as well as brominated styrene / butadiene block copolymers There are no particular limitations on the structural units.
  • the flame retardant aid include initiators such as cumene hydroperoxide, dicumyl peroxide, t-butyl hydroperoxide, and 2,3-dimethyl-2,3-diphenylbutane.
  • the external additive include, for example, (i) fatty acid triglycerides such as lauric acid triglyceride, stearic acid triglyceride, and linoleic acid triglyceride; (ii) fatty acid diglycerides such as lauric acid diglyceride, stearic acid diglyceride, and linoleic acid diglyceride; Fatty acid monoglycerides such as lauric acid monoglyceride, stearic acid monoglyceride, linoleic acid monoglyceride, (iii) fatty acid metal salts such as zinc stearate, calcium stearate, magnesium stearate, aluminum stearate, zinc laurate, calcium laurate, (iv) poly Oxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, poly Carboxylate ethylene laurate, polyoxyethylene palmitate, polyoxyethylene ste
  • These external additives may be used alone or in a combination of two or more. These external additives may be added to the aqueous system (dispersion medium) when the foaming thermoplastic resin particles are impregnated with the foaming agent, or added after dehydration or drying to coat the surface of the foamable thermoplastic resin particles. May be.
  • the addition timing of the external additive does not depend on the method of coating the expandable thermoplastic resin particles with the external additive.
  • the preferred method of coating the expandable thermoplastic resin particles with an external additive is to attach the external additive after drying the expandable thermoplastic resin particles, and mix and stir the expandable thermoplastic resin particles and the external additive. It is a method to do.
  • polymerization initiators can be used as the initiator.
  • an organic peroxide benzoyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, isopropyl-t-butyl peroxycarbonate, butyl perbenzoate, t-butylperoxy-2-ethylhexanoate, t-butyl perpivalate, t-butyl peroxyisopropyl carbonate, di-t-butyl peroxyhexahydroterephthalate, 1,1-di (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1 -Bis (t-amylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-butylperoxy) cyclohexane, t-butylperoxy-2-ethylhexyl monocarbonate, etc .; Azobisisobutamate, t
  • the charge amount of the expandable thermoplastic resin particles according to an embodiment of the present invention is preferably ⁇ 1.0 kV to 1.0 kV, more preferably ⁇ 0.7 kV to 0.7 kV, More preferably, it is 0.5 kV to 0.5 kV.
  • a known method can be applied to the method for producing the expandable thermoplastic resin particles of the present invention.
  • a method of impregnating particles obtained by suspension polymerization in an aqueous medium with a foaming agent a method of impregnating pellets produced by bulk polymerization in an aqueous medium with a foaming agent
  • the kneaded molten resin is extruded into a cutter chamber filled with circulating water through a die attached to the tip of the extruder, and foamed into the resin produced by cutting the molten resin with a rotary cutter in contact with the die immediately after extrusion.
  • the foamable thermoplastic resin particles of the present invention can be foamed by a known method to obtain a thermoplastic resin foam. Examples thereof include a method of once preparing pre-expanded particles and then filling the mold with the pre-expanded particles and molding, or a method of directly filling the mold with expandable thermoplastic resin particles and foam-molding. Examples of the foam production method include the following methods. By heating the expandable thermoplastic resin particles of the present invention at about 80 to 110 ° C. with water vapor in a rotary stirring type prefoaming device, prefoamed particles having a bulk ratio of about 30 to 100 ml / g are obtained. The obtained pre-expanded particles are filled into a mold having a desired shape, and heated at about 105 to 145 ° C. using water vapor or the like to obtain a thermoplastic resin foam.
  • a method for producing expandable thermoplastic resin particles according to an embodiment of the present invention is a method for producing expandable thermoplastic resin particles, wherein a foaming agent is brought into contact with the thermoplastic resin particles to bring the thermoplastic resin particles into contact with the thermoplastic resin particles. Impregnating with a foaming agent; and N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A) and N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B). Applying an aqueous solution to the surface of the expandable thermoplastic resin particles, wherein the N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A) has an alkyl group having 8 to 8 carbon atoms.
  • thermoplastic resin particles for producing thermoplastic resin particles and a method for impregnating thermoplastic resin particles with a foaming agent in the step of impregnating the foaming agent.
  • Examples thereof include the methods described in the section “Production method”.
  • each embodiment of the aqueous solution containing (A) and / or (B), and a method for applying the aqueous solution to the surface of the expandable thermoplastic resin particles may include the above-mentioned [1-3. Examples and methods described in the section "Antistatic agent" can be given.
  • an aqueous solution containing the above-mentioned “N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A) and N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B)” In the step of applying to the surface of the expandable thermoplastic resin particles, an aqueous solution containing the salt A (A) of N-hydroxyethyl-N-2-hydroxyalkylamine is applied to the surface of the expandable thermoplastic resin particles. And a step of applying an aqueous solution containing N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B) to the surface of the expandable thermoplastic resin particles.
  • the method for producing expandable thermoplastic resin particles may be as follows: A method for producing expandable thermoplastic resin particles, comprising: (I) contacting the thermoplastic resin particles with a foaming agent to impregnate the thermoplastic resin particles with the foaming agent; and (Ii) (ii-a) N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A) and N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B) Applying an aqueous solution to the surface of the expandable thermoplastic resin particles, or (Ii-b) a step of applying an aqueous solution containing the salt A (A) of N-hydroxyethyl-N-2-hydroxyalkylamine to the surface of the expandable thermoplastic resin particles, and N-hydroxyethyl-N-2- Applying an aqueous solution containing a hydroxyalkylamine salt B (B) to the surface of the expandable thermoplastic resin particles;
  • a method for producing expandable thermoplastic resin particles comprising: (
  • N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A) and N-hydroxyethyl-N— in the aqueous solution are used.
  • concentration of the 2-hydroxyalkylamine salt B (B) is preferably 3 to 25% by weight.
  • thermoplastic resin pre-expanded particles according to one embodiment of the present invention are preferably thermoplastic resin pre-expanded particles obtained by foaming the expandable thermoplastic resin particles according to one embodiment of the present invention.
  • the thermoplastic resin pre-expanded particles according to an embodiment of the present invention include, for example, [1. It is a thermoplastic resin pre-expanded particle obtained by foaming the expandable thermoplastic resin particle described in the section of “Expandable thermoplastic resin particle”, or [2. It is preferably a thermoplastic resin pre-expanded particle obtained by foaming the expandable thermoplastic resin particles produced by the production method described in the section of “Production method of expandable thermoplastic resin particles”.
  • thermoplastic resin pre-expanded particles are thermoplastic resin pre-expanded particles obtained by foaming expandable thermoplastic resin particles containing thermoplastic resin particles and a foaming agent, and N
  • the surface of the pre-expanded particles of the thermoplastic resin is obtained by the salt A (A) of -hydroxyethyl-N-2-hydroxyalkylamine and the salt B (B) of N-hydroxyethyl-N-2-hydroxyalkylamine.
  • the N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A) is coated, the alkyl group has 8 to 12 carbon atoms, one amino group in the molecule, and two hydroxyl groups
  • the N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B) has an alkyl group with 14 carbon atoms, one amino group in the molecule, and One of the having a hydroxyl group.
  • thermoplastic resin pre-expanded particles according to an embodiment of the present invention have the above-described configuration, the thermoplastic resin pre-expanded particles have an advantage of having a low charge amount, that is, having an antistatic effect. Moreover, since the thermoplastic resin pre-expanded particles according to an embodiment of the present invention have the above-described configuration, it is possible to provide a foam having a low charge amount, that is, an antistatic effect.
  • the bulk magnification (also referred to as bulk density) of the pre-expanded particles is not particularly limited.
  • the charge amount of the thermoplastic resin pre-expanded particles according to an embodiment of the present invention is preferably ⁇ 1.0 kV to 1.0 kV, more preferably ⁇ 0.7 kV to 0.7 kV, More preferably, it is 0.5 kV to 0.5 kV.
  • the method for producing the pre-expanded thermoplastic resin particles according to an embodiment of the present invention is not particularly limited.
  • a method for producing pre-expanded thermoplastic resin particles according to an embodiment of the present invention is a method for producing pre-expanded thermoplastic resin particles, the step of foaming expandable thermoplastic resin particles, and N-hydroxyethyl
  • An aqueous solution containing the salt A (A) of N-2-hydroxyalkylamine and the salt B (B) of N-hydroxyethyl-N-2-hydroxyalkylamine is used as the surface of the thermoplastic resin pre-expanded particles.
  • the N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A) has an alkyl group having 8 to 12 carbon atoms, one amino group in the molecule, And the N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B) having two hydroxyl groups, the alkyl group has 14 carbon atoms and one amino group in the molecule. And a two hydroxyl groups. According to this configuration, it is possible to obtain thermoplastic resin pre-expanded particles having a low charge amount, that is, having an antistatic effect.
  • the method for applying the aqueous solution containing (A) and / or (B) to the surface of the thermoplastic resin pre-expanded particles is not particularly limited.
  • the method similar to the method of applying the aqueous solution containing (A) and / or (B) to the surface of the expandable thermoplastic resin particles described in the section of “Antistatic agent” can be used.
  • an aqueous solution containing the above-mentioned “N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A) and N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B)” In the step of applying to the surface of the thermoplastic resin pre-expanded particles, an aqueous solution containing the salt A (A) of N-hydroxyethyl-N-2-hydroxyalkylamine is applied to the surface of the thermoplastic resin pre-expanded particles. And a step of applying an aqueous solution containing N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B) to the surface of the pre-expanded particles of the thermoplastic resin.
  • the method for producing thermoplastic resin pre-expanded particles may be in the following manner: A method for producing thermoplastic resin pre-expanded particles, (I) a step of foaming the expandable thermoplastic resin particles, and (Ii) (ii-a) N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A) and N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B) Applying an aqueous solution to the surface of the thermoplastic resin pre-expanded particles, or (Ii-b) a step of applying an aqueous solution containing the salt A (A) of N-hydroxyethyl-N-2-hydroxyalkylamine to the surface of the thermoplastic resin pre-expanded particles, and N-hydroxyethyl-N-2- Applying an aqueous solution containing a hydroxyalkylamine salt B (B) to the surface of the thermoplastic resin pre-expanded particles;
  • the salt A (A) of the N-hydroxyethyl-N-2-hydroxyalkylamine and the N-hydroxyethyl- The concentration of the N-2-hydroxyalkylamine salt B (B) is preferably 3 wt% to 25 wt%.
  • thermoplastic resin pre-expanded particles for other specific aspects relating to the thermoplastic resin pre-expanded particles and the method for producing the thermoplastic resin pre-expanded particles according to one embodiment of the present invention, [1. Description of expandable thermoplastic resin particles] can be incorporated.
  • thermoplastic resin foam is preferably a thermoplastic resin foam obtained by in-mold molding the thermoplastic resin pre-expanded particles according to one embodiment of the present invention.
  • the thermoplastic resin foam according to an embodiment of the present invention is, for example, [3.
  • a thermoplastic resin foam obtained by in-mold molding of the thermoplastic resin pre-expanded particles described in the section of “Thermoplastic resin pre-expanded particles” is preferable.
  • the thermoplastic resin foam according to another embodiment of the present invention is preferably a thermoplastic resin foam formed by foaming and molding the expandable thermoplastic resin particles according to an embodiment of the present invention.
  • the thermoplastic resin foam according to an embodiment of the present invention is, for example, [1. It is a thermoplastic resin foam obtained by foaming and in-mold molding the foamable thermoplastic resin particles described in the section of [Pre-foamed thermoplastic resin particles], or [2. It is preferable that the foamed thermoplastic resin particles are produced by foaming the foamable thermoplastic resin particles produced by the production method described in the section of “Production method of expandable thermoplastic resin particles” and molded in the mold.
  • thermoplastic resin foam according to another embodiment of the present invention is a thermoplastic resin foam formed by foaming and molding foamable thermoplastic resin particles containing thermoplastic resin particles and a foaming agent, N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A) and N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B) give the surface of the thermoplastic resin foam.
  • the N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A) is coated, the alkyl group has 8 to 12 carbon atoms, one amino group in the molecule, and two hydroxyl groups
  • the N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B) has an alkyl group with 14 carbon atoms, one amino group in the molecule, and two hydrides. Having a hexyl group.
  • thermoplastic resin foam according to an embodiment of the present invention has the above-described configuration, it has an advantage that it has a low charge amount, that is, has an antistatic effect.
  • the charge amount of the thermoplastic resin foam according to an embodiment of the present invention is preferably ⁇ 1.0 kV to 1.0 kV, more preferably ⁇ 0.7 kV to 0.7 kV, and ⁇ 0 More preferably, it is from 5 kV to 0.5 kV.
  • thermoplastic resin foam is not particularly limited.
  • a method for producing a thermoplastic resin foam according to an embodiment of the present invention is a method for producing a thermoplastic resin foam, the step of molding thermoplastic resin pre-expanded particles, and N-hydroxyethyl-N An aqueous solution containing a salt of A-2-hydroxyalkylamine A (A) and a salt of N-hydroxyethyl-N-2-hydroxyalkylamine B (B) is applied to the surface of the thermoplastic resin foam.
  • the N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A) includes an alkyl group having 8 to 12 carbon atoms, one amino group in the molecule, and two salts
  • the salt B (B) of N-hydroxyethyl-N-2-hydroxyalkylamine having a hydroxyl group has an alkyl group with 14 carbon atoms, one amino group in the molecule, and two hydroxyl groups. Having a Rokishiru group. According to this configuration, a thermoplastic resin foam having a low charge amount, that is, having an antistatic effect can be obtained.
  • thermoplastic resin foam As a method for producing a thermoplastic resin foam according to another embodiment of the present invention, a foamed thermoplastic resin particle is filled in a mold and foam-molded, and the obtained thermoplastic resin foam is obtained. An aqueous solution containing N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A) and N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B) is applied to the body surface. And a method comprising the step of:
  • thermoplastic resin pre-expanded particles As a method of molding the thermoplastic resin pre-expanded particles in a mold, a known method can be used. For example, there is a so-called in-mold foam molding method in which the thermoplastic resin pre-foamed particles are filled in a mold, and a foam molded body (foam) is obtained by heating by blowing steam or the like. Specifically, the above [1-7. Examples thereof include the method described in the section of [Foamed].
  • the method for applying the aqueous solution containing (A) and / or (B) to the surface of the thermoplastic resin foam is not particularly limited.
  • the aqueous solution of the antistatic agent is applied to the foam using a spray nozzle in a pipe.
  • a method of spreading an aqueous solution of an antistatic agent on a foam using a brush or the like is not particularly limited.
  • an aqueous solution containing the above-mentioned “N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A) and N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B)” In the step of applying to the surface of the thermoplastic resin foam, the step of applying an aqueous solution containing the salt A (A) of N-hydroxyethyl-N-2-hydroxyalkylamine to the surface of the thermoplastic resin foam and A step of applying an aqueous solution containing the salt B (B) of N-hydroxyethyl-N-2-hydroxyalkylamine to the surface of the thermoplastic resin foam may also be included.
  • the method for producing a thermoplastic resin foam may be as follows: A method for producing a thermoplastic resin foam, (I) a step of molding thermoplastic resin pre-expanded particles, and (Ii) (ii-a) N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A) and N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B) Applying an aqueous solution to the surface of the thermoplastic resin foam, or (Ii-b) a step of applying an aqueous solution containing the salt A (A) of N-hydroxyethyl-N-2-hydroxyalkylamine to the surface of the thermoplastic resin foam, and N-hydroxyethyl-N-2-hydroxy Applying an aqueous solution containing an alkylamine salt B (B) to the surface of the thermoplastic resin foam;
  • the N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A) includes an alkyl group having 8 to
  • the N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A) and the N-hydroxyethyl-N in the aqueous solution are used.
  • the concentration of the salt of -2-hydroxyalkylamine B (B) is preferably 3% by weight to 25% by weight.
  • An embodiment of the present invention may have the following configuration.
  • the blending ratio of the salt A (A) of the N-hydroxyethyl-N-2-hydroxyalkylamine and the salt B (B) of the N-hydroxyethyl-N-2-hydroxyalkylamine is:
  • the foamable thermoplastic resin particles according to [1], wherein (A) :( B) 1: 99 to 50:50.
  • thermoplastic resin foam wherein the thermoplastic resin pre-expanded particles according to [4] are molded in-mold.
  • Thermoplastic resin pre-foamed particles obtained by foaming foamable thermoplastic resin particles containing thermoplastic resin particles and a foaming agent, wherein N-hydroxyethyl-N-2-hydroxyalkylamine salt A ( A) and N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B) are coated on the surface of the thermoplastic resin pre-foamed particles, and the N-hydroxyethyl-N-2-
  • the salt A (A) of hydroxyalkylamine has 8 to 12 carbon atoms in the alkyl group, has one amino group and two hydroxyl groups in the molecule
  • the N-hydroxyethyl-N-2- A salt of hydroxyalkylamine B (B) is characterized in that the alkyl group has 14 carbon atoms and has one amino group and two hydroxyl groups in the molecule.
  • Plastic resin pre-expanded particles obtained by foaming foamable thermoplastic resin particles containing thermoplastic resin particles and a foaming agent, wherein N-hydroxy
  • thermoplastic resin foam obtained by foaming and molding foamable thermoplastic resin particles containing thermoplastic resin particles and a foaming agent, and a salt of N-hydroxyethyl-N-2-hydroxyalkylamine
  • the thermoplastic resin foam surface is coated with A (A) and N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B), and the N-hydroxyethyl-N-2 -Hydroxyalkylamine salt
  • a (A) has an alkyl group having 8 to 12 carbon atoms, one amino group and two hydroxyl groups in the molecule, and the N-hydroxyethyl-N-2
  • the salt of hydroxyalkylamine B (B) is a thermoplastic resin characterized in that the alkyl group has 14 carbon atoms and has one amino group and two hydroxyl groups in the molecule. Fat foam.
  • a process for producing expandable thermoplastic resin particles comprising contacting a thermoplastic resin particle with a foaming agent and impregnating the thermoplastic resin particle with the foaming agent; and N-hydroxyethyl-N-2 Applying an aqueous solution containing a salt of hydroxyalkylamine A (A) and a salt of N-hydroxyethyl-N-2-hydroxyalkylamine B (B) to the surface of the expandable thermoplastic resin particles
  • the N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A) has an alkyl group with 8 to 12 carbon atoms, one amino group in the molecule, and two hydroxyl groups
  • the N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B) has an alkyl group with 14 carbon atoms, one amino group in the molecule, and two hydro And having a sill group, method for producing expandable thermoplastic resin particles.
  • the concentrations of the N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A) and the N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B) in the aqueous solution are: [7] The method for producing expandable thermoplastic resin particles according to [7], wherein the content is 3 to 25% by weight.
  • a method for producing pre-expanded thermoplastic resin particles the step of foaming expandable thermoplastic resin particles, N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A), N- Applying an aqueous solution containing the salt B (B) of hydroxyethyl-N-2-hydroxyalkylamine to the surface of the thermoplastic resin pre-expanded particles, and the N-hydroxyethyl-N-2 -Hydroxyalkylamine salt A (A) has an alkyl group having 8 to 12 carbon atoms, one amino group and two hydroxyl groups in the molecule, and the N-hydroxyethyl-N-2
  • the salt of hydroxyalkylamine B (B) is a thermoplastic resin characterized in that the alkyl group has 14 carbon atoms and has one amino group and two hydroxyl groups in the molecule.
  • the concentrations of the N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A) and the N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B) in the aqueous solution are: [9] The method for producing pre-expanded thermoplastic resin particles according to [9], which is 3 to 25% by weight.
  • a method for producing a thermoplastic resin foam the step of molding pre-expanded thermoplastic resin particles, N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A), and N-hydroxy Applying an aqueous solution containing the salt B (B) of ethyl-N-2-hydroxyalkylamine to the surface of the thermoplastic resin foam, the N-hydroxyethyl-N-2-hydroxy
  • the alkylamine salt A (A) has an alkyl group having 8 to 12 carbon atoms, one amino group and two hydroxyl groups in the molecule, and the N-hydroxyethyl-N-2-hydroxy
  • the alkylamine salt B (B) is a thermoplastic resin foam characterized by having an alkyl group having 14 carbon atoms and having one amino group and two hydroxyl groups in the molecule. The method of production.
  • the concentrations of the N-hydroxyethyl-N-2-hydroxyalkylamine salt A (A) and the N-hydroxyethyl-N-2-hydroxyalkylamine salt B (B) in the aqueous solution are: [11] The method for producing a thermoplastic resin foam according to [11], wherein the thermoplastic resin foam is 3 to 25% by weight.
  • thermoplastic resin examples and Comparative Examples are given below, but the present invention is not limited by these.
  • a polystyrene resin is used as the thermoplastic resin.
  • the thermoplastic resin is not limited to the polystyrene resin.
  • the solution adjustment method and measurement evaluation method were performed as follows.
  • ⁇ Preparation of aqueous solution of antistatic agent> In a 500 ml beaker, (i) 100 parts by weight of pure water, (ii) 3.3 parts by weight of isopropanol, (iii) the alkyl group has 12 carbon atoms, and has one amino group and two hydroxyl groups in the molecule.
  • ⁇ Charge amount of foaming thermoplastic resin particles The expandable polystyrene resin particles were put in a polyethylene bag (OK bag No. 15, manufactured by Okura Kogyo Co., Ltd.) and stored overnight in a thermostatic chamber at 23 ° C. and 50% humidity. After storage, 300 g of expandable polystyrene resin particles were placed in another polyethylene bag (OK bag No. 15) and shaken 100 times with the mouth tied.
  • the mouth of the polyethylene bag is opened, and the amount of charge on the surface of the expandable polystyrene resin particles is measured three times by a static electricity measuring device (Statidon DX, manufactured by Sicid Electrostatic), and the average value thereof is coated with expandable particles (expandable polystyrene). Charge amount of the resin particles).
  • the measurement of the charge amount of the expandable polystyrene resin particles using the static electricity measuring device was performed in an atmosphere at a measurement distance of 30 mm, the charge amount measurement at 23 ° C., and a relative humidity of 50%. In this measurement method, a charging amount of ⁇ 1.0 kV to 1.0 kV was regarded as acceptable.
  • the measurement of the charge amount of the expandable polystyrene resin particles using the static electricity measuring device was performed in an atmosphere at a measurement distance of 30 mm, the charge amount measurement at 23 ° C., and a relative humidity of 50%. In this measurement method, a charging amount of ⁇ 1.0 kV to 1.0 kV was regarded as acceptable.
  • the expandable polystyrene resin particles were put into a pre-foaming machine equipped with a stirrer, and foamed by heating with steam to obtain polystyrene resin pre-expanded particles (hereinafter referred to as pre-expanded particles) having an apparent magnification of 5 to 80 times.
  • pre-expanded particles polystyrene resin pre-expanded particles having an apparent magnification of 5 to 80 times.
  • the crusher was stopped and the unfoamed pre-foamed particles were sent through a net having an opening of 1 cm to obtain pre-foamed particles.
  • Pre-expanded particles that did not pass through the net were recovered as blocked pre-expanded particles and weighed.
  • the ratio of the weight of the recovered pre-expanded particles (blocked pre-expanded particles) to the weight of the expanded polystyrene resin particles added was evaluated in terms of parts by weight based on the following criteria.
  • Pre-expanded particle charge The polystyrene resin pre-expanded particles were placed in a polyethylene bag (OK bag No. 15, manufactured by Okura Kogyo Co., Ltd.) and stored overnight in a temperature-controlled room at 23 ° C. and 50% humidity. After storage, 20 g of polystyrene resin pre-expanded particles were placed in another polyethylene bag (OK bag No. 15) and shaken 100 times with the mouth tied.
  • the mouth of the polyethylene bag is opened, and the amount of charge on the surface of the polystyrene resin pre-expanded particles is measured three times by a static electricity measuring device (Statidon DX, manufactured by Sicid Electrostatic), and the average value is coated pre-expanded particles (polystyrene resin).
  • the amount of charge of the pre-expanded particles The measurement of the charge amount of the polystyrene resin pre-expanded particles by the static electricity measuring device was performed in an atmosphere of a measurement distance of 30 mm, a charge amount measurement of 23 ° C., and a relative humidity of 50%. In this measurement method, a charging amount of ⁇ 1.0 kV to 1.0 kV was regarded as acceptable.
  • the measurement of the charge amount of the polystyrene resin pre-expanded particles by the static electricity measuring device was performed in an atmosphere with a measurement distance of 30 mm, a charge amount measurement of 23 ° C. and a relative humidity of 50%). In this measurement method, a charging amount of ⁇ 1.0 kV to 1.0 kV was regarded as acceptable.
  • ⁇ Foam charge amount> The foam was cut into a sample having a size of 100 mm (length) ⁇ 100 mm (width) ⁇ 10 mm (thickness). The charge amount of the surface of the obtained sample having the surface skin layer (that is, the surface not cut) was measured. After the sample was dried for 12 hours in a 35 ° C. drying chamber, the sample was taken out from the thermostatic chamber, and immediately after using a polyethylene bag (OK bag No. 15, Okura Kogyo Co., Ltd.), a foam ( Sample) The entire surface was quickly rubbed 5 times, and immediately after that, the surface charge amount of the foam surface within 1 second was measured. Measurement was performed using Statidon DX, manufactured by Sicid Electrostatic.
  • the measurement of the amount of charge on the surface of the foam using the static electricity measuring device was performed in an atmosphere of a measurement distance of 30 mm, a charge amount of 23 ° C., and a relative humidity of 50%. In this measurement method, a charging amount of ⁇ 1.0 kV to 1.0 kV was regarded as acceptable.
  • ⁇ Foam charge amount (immediate effect)> The foam was cut into a sample having a size of 100 mm (length) ⁇ 100 mm (width) ⁇ 10 mm (thickness). The charge amount of the surface of the obtained sample having the surface skin layer (that is, the surface not cut) was measured. After the antistatic agent is coated, the foam (sample) within 1 hour is immediately rubbed with the polyethylene foam (OK bag No. 15, manufactured by Okura Kogyo Co., Ltd.) quickly for 5 reciprocations. Immediately after that, the surface charge amount of the foam surface within 1 second was measured. Measurement was performed using Statidon DX, manufactured by Sicid Electrostatic.
  • the measurement of the amount of charge on the surface of the foam by the static electricity measuring device was performed in an atmosphere at a measurement distance of 30 mm, and the charge amount was measured at 23 ° C. and a relative humidity of 50%. In this measurement method, a charging amount of ⁇ 1.0 kV to 1.0 kV was regarded as acceptable.
  • Example 1 Manufacture of expandable thermoplastic resin particles>
  • thermoplastic resin pre-expanded particles Using the obtained expandable polystyrene resin particles, pre-foaming was carried out at a bulk magnification of 65 times under the condition of the blowing vapor pressure of 0.1 MPa using a pressure pre-foaming machine [Daikai Kogyo, CH-100]. . Thereafter, the pre-expanded particles thus obtained were left to stand at room temperature for 1 day for curing and drying. In the production of the pre-foamed particles, the blocking amount was measured by the above-described method to evaluate the blocking. The results are shown in Table 1.
  • thermoplastic resin foam ⁇ Manufacture of thermoplastic resin foam>
  • the obtained polystyrene resin pre-expanded particles were filled into a plate-shaped mold having a thickness of 25 mm, a length of 450 mm and a width of 300 mm using a molding machine [manufactured by Daisen Co., Ltd., KR-57].
  • In-mold molding was performed under molding conditions of 0.03 to 0.09 MPa to obtain a box-shaped foam.
  • the charge amount of the obtained foam was measured according to the method described above. The results are shown in Table 1.
  • Example 2 The total number of antistatic agents added to N-hydroxyethyl-N-2-hydroxyalkylamine A (A) and N-hydroxyethyl-N-2-hydroxyalkylamine B (B) was changed to 0.050 parts by weight. Except that, expandable polystyrene resin particles, pre-expanded particles, and foam were obtained by the same operation as in Example 1. The evaluation results are shown in Table 1.
  • Example 4 Expandable polystyrene-based resin particles and pre-expanded particles are the same as in Example 1 except that the added number of styrene monomers is 100 parts by weight and that of butyl acrylate monomer is changed to 0 parts by weight. A foam was obtained. The evaluation results are shown in Table 1.
  • Example 5 Except that the styrene monomer was changed to a methyl methacrylate monomer and the butyl acrylate monomer was changed to a methyl acrylate monomer, the same procedure as in Example 1 was carried out. Pre-expanded particles and foam were obtained. The evaluation results are shown in Table 1.
  • Example 6 Manufacture of expandable thermoplastic resin particles>
  • thermoplastic resin pre-expanded particles Using the obtained expandable polystyrene resin particles, pre-foaming was carried out at a bulk magnification of 65 times under the condition of the blowing vapor pressure of 0.1 MPa using a pressure pre-foaming machine [Daikai Kogyo, CH-100]. . Thereafter, the pre-expanded particles thus obtained were left to stand at room temperature for 1 day for curing and drying.
  • the charge amount of the pre-expanded particles after drying specifically, the charge amount of the pre-expanded particles within 1 hour from the coating of the antistatic agent and the charge amount of the pre-expanded particles after overnight storage were measured according to the above-mentioned method. .
  • the charge amount of the pre-expanded particles within one hour from the coating of the antistatic agent and the charge amount of the pre-expanded particles after overnight storage were both -0.1 kV.
  • Table 2 The results are shown in Table 2.
  • Example 7 In a 6 L autoclave attached to a stirrer, 100 parts by weight of pure water, 0.16 parts by weight of tricalcium phosphate, 0.01 parts by weight of sodium dodecylbenzenesulfonate, 0.25 parts by weight of benzoyl peroxide as an initiator, and 1 , 1-bis (t-butylperoxy) cyclohexane 0.15 parts by weight was charged. Subsequently, while stirring the raw material charged at 250 rpm, 95 parts by weight of styrene monomer and 5 parts by weight of butyl acrylate monomer were charged into the autoclave, and then the temperature in the autoclave was increased to 98 ° C. Allowed to warm. Subsequently, the temperature in the autoclave was maintained at 98 ° C. for 4 hours to obtain polystyrene resin particles.
  • thermoplastic resin pre-expanded particles Using the obtained expandable polystyrene resin particles, pre-foaming was carried out at a bulk magnification of 65 times under the condition of the blowing vapor pressure of 0.1 MPa using a pressure pre-foaming machine [Daikai Kogyo, CH-100]. . Thereafter, the pre-expanded particles thus obtained were left to stand at room temperature for 1 day for curing and drying.
  • thermoplastic resin foam ⁇ Manufacture of thermoplastic resin foam>
  • the obtained polystyrene resin pre-expanded particles were filled into a plate-shaped mold having a thickness of 25 mm, a length of 450 mm and a width of 300 mm using a molding machine [manufactured by Daisen Co., Ltd., KR-57].
  • In-mold molding was performed under molding conditions of 0.03 to 0.09 MPa to obtain a box-shaped foam.
  • the amount of charge of the foam after drying specifically, the amount of charge of the foam within 1 hour from the coating of the antistatic agent and the amount of charge of the foam after drying for 12 hours were measured according to the above-mentioned method. As a result, the charge amount of the foam within 1 hour after coating with the antistatic agent was ⁇ 0.3 kV, and the charge amount of the foam after drying for 12 hours was ⁇ 0.2 kV. The results are shown in Table 2.
  • the powder (B) and expandable polystyrene resin particles were mixed and the number of added antistatic agents was changed to 0.015 parts by weight. Resin particles, pre-expanded particles, and foam were obtained. The evaluation results are shown in Table 1.
  • the powder (B) and expandable polystyrene resin particles were mixed and the number of added antistatic agents was changed to 0.050 part by weight. Resin particles, pre-expanded particles, and foam were obtained. The evaluation results are shown in Table 1.
  • the powder (B) and the expandable polystyrene resin particles are mixed so as to cover the surface of the expandable polystyrene resin particles in a powder state, and the antistatic agent.
  • Expandable polystyrene resin particles, pre-expanded particles, and foam were obtained by the same operation as in Example 1 except that the number of added parts was changed to 0.100 parts by weight. The evaluation results are shown in Table 1.
  • the powder (B) and expandable polystyrene resin particles were mixed and the number of added antistatic agents was changed to 0.015 parts by weight. Resin particles, pre-expanded particles, and foam were obtained. The evaluation results are shown in Table 1.
  • the powder (A) and the expandable polystyrene resin particles were mixed and the addition amount of the antistatic agent was changed to 0.015 parts by weight. Resin particles, pre-expanded particles, and foam were obtained. The evaluation results are shown in Table 1.
  • thermoplastic resin foam obtained by foaming thermoplastic resin pre-foamed particles, which is made of foamable thermoplastic resin particles, is a fish box, an agricultural box, a food container, It can be suitably used for a wide range of applications such as cushioning materials for home appliances, and insulation materials for building materials.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

L'invention concerne des particules de résine thermoplastique expansibles, des particules pré-expansées de résine thermoplastique et une mousse de résine thermoplastique, qui permettent d'obtenir efficacement des effets antistatiques, les particules de résine thermoplastique expansibles comprenant des particules de résine thermoplastique et un agent d'expansion, les surfaces des particules de résine thermoplastique expansibles étant revêtues d'un sel A (A) et d'un sel (B) de deux types d'hydroxyalkylamines, et la quantité totale déposée de (A) et de (B) étant de 0,005 à 0,075 parties en poids pour 100 parties en poids des particules de résine thermoplastique expansibles.
PCT/JP2019/013794 2018-03-28 2019-03-28 Particules de résine thermoplastique expansibles, particules pré-expansées de résine thermoplastique et mousse de résine thermoplastique Ceased WO2019189662A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023162647A1 (fr) * 2022-02-25 2023-08-31 株式会社カネカ Particules de résine expansibles, leur procédé de production, particules expansées et mousse moulée

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0224332A (ja) * 1988-07-12 1990-01-26 Kanegafuchi Chem Ind Co Ltd 発泡性スチレン系樹脂粒子の製造方法
JPH07278340A (ja) * 1994-04-14 1995-10-24 Dainippon Ink & Chem Inc 発泡性スチレン系樹脂粒子およびその製造方法
JP2009256470A (ja) * 2008-04-17 2009-11-05 Kaneka Corp ポリプロピレン系樹脂発泡粒子、型内発泡成形体および発泡粒子の製造方法
JP2013203470A (ja) * 2012-03-29 2013-10-07 Sekisui Plastics Co Ltd ガラス搬送用容器
JP2016180073A (ja) * 2015-03-25 2016-10-13 株式会社ジェイエスピー 発泡粒子成形体及びパネル梱包容器
JP2017114987A (ja) * 2015-12-22 2017-06-29 株式会社カネカ 低帯電量の発泡性スチレン系樹脂粒子、予備発泡粒子及び発泡成形体の製造方法
JP2018030923A (ja) * 2016-08-23 2018-03-01 株式会社ジェイエスピー 複合樹脂発泡粒子、帯電防止性複合樹脂発泡粒子、複合樹脂発泡粒子成形体

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0224332A (ja) * 1988-07-12 1990-01-26 Kanegafuchi Chem Ind Co Ltd 発泡性スチレン系樹脂粒子の製造方法
JPH07278340A (ja) * 1994-04-14 1995-10-24 Dainippon Ink & Chem Inc 発泡性スチレン系樹脂粒子およびその製造方法
JP2009256470A (ja) * 2008-04-17 2009-11-05 Kaneka Corp ポリプロピレン系樹脂発泡粒子、型内発泡成形体および発泡粒子の製造方法
JP2013203470A (ja) * 2012-03-29 2013-10-07 Sekisui Plastics Co Ltd ガラス搬送用容器
JP2016180073A (ja) * 2015-03-25 2016-10-13 株式会社ジェイエスピー 発泡粒子成形体及びパネル梱包容器
JP2017114987A (ja) * 2015-12-22 2017-06-29 株式会社カネカ 低帯電量の発泡性スチレン系樹脂粒子、予備発泡粒子及び発泡成形体の製造方法
JP2018030923A (ja) * 2016-08-23 2018-03-01 株式会社ジェイエスピー 複合樹脂発泡粒子、帯電防止性複合樹脂発泡粒子、複合樹脂発泡粒子成形体

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023162647A1 (fr) * 2022-02-25 2023-08-31 株式会社カネカ Particules de résine expansibles, leur procédé de production, particules expansées et mousse moulée

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