WO2013147040A1 - Particules de résine composites, particules de résine composites expansibles, particules pré-expansées, mousse moulée, et matériau de cœur pour pare-chocs - Google Patents

Particules de résine composites, particules de résine composites expansibles, particules pré-expansées, mousse moulée, et matériau de cœur pour pare-chocs Download PDF

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Publication number
WO2013147040A1
WO2013147040A1 PCT/JP2013/059303 JP2013059303W WO2013147040A1 WO 2013147040 A1 WO2013147040 A1 WO 2013147040A1 JP 2013059303 W JP2013059303 W JP 2013059303W WO 2013147040 A1 WO2013147040 A1 WO 2013147040A1
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resin particles
composite resin
particles
resin
mass
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PCT/JP2013/059303
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English (en)
Japanese (ja)
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正彦 小澤
浩司 森
丈晴 中野
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積水化成品工業株式会社
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Priority to DE112013001815.2T priority Critical patent/DE112013001815T5/de
Publication of WO2013147040A1 publication Critical patent/WO2013147040A1/fr

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • C08J9/232—Forming foamed products by sintering expandable particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/034—Post-expanding of foam beads or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/18—Binary blends of expanding agents
    • C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
    • 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
    • C08J2207/00—Foams characterised by their intended use
    • 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
    • C08J2325/00—Characterised by the use 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 aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/12—Polypropene

Definitions

  • the present invention relates to composite resin particles, expandable composite resin particles, pre-expanded particles, foamed molded products, and bumper core materials. Specifically, the present invention relates to composite resin particles capable of obtaining a foamed molded article excellent in impact resistance and heat dimensional stability, and expandable composite resin particles obtained from the composite resin particles, pre-expanded particles The present invention relates to a foam molded body and a bumper core material.
  • foamed molded products containing polystyrene resin as a resin component have excellent physical properties such as molding processability, heat insulation, impact resistance and buffering properties. Widely used as a member.
  • the patent document 1, 2 and 3 describe the foaming molding which contains a polystyrene-type resin and a polyolefin-type resin as a resin component.
  • an automotive foam molded body such as a bumper core material is required to have improved energy absorption characteristics, that is, higher impact resistance.
  • the foamed molded body is also required to have high dimensional stability under a high temperature environment, that is, excellent heating dimensional stability in order to prevent malfunction of the detection function.
  • the present invention has been made in view of the above problems, and is obtained from composite resin particles capable of obtaining a foamed molded article excellent in impact resistance and heat dimensional stability, and obtained from the composite resin particles. It is an object of the present invention to provide expandable composite resin particles, pre-expanded particles, a foam molded article, and a bumper core material.
  • the present inventors have determined that, as a resin component, from a composite resin particle containing a polyolefin resin having a specific range of Vicat softening point and dispersity and a polystyrene resin, impact resistance and heat dimensional stability.
  • the present inventors have found that an excellent foam molded article can be provided, and have come to carry out the present invention.
  • the resin component includes 100 parts by mass of polyolefin resin and 100 to 400 parts by mass of polystyrene resin, and the polyolefin resin has a Vicat softening point of 110 to 125 ° C. and 1.5 to 4.8.
  • Composite resin particles having a degree of dispersion of 5 are provided.
  • foamable composite resin particles capable of obtaining a foamed molded article excellent in impact resistance and heat dimensional stability.
  • pre-expanded particles capable of obtaining a foamed molded article excellent in impact resistance and heat dimensional stability are provided.
  • a foamed molded article excellent in impact resistance and heat dimensional stability is provided.
  • a core material for a bumper excellent in impact resistance and heating dimensional stability is provided.
  • composite resin particles capable of obtaining a foamed molded article excellent in impact resistance and heat dimensional stability it is possible to provide composite resin particles capable of obtaining a foamed molded article having excellent energy absorption characteristics and heat dimensional stability under a high temperature environment.
  • the composite resin particles when the composite resin particles contain 100 parts by mass of a polyolefin resin and 100 to 300 parts by mass of a polystyrene resin as resin components, a foamed molded article having superior impact resistance and heat dimensional stability can be obtained.
  • the composite resin particle which can be obtained can be provided.
  • the composite resin particles when the composite resin particles have a dispersity of 2.0 to 4.5, the composite resin particles capable of obtaining a foamed molded article superior in impact resistance and heat dimensional stability are obtained. Can be provided.
  • the polyolefin resin is a polyethylene resin or a polypropylene resin
  • the composite resin particles when the composite resin particles have a Vicat softening point of 110 to 130 ° C., it is possible to provide composite resin particles that can obtain a foamed molded article that is superior in impact resistance and heat dimensional stability.
  • the composite resin particles when the composite resin particles contain 0.5 to 3.0 parts by mass of carbon black with respect to 100 parts by mass of the resin component, the composite resin particles contain carbon black as a colorant in a suitable ratio.
  • composite resin particles capable of obtaining a foamed molded article having excellent impact resistance and heat dimensional stability and also excellent design properties can be provided.
  • foamable composite resin particles capable of obtaining a foamed molded article having excellent impact resistance and heat dimensional stability from the composite resin particles as described above.
  • the foamed molded product has a density of 0.020 to 0.10 g / cm 3 , it is possible to provide a foamed molded product that is superior in impact resistance and heat dimensional stability.
  • the present invention includes 100 parts by mass of a polyolefin resin and 100 to 400 parts by mass of a polystyrene resin as resin components, and the polyolefin resin has a Vicat softening point of 110 to 125 ° C. and a dispersity of 1.5 to 4.8. It relates to composite resin particles having
  • the composite resin particles of the present invention contain a polyolefin resin and a polystyrene resin in suitable proportions.
  • the composite resin particle has characteristics such as rigidity, heat insulation, light weight, water resistance and foaming moldability possessed by polystyrene resin and chemical resistance, heat resistance and impact resistance possessed by polyolefin resin (impact Absorptivity) and the like.
  • the polyolefin resin has a Vicat softening point of 110 to 125 ° C. and a dispersity of 1.5 to 4.8. For this reason, the impact resistance and heat dimensional stability of foamed moldings obtained from polyolefin resin and composite resin particles containing polyolefin resin are improved by suitably setting the polymer chain and structure in polyolefin resin. Can be made. As a result, the foam molded product obtained from such composite resin particles can be widely used as a component packing material, an automobile member, a cushioning material, or a bumper core material, particularly as a bumper core material.
  • the degree of dispersion (Mw / Mn) means a value indicating the degree of monodispersity of the chain length distribution obtained using the number average molecular weight (Mn) and the weight average molecular weight (Mw).
  • the present invention it is possible to provide composite resin particles capable of obtaining a foamed molded article excellent in impact resistance and heat dimensional stability.
  • the composite resin particles of the present invention will be described more specifically.
  • the composite resin particle means a resin particle obtained by combining a plurality of resin components. Specific examples include resin particles obtained by modifying a polyolefin resin with a polystyrene resin derived from a styrene monomer. “Composite” means that a polyolefin resin and a polystyrene resin are present in the particle, and “modification” means impregnating and polymerizing a styrene monomer in the polyolefin resin. To do.
  • the composite resin particles of the present invention contain a polyolefin resin and a polystyrene resin in a suitable ratio. Specifically, the composite resin particles contain 100 to 400 parts by mass, preferably 100 to 300 parts by mass, and more preferably 150 to 230 parts by mass of a polystyrene resin with respect to 100 parts by mass of the polyolefin resin. When the composite resin particles contain 100 parts by mass of polyolefin resin, specific values of polystyrene resin content are 100, 130, 150, 180, 200, 230, 240, 250, 270, 300, 350, 400 parts by mass and the like can be mentioned.
  • the ratio of the polystyrene resin in the composite resin particles becomes low, and the composite resin particles may not be able to obtain sufficient characteristics derived from the polystyrene resin.
  • the amount of the polystyrene resin is more than 400 parts by mass, the ratio of the polyolefin resin in the composite resin particles becomes low, and the characteristics derived from the polyolefin resin may not be sufficiently obtained.
  • the composite resin particles preferably have a Vicat softening point of 110 to 130 ° C., more preferably 110 to 125 ° C.
  • the Vicat softening point is one of the indices representing the heat resistance of the resin, and the composite resin particles are measured according to the method described in JIS K7196: 1991 “Softening temperature test method by thermomechanical analysis of thermoplastic film and sheet”. What you did. Specific measurement methods are as in the following examples.
  • the Vicat softening point of the composite resin particle means the Vicat softening point of the composite resin particle itself containing the composite resin particle when the composite resin particle contains other components other than the resin component such as carbon black.
  • the Vicat softening point of the composite resin particle means the Vicat softening point of the resin component itself of the composite resin particle.
  • Specific numerical values of the Vicat softening point of the composite resin particles are 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130 ° C. and the like.
  • the composite resin particles When the Vicat softening point of the composite resin particles is lower than 110 ° C., the composite resin particles may not have sufficient heat resistance. On the other hand, when the Vicat softening point of the composite resin particles is higher than 130 ° C., the foamable composite resin particles may not have sufficient foamability.
  • the composite resin particles preferably have an average particle diameter of 0.71 to 2.5 mm, more preferably 0.85 to 1.6 mm.
  • the shape is preferably spherical to substantially spherical. Specific numerical values of the average particle diameter of the composite resin particles are 0.71, 0.75, 0.80, 0.85, 0.90, 0.95, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5 mm, etc. It is done.
  • the polyolefin resin is not particularly limited, and means an olefin homopolymer or a copolymer of an olefin monomer as a main component and another monomer copolymerizable with the olefin monomer.
  • the main component of the olefin monomer means that the olefin monomer occupies 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more of the total monomers. .
  • Specific values of the proportion of the olefinic monomer when the total monomer is 100% by mass are 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100% by mass. Etc.
  • examples of the polyolefin resin include an ⁇ -olefin resin such as a polyethylene resin, a polypropylene resin, and a polybutylene resin. Moreover, since a desired physical property can be obtained more easily, a polyethylene resin, a polypropylene resin, and a combination thereof are preferable as the polyolefin resin.
  • the polyolefin resin of the present invention has a Vicat softening point of 110 to 125 ° C, preferably 112 to 125 ° C, more preferably 113 to 123 ° C.
  • the Vicat softening point is one of the indices representing the heat resistance of the resin.
  • the Vicat softening point is measured according to the method described in JIS K7206: 1999 “Plastics—Thermoplastics—Vicat softening temperature test method”. .
  • Specific values of the Vicat softening point of the polyolefin resin include 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125 ° C., and the like. .
  • the composite resin particles When the Vicat softening point of the polyolefin resin is lower than 110 ° C., the composite resin particles may not have sufficient heat resistance. On the other hand, when the Vicat softening point of the polyolefin resin is higher than 125 ° C., the expandable composite resin particles may not have sufficient expandability.
  • the polyethylene resin preferably has a weight average molecular weight (Mw) of 60 ⁇ 10 3 to 200 ⁇ 10 3 , more preferably 70 ⁇ 10 3 to 190 ⁇ 10 3 .
  • Mw weight average molecular weight
  • Specific numerical values of the weight average molecular weight of the polyethylene resin include 60 ⁇ 10 3 , 70 ⁇ 10 3 , 80 ⁇ 10 3 , 90 ⁇ 10 3 , 100 ⁇ 10 3 , 150 ⁇ 10 3 , 160 ⁇ 10 3 , 170 * 10 ⁇ 3 >, 180 * 10 ⁇ 3 >, 190 * 10 ⁇ 3 >, 200 * 10 ⁇ 3 > etc. are mentioned.
  • the composite resin particles When the weight average molecular weight is lower than 60 ⁇ 10 3 , the composite resin particles may not have sufficient heat resistance. On the other hand, when the weight average molecular weight is higher than 200 ⁇ 10 3 , the expandable composite resin particles may not have sufficient expandability.
  • the polyethylene resin preferably has a number average molecular weight (Mn) of 10 ⁇ 10 3 to 80 ⁇ 10 3 , more preferably 15 ⁇ 10 3 to 80 ⁇ 10 3 .
  • Mn number average molecular weight
  • Specific numerical values of the number average molecular weight of the polyethylene resin are 10 ⁇ 10 3 , 15 ⁇ 10 3 , 20 ⁇ 10 3 , 30 ⁇ 10 3 , 40 ⁇ 10 3 , 50 ⁇ 10 3 , 60 ⁇ 10 3 , 70 * 10 ⁇ 3 >, 80 * 10 ⁇ 3 > etc. are mentioned.
  • the composite resin particles may not have sufficient heat resistance.
  • the expandable composite resin particles may not have sufficient expandability.
  • the polypropylene resin preferably has a weight average molecular weight of 200 ⁇ 10 3 to 400 ⁇ 10 3 , more preferably 250 ⁇ 10 3 to 390 ⁇ 10 3 .
  • Specific numerical values of the weight average molecular weight of the polypropylene resin include 200 ⁇ 10 3 , 230 ⁇ 10 3 , 250 ⁇ 10 3 , 300 ⁇ 10 3 , 310 ⁇ 10 3 , 320 ⁇ 10 3 , 330 ⁇ 10 3 , 340 * 10 ⁇ 3 >, 350 * 10 ⁇ 3 >, 360 * 10 ⁇ 3 >, 370 * 10 ⁇ 3 >, 380 * 10 ⁇ 3 >, 390 * 10 ⁇ 3 >, 400 * 10 ⁇ 3 > etc. are mentioned.
  • the composite resin particles When the weight average molecular weight is lower than 200 ⁇ 10 3 , the composite resin particles may not have sufficient heat resistance. On the other hand, when the weight average molecular weight is higher than 400 ⁇ 10 3 , the expandable composite resin particles may not have sufficient expandability.
  • the polypropylene resin preferably has a number average molecular weight (Mn) of 70 ⁇ 10 3 to 160 ⁇ 10 3 , more preferably 80 ⁇ 10 3 to 150 ⁇ 10 3 .
  • Mn number average molecular weight
  • Specific numerical values of the number average molecular weight of the polypropylene resin include 70 ⁇ 10 3 , 75 ⁇ 10 3 , 80 ⁇ 10 3 , 90 ⁇ 10 3 , 100 ⁇ 10 3 , 110 ⁇ 10 3 , 120 ⁇ 10 3 , 130 ⁇ 10 3, 140 ⁇ 10 3, 150 ⁇ 10 3, 155 ⁇ 10 3, 160 ⁇ 10 3 , and the like.
  • the composite resin particles may not have sufficient heat resistance.
  • the expandable composite resin particles may not have sufficient expandability.
  • the polyolefin resin of the present invention has a dispersity (Mw / Mn) of 1.5 to 4.8, preferably 2.0 to 4.5.
  • Specific numerical values of the dispersibility of the polyolefin resin include 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 3.0, 3.5, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4. 8 etc. are mentioned.
  • the manufacturing cost may be a problem.
  • the degree of dispersion is higher than 4.8, the impact resistance of the foamed molded product may be lowered.
  • the polyethylene resin is preferably 0.927 to 0.950 kg / m 3 , more preferably 0.927 to 0.945 kg / m 3 , and still more preferably 0.930. It has a density of ⁇ 0.945 kg / m 3 .
  • specific numerical values of the density of the polyethylene resin are 0.927, 0.928, 0.929, 0.930, 0.931, 0.932, 0.933, 0.934, 0.935.
  • the composite resin particles may not have sufficient heating dimensional stability.
  • the density of the polyethylene resin is higher than 0.950 kg / m 3 , the resin component may not be sufficiently softened during the polymerization process, and the expandable composite resin particles may not have sufficient expandability.
  • the polyolefin resin is preferably 1.0-10.0 g / 10 min, more preferably 1.0-7.0 g / min. It has a melt flow rate of 10 minutes.
  • specific numerical values of the melt flow rate of the polyolefin resin are 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.7, 2.0, 2.5, 3.0, 4.0, 5.0, 6.0, 6.5, 6.8, 7.0, 7.2, 7.4, 7.6, 7.8, 8. 0, 8.2, 8.4, 8.6, 8.8, 9.0, 9.2, 9.4, 9.6, 9.8, 10.0 g / 10 min.
  • the polyolefin resin is preferably 1.0 to 10.0 g / 10 min, more preferably 2.0 to 9. It has a melt flow rate of 0 g / 10 min.
  • specific numerical values of the melt flow rate of the polyolefin resin are 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 3.0, 4.0, 5.0, 6.0, 7. 0, 7.5, 8.0, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0 g / 10 min, etc. are mentioned.
  • melt flow rate of these polyolefin resins is lower than 1.0 g / 10 min, it may be impossible to obtain a foam having a predetermined multiple.
  • melt flow rate of the polyolefin-based resin is higher than 10.0 g / 10 minutes, it may be impossible to obtain a predetermined multiple of foam.
  • the polyolefin resin in the composite resin particles has such Vicat softening point, weight average molecular weight, number average molecular weight, dispersity, density and melt flow rate, expandable composite resin particles obtained from the composite resin particles, pre-expanded
  • the polyolefin resin in the particles, the molded foam and the bumper core material also has substantially the same Vicat softening point, weight average molecular weight, number average molecular weight, dispersity, density and melt flow rate, respectively.
  • Polyolefin resins such as polyethylene resins and polypropylene resins can be produced according to known methods. Furthermore, in the case of producing a polyethylene resin and a polypropylene resin having the above characteristics, a polymerization method using a metallocene compound as a catalyst is preferable because they can be produced more easily.
  • metallocene compound examples include known metallocene compounds.
  • a metallocene compound containing a tetravalent transition metal element can be preferably used.
  • the composite resin particle contains a polystyrene resin as a resin component.
  • the composite resin particles can have excellent properties such as rigidity, heat insulation, light weight, water resistance, and foam moldability of the polystyrene resin.
  • the polystyrene resin means a styrene homopolymer or a copolymer of a styrene monomer as a main component and another monomer component copolymerizable with the styrene monomer.
  • the styrene monomer as a main component means that the styrene monomer occupies 50 parts by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more in 100 parts by mass of all monomer components. Means. Specific values of the proportion of the styrenic monomer when the total monomer is 100% by mass are 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100% by mass. Etc.
  • the copolymer component contained in the polystyrene resin a known monomer can be used as long as it does not affect the desired physical properties. Specifically, cyclic olefin monomers, diene monomers, vinyl chloride, vinylidene chloride, acrylonitrile, vinyl acetate, acrylic acid, methacrylic acid, maleic acid, ethyl acrylate, butyl acrylate, methyl methacrylate, Mention may be made of vinylic monomers such as maleic anhydride and methylstyrene. Moreover, these can also be used by 1 type (s) or 2 or more types.
  • carbon black is preferably used in an amount of 0.5 to 3.0 parts by mass with respect to 100 parts by mass of the resin component. More preferably, the content is 0.5 to 2.0 parts by mass. Specific numerical values of the carbon black content in the composite resin particles are 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1 with respect to 100 parts by mass of the resin component. 0.5, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, 3.0 parts by mass and the like.
  • the composite resin particles When the amount of carbon black is less than 0.5 parts by mass, the composite resin particles may not have sufficient colorability. On the other hand, when carbon black is contained more than 3.0 parts by mass, the composite resin particles may not have impact resistance.
  • Known carbon black can be used. Specific examples include carbon-based materials such as furnace black, channel black, thermal black, acetylene black, graphite, and carbon fiber.
  • a composition containing carbon black a so-called master batch may be added.
  • the master batch contains carbon black in a proportion of preferably 30 to 50 parts by mass, more preferably 35 to 45 parts by mass with respect to 100 parts by mass of the master batch.
  • the specific value of the carbon black content in the master batch is 30, 31, 32, 33, 34, 35, 37, 40, 43, 45, 46, 47 with respect to 100 parts by mass of the master batch. 48, 49, 50 parts by mass, and the like.
  • the base resin contained in the master batch is preferably an olefin resin.
  • composite resin particles and the following expandable composite resin particles, pre-expanded particles, and foamed molded article may contain other additives as appropriate.
  • specific examples include a bubble regulator, a coating agent, a light stabilizer, an ultraviolet absorber, a pigment, a dye, an antifoaming agent, a heat stabilizer, a lubricant, and an antistatic agent.
  • the mass and mass ratio of the raw material monomer, raw material resin, and other components, and the mass and mass of the composite resin particles, expandable composite resin particles, pre-expanded particles, resin components in the foamed molded product, and other components is substantially the same.
  • the qualitative and quantitative determination of the raw materials contained in the composite resin particles, expandable composite resin particles, pre-expanded particles and foamed molded products can be performed by nuclear magnetic resonance spectroscopy (NMR), infrared spectroscopy (IR), gel permeation. It can carry out according to a well-known method using chromatography (GPC) etc.
  • NMR nuclear magnetic resonance spectroscopy
  • IR infrared spectroscopy
  • GPC chromatography
  • the foamable composite resin particles of the present invention also use the composite resin particles as described above as a raw material, a foamed molded article excellent in impact resistance and heat dimensional stability can be obtained therefrom.
  • the expandable composite resin particle means a composite resin particle exhibiting heat foamability, which is obtained by impregnating a composite resin particle with a foaming agent.
  • the foaming agent content in the expandable composite resin particles is preferably 5 to 15 parts by mass, more preferably 8 to 10 parts by mass with respect to 100 parts by mass of the composite resin particles as the resin component. .
  • Specific numerical values of the foaming agent content in the expandable composite resin particles are 5, 6, 7, 8, 9, 10, 11, 12, 13, with respect to 100 parts by mass of the composite resin particles as the resin component. 14, 15 parts by mass and the like.
  • the foaming agent When the foaming agent is lower than 5 parts by mass, the amount of the foaming agent is insufficient, and the foamable composite resin particles may not have sufficient foamability. On the other hand, when the amount of the foaming agent is more than 15 parts by mass, the amount of the foaming agent is excessive, and in this case as well, the foamable composite resin particles may not have sufficient foamability.
  • foaming agent a known foaming agent having volatility can be used.
  • any of n-butane, i-butane, n-pentane and i-pentane which can introduce greater foaming performance into the foamable composite resin particles, is preferable.
  • a foaming agent may be used independently and may use 2 or more types.
  • the expandable composite resin particles preferably have an average particle diameter of 0.71 to 2.5 mm, more preferably 0.85 to 1.6 mm. Specific numerical values of the average particle diameter of the expandable composite resin particles are 0.71, 0.75, 0.80, 0.85, 0.90, 0.95, 1.0, 1.1, 1. 2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5mm etc. are mentioned.
  • the shape is preferably spherical to substantially spherical.
  • pre-expanded particles of the present invention also use the composite resin particles as a raw material, a foamed molded article excellent in impact resistance and heat dimensional stability can be obtained therefrom.
  • the pre-expanded particles mean resin particles obtained by heating and foaming the expandable composite resin particles as described above to a predetermined bulk density.
  • the pre-expanded particles preferably have a bulk density of 0.020 to 0.10 g / cm 3 , more preferably 0.025 to 0.10 g / cm 3 .
  • a bulk density of the pre-expanded particles 0.020, 0.021, 0.022, 0.023, 0.024, 0.025, 0.026, 0.028, 0.030, 0 0.040, 0.050, 0.060, 0.070, 0.080, 0.090, 0.095, 0.098, 0.099, 0.10 g / cm 3 and the like.
  • the strength and heat resistance of the obtained foamed molded product may be lowered.
  • it is higher than 0.10 g / cm 3 the weight of the obtained foamed molded product may increase.
  • the pre-expanded particles preferably have an average particle diameter of 1.0 to 9.0 mm, more preferably 2.0 to 6.4 mm.
  • Specific numerical values of the average particle diameter of the pre-expanded particles are 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.2, 6.4, 6.6, 6.8, 7. 0, 7.2, 7.4, 7.6, 7.8, 8.0, 8.2, 8.4, 8.6, 8.8, 9.0 mm and the like.
  • the shape is preferably spherical to approximately spherical.
  • the foamed molded product means a resin molded product obtained by thermally fusing the pre-expanded particles as described above.
  • the foamed molded article can have more excellent heat resistance and impact resistance, it preferably has a density of 0.020 to 0.10 g / cm 3 , more preferably 0.025 to 0.10 g / cm 3 .
  • Specific numerical values of the density of the foam molded article are 0.020, 0.021, 0.022, 0.023, 0.024, 0.025, 0.026, 0.028, 0.030, 0.0. 040, 0.050, 0.060, 0.070, 0.080, 0.090, 0.095, 0.096, 0.097, 0.098, 0.099, 0.10 g / cm 3 etc. Can be mentioned.
  • the density is lower than 0.020 g / cm 3 , the strength and heat resistance of the obtained foamed molded product may be lowered.
  • it is higher than 0.10 g / cm 3 , the weight of the obtained foamed molded product may increase.
  • the foamed molded product of the present invention preferably exhibits an absorbed energy of 1.2 to 3.0 J, more preferably 1.3 to 3.0 J, in the impact test of ASTM D3763-92.
  • Specific numerical values of the absorbed energy exhibited by the foam molded article are 1.2, 1.3, 1.4, 1.5, 1.7, 2.0, 2.3, 2.5, 2.6, 2.7, 2.8, 2.9, and 3.0J.
  • the foamed molded article exhibits a heating dimensional change rate of preferably 1.0% or less, more preferably 0.8% or less, in a heating dimensional change test of JIS K6767: 1999.
  • a heating dimensional change rate preferably 1.0% or less, more preferably 0.8% or less, in a heating dimensional change test of JIS K6767: 1999.
  • specific numerical values of the heating dimensional change rate exhibited by the foam molded article 0.00%, 0.10%, 0.20%, 0.30%, 0.40%, 0.50%, 0.60% 0.65%, 0.66%, 0.67%, 0.68%, 0.69%, 0.70%, 0.71%, 0.72%, 0.73%, 0.74% 0.75% 0.76% 0.77% 0.78% 0.79% 0.80% 0.81% 0.82% 0.83% 0.84% 0.85%, 0.86%, 0.87%, 0.88%, 0.89%, 0.90%, 0.91%, 0.92%, 0.93%, 0.94% 0.95%, 0.96%, 0.97%,
  • the composite resin particles can be produced, for example, as follows. That is, 100 parts by mass of polyolefin resin particles, 100 to 400 parts by mass of a styrene monomer, and a polymerization initiator are dispersed in an aqueous suspension. In addition, you may mix and use a styrene-type monomer and a polymerization initiator previously.
  • the polyolefin resin particles can be obtained by a known method.
  • a polyolefin resin is melt-kneaded in an extruder together with an inorganic nucleating agent and additives as necessary to obtain a strand, and the obtained strand is cut in air, cut in water, The method of granulating by cutting while heating is mentioned.
  • the inorganic nucleating agent examples include talc, silicon dioxide, mica, clay, zeolite, calcium carbonate and the like.
  • the amount of the inorganic nucleating agent used is preferably 2 parts by mass or less, more preferably 0.2 to 1.5 parts by mass with respect to 100 parts by mass of the polyethylene resin. Specific values for the amount of the inorganic nucleating agent used are 0.2, 0.5, 1.0, 1.3, 1.5, 1.7, 1.8 with respect to 100 parts by mass of the polyethylene resin. 1.9, 2 mass parts, etc. are mentioned.
  • the aqueous medium constituting the aqueous suspension include water and a mixed medium of water and a water-soluble solvent (for example, lower alcohol).
  • polymerization initiator those generally used as an initiator for suspension polymerization of a styrene monomer can be used.
  • These polymerization initiators may be used alone or in combination of two or more.
  • the amount of the polymerization initiator used is preferably 0.1 to 0.9 parts by mass and more preferably 0.2 to 0.5 parts by mass with respect to 100 parts by mass of the styrene monomer. Specific values of the amount of the polymerization initiator used are 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0 with respect to 100 parts by mass of the styrene monomer. 0.7, 0.8, 0.9 parts by mass and the like. If it is less than 0.1 part by mass, it may take too much time to polymerize the styrene monomer. If the polymerization initiator exceeds 0.9 parts by mass, the molecular weight of the styrene resin may be lowered.
  • a dispersant may be added to the aqueous suspension as necessary.
  • the dispersant is not particularly limited, and any known dispersant can be used. Specific examples include hardly soluble inorganic substances such as calcium phosphate, magnesium pyrophosphate, sodium pyrophosphate, magnesium oxide. Further, a surfactant such as sodium dodecylbenzenesulfonate may be used.
  • the obtained dispersion is heated to a temperature at which the styrene monomer is not substantially polymerized to impregnate the polyolefin resin particles with the styrene monomer.
  • a suitable time for impregnating the polyolefin resin particles with the styrene monomer is 30 minutes to 2 hours. Specific values for the impregnation time of the styrene monomer include 30 minutes, 45 minutes, 1 hour, 1 hour 15 minutes, 1 hour 30 minutes, 1 hour 45 minutes, 2 hours, and the like. If the polymerization proceeds before being sufficiently impregnated, a polymer powder of a styrene resin may be produced.
  • the temperature at which the monomer is not substantially polymerized is advantageous in that the higher the temperature, the higher the impregnation rate. However, it is necessary to determine the temperature considering the decomposition temperature of the polymerization initiator.
  • styrene monomer is polymerized.
  • the polymerization is not particularly limited, but is preferably performed at 115 to 140 ° C. for 1.5 to 5 hours.
  • Specific values of the polymerization temperature include 115, 120, 125, 130, 135, 140 ° C., and the like.
  • Specific values for the polymerization time include 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5 hours, and the like.
  • the polymerization is usually carried out in an airtight container that can be pressurized.
  • the impregnation and polymerization of the styrene monomer may be performed in a plurality of times. By dividing into multiple times, the generation of polystyrene polymer powder can be minimized.
  • the polymerization may be carried out while impregnating the styrene monomer with the polyolefin resin particles instead of impregnating the styrene monomer.
  • Composite resin particles can be obtained by the above process.
  • the expandable resin particles can be obtained by impregnating the composite resin particles during or after the polymerization with a foaming agent.
  • This impregnation can be performed by a method known per se.
  • the impregnation during the polymerization can be performed by performing the polymerization reaction in a sealed container and press-fitting a foaming agent into the container.
  • the impregnation after the completion of the polymerization is performed by press-fitting a foaming agent in a sealed container.
  • the pre-expanded particles can be obtained by pre-expanding the expandable resin particles to a predetermined bulk density by a known method.
  • the pre-expanded particle manufacturing method preferably uses heated steam of 0.05 to 0.15 MPa, more preferably 0.06 to 0.10 MPa.
  • a step of pre-foaming the expandable composite resin particles are 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13. 0.14, 0.15 MPa, and the like. In this case, it is possible to reduce manufacturing cost and manufacturing time by using higher-pressure heating steam.
  • the foamed molded product can be obtained by filling the pre-foamed particles in a mold of a foam molding machine and heat-sealing the foamed particles while foaming the pre-foamed particles by heating again.
  • Water vapor can be suitably used as the heating medium.
  • the foamed molded product of the present invention has excellent impact resistance and heat dimensional stability.
  • the foam molded article is suitably used in applications that require excellent impact resistance and heat dimensional stability, such as parts packaging materials, automobile members, cushioning materials, or bumper core materials, particularly bumper core materials. be able to.
  • the gel permeation chromatography (GPC) apparatus used for the measurement is HLC-8121GPC / HT manufactured by Tosoh Corporation, TSKgel GMHhr-H (20) HT manufactured by Tosoh Corporation is used as the column, and the column temperature is set to 140 ° C. Set and use 1,2,4-trichlorobenzene as eluent.
  • the measurement sample is adjusted to a concentration of 1.0 mg / mL, and the amount injected into the GPC device is 0.3 mL.
  • the calibration curve for each molecular weight is calibrated using a polyethylene sample or polypropylene sample with a known molecular weight.
  • Mn and Mw are determined as polystyrene equivalent values.
  • dispersity (Mw / Mn) is measured using the obtained Mn and Mw.
  • the density of the resin is measured by a density gradient tube method in accordance with JIS K6922-1: 1998.
  • MFR Polyethylene resin melt flow rate
  • Vicat softening point of polyolefin resin Vicat softening temperature
  • the temperature of the suspension containing the polyethylene resin particles is adjusted to 60 ° C., and the styrene monomer is added in a fixed amount over 30 minutes, and then stirred for 1 hour so that the first styrene is contained in the polyethylene resin particles.
  • the monomer was impregnated.
  • the temperature of the reaction system was raised to 135 ° C. and held for 3 hours, and the styrene monomer was polymerized (first polymerization) in the polyethylene resin particles.
  • the obtained expandable composite resin particles were immediately supplied to a pre-foaming machine (product name “PSX40” manufactured by Kasahara Kogyo Co., Ltd.) and pre-foamed using steam at a pressure of 0.05 MPa to obtain a bulk density of 0.033 g / cm. Three pre-expanded particles were obtained.
  • a pre-foaming machine product name “PSX40” manufactured by Kasahara Kogyo Co., Ltd.
  • the pre-expanded particles were allowed to stand at room temperature for 1 day and then filled into a mold of a molding machine. Then, steam having a pressure of 0.18 MPa is supplied into the mold for 30 seconds to foam-mold the pre-expanded particles, and a bumper having a rectangular parallelepiped shape of 400 mm long ⁇ 300 mm wide ⁇ 30 mm high and having a density of 0.033 g / cm 3 . A core material was manufactured. Both the fusion rate and appearance of the obtained bumper core material were good.
  • the temperature of the suspension containing the polyethylene resin particles is adjusted to 60 ° C., and the styrene monomer is added in a fixed amount over 30 minutes, and then stirred for 1 hour so that the first styrene is contained in the polyethylene resin particles.
  • the monomer was impregnated.
  • the temperature of the reaction system was raised to 135 ° C. and held for 3 hours, and the styrene monomer was polymerized (first polymerization) in the polyethylene resin particles.
  • the temperature of the reaction system was lowered to 125 ° C., and a second styrene monomer obtained by dissolving 100.8 g of dicumyl peroxide as a polymerization initiator in 22 kg of styrene monomer was 4.6 kg per hour.
  • the second styrene monomer was impregnated into the polyethylene resin particles to cause polymerization (second polymerization).
  • the mixture was held at 125 ° C. for 1 hour, then heated to 140 ° C. and held for 3 hours to complete the polymerization to obtain composite resin particles.
  • the obtained expandable composite resin particles were immediately supplied to a pre-foaming machine (manufactured by Kasahara Kogyo Co., Ltd., product name “PSX40”) and pre-foamed using steam at a pressure of 0.05 MPa to obtain a bulk density of 0.033 g / cm. Three pre-expanded particles were obtained.
  • the pre-expanded particles were allowed to stand at room temperature for 1 day and then filled into a mold of a molding machine. Then, steam having a pressure of 0.18 MPa is supplied into the mold for 30 seconds to foam-mold the pre-expanded particles, and a bumper having a rectangular parallelepiped shape of 400 mm long ⁇ 300 mm wide ⁇ 30 mm high and having a density of 0.033 g / cm 3 . A core material was manufactured. Both the fusion rate and appearance of the obtained bumper core material were good.
  • Example 3 Polyethylene resin (Ube) instead of polyethylene resin (manufactured by Prime Polymer, product name “SP4020”, density: 0.937 g / cm 3 , Vicat softening point: 117 ° C., melt flow rate: 1.8 g / 10 min)
  • Polyethylene resin manufactured by Prime Polymer, product name “SP4020”, density: 0.937 g / cm 3 , Vicat softening point: 117 ° C., melt flow rate: 1.8 g / 10 min
  • the others were the same as in Example 1.
  • Example 4 Polyethylene resin (Ube) instead of polyethylene resin (manufactured by Prime Polymer, product name “SP4020”, density: 0.937 g / cm 3 , Vicat softening point: 117 ° C., melt flow rate: 1.8 g / 10 min) (Made by Maruzen Polyethylene Co., Ltd., product name “4040FC”, density: 0.938 g / cm 3 , Vicat softening point: 120 ° C., melt flow rate: 3.5 g / 10 min) The others were the same as in Example 1.
  • the temperature of the suspension containing the polyethylene resin particles is adjusted to 60 ° C., and the styrene monomer is added in a fixed amount over 30 minutes, and then stirred for 1 hour so that the first styrene is contained in the polyethylene resin particles.
  • the monomer was impregnated.
  • the temperature of the reaction system was raised to 135 ° C. and held for 3 hours, and the styrene monomer was polymerized (first polymerization) in the polyethylene resin particles.
  • the temperature of the reaction system was lowered to 115 ° C., and a second styrene monomer obtained by dissolving 33.6 g of t-butyl peroxybenzoate as a polymerization initiator in 16 kg of styrene monomer was 4 per hour.
  • polymerization second polymerization
  • the mixture was held at 115 ° C. for 1 hour, then heated to 140 ° C. and held for 3 hours to complete the polymerization, thereby obtaining composite resin particles.
  • the obtained expandable composite resin particles were immediately supplied to a pre-foaming machine (product name “PSX40” manufactured by Kasahara Kogyo Co., Ltd.) and pre-foamed using steam at a pressure of 0.05 MPa to obtain a bulk density of 0.033 g / cm. Three pre-expanded particles were obtained.
  • a pre-foaming machine product name “PSX40” manufactured by Kasahara Kogyo Co., Ltd.
  • the pre-expanded particles were allowed to stand at room temperature for 1 day and then filled into a mold of a molding machine. Then, steam with a pressure of 0.18 MPa is supplied into the mold for 30 seconds to foam-mold the pre-expanded particles, and a bumper having a rectangular parallelepiped shape with a length of 400 mm ⁇ width of 300 mm ⁇ height of 30 mm and a density of 0.033 g / cm 3 . A core material was manufactured. Both the fusion rate and appearance of the obtained bumper core material were good.
  • the temperature of the suspension containing the polyethylene resin particles is adjusted to 60 ° C., and the styrene monomer is added in a fixed amount over 30 minutes, and then stirred for 1 hour so that the first styrene is contained in the polyethylene resin particles.
  • the monomer was impregnated.
  • the temperature of the reaction system was raised to 135 ° C. and held for 3 hours, and the styrene monomer was polymerized (first polymerization) in the polyethylene resin particles.
  • the obtained expandable composite resin particles were immediately supplied to a pre-foaming machine (product name “PSX40” manufactured by Kasahara Kogyo Co., Ltd.) and pre-foamed using steam at a pressure of 0.10 MPa to obtain a bulk density of 0.025 g / cm. Three pre-expanded particles were obtained.
  • a pre-foaming machine product name “PSX40” manufactured by Kasahara Kogyo Co., Ltd.
  • the pre-expanded particles were allowed to stand at room temperature for 1 day and then filled into a mold of a molding machine. Then, steam having a pressure of 0.23 MPa is supplied into the mold for 30 seconds to foam-mold the pre-expanded particles, and a bumper having a rectangular parallelepiped shape of length 400 mm ⁇ width 300 mm ⁇ height 30 mm and a density of 0.025 g / cm 3 . A core material was manufactured. Both the fusion rate and appearance of the obtained bumper core material were good.
  • a polypropylene resin product name “RFG4VA” manufactured by Nippon Polypro Co., Ltd. (melting point: 135 ° C., density: 0.900 g / cm 3 , melt flow rate: 6.0 g / 10 min, Vicat softening point: 115 ° C.) 100 parts by mass is supplied to an extruder, melted and kneaded, and granulated by an underwater cut method to form an oval (egg-like) shape.
  • Polypropylene resin particles polyolefin resin particles
  • the average weight of the polypropylene resin particles at this time was 0.8 mg.
  • the temperature of the suspension containing the polypropylene system is adjusted to 60 ° C., and the styrene monomer is added in a fixed amount over 30 minutes, and then stirred for 1 hour, so that the first styrene monomer is contained in the polypropylene resin particles.
  • the body was impregnated.
  • the temperature of the reaction system was raised to 140 ° C., the same as the melting point of the polypropylene resin, and maintained for 2 hours, and the styrene monomer was polymerized (first polymerization) in the polypropylene resin particles.
  • the temperature of the reaction system was lowered to 125 ° C., and a second styrene monomer in which 72 g of dicumyl peroxide was dissolved in 16 kg of styrene monomer as a polymerization initiator was continuously added at a rate of 4 kg per hour.
  • the second resin was polymerized (second polymerization) while impregnating the polypropylene resin particles with the second styrene monomer.
  • the mixture was held at 120 ° C. for 1 hour, then heated to 143 ° C. and held for 3 hours to complete the polymerization, thereby obtaining composite resin particles.
  • the obtained expandable composite resin particles were immediately supplied to a pre-foaming machine (manufactured by Kasahara Kogyo Co., Ltd., product name “PSX40”) and pre-foamed using steam at a pressure of 0.05 MPa to obtain a bulk density of 0.025 g / cm. Three pre-expanded particles were obtained.
  • the pre-expanded particles were allowed to stand at room temperature for 1 day and then filled into a mold of a molding machine. Then, steam with a pressure of 0.18 MPa is supplied into the mold for 30 seconds to foam-mold the pre-expanded particles, and a bumper having a rectangular parallelepiped shape of length 400 mm ⁇ width 300 mm ⁇ height 30 mm and a density of 0.025 g / cm 3 . A core material was manufactured. Both the fusion rate and appearance of the obtained bumper core material were good.
  • the temperature of the suspension containing the polypropylene system is adjusted to 60 ° C., and the styrene monomer is added in a fixed amount over 30 minutes, and then stirred for 1 hour, so that the first styrene monomer is contained in the polypropylene resin particles.
  • the body was impregnated.
  • the temperature of the reaction system was raised to 140 ° C., the same as the melting point of the polypropylene resin, and maintained for 2 hours, and the styrene monomer was polymerized (first polymerization) in the polypropylene resin particles.
  • the temperature of the reaction system was lowered to 120 ° C., and a second styrene monomer in which 72 g of dicumyl peroxide was dissolved in 16 kg of styrene monomer as a polymerization initiator was continuously added at a rate of 4 kg per hour.
  • the second resin was polymerized (second polymerization) while impregnating the polypropylene resin particles with the second styrene monomer.
  • the mixture was held at 120 ° C. for 1 hour, then heated to 143 ° C. and held for 3 hours to complete the polymerization, thereby obtaining composite resin particles.
  • the obtained expandable composite resin particles were immediately supplied to a pre-foaming machine (product name “PSX40” manufactured by Kasahara Kogyo Co., Ltd.) and pre-foamed using steam at a pressure of 0.1 MPa to obtain a bulk density of 0.033 g / cm. Three pre-expanded particles were obtained.
  • a pre-foaming machine product name “PSX40” manufactured by Kasahara Kogyo Co., Ltd.
  • the pre-expanded particles were allowed to stand at room temperature for 1 day and then filled into a mold of a molding machine. Then, steam with a pressure of 0.25 MPa was supplied into the mold for 30 seconds to foam-mold the pre-expanded particles, and a bumper having a rectangular parallelepiped shape with a length of 400 mm ⁇ width of 300 mm ⁇ height of 30 mm and a density of 0.033 g / cm 3 A core material was manufactured. Both the fusion rate and appearance of the obtained bumper core material were good.
  • the temperature of the suspension containing the polyethylene resin particles is adjusted to 60 ° C., and the styrene monomer is added in a fixed amount over 30 minutes, and then stirred for 1 hour so that the first styrene is contained in the polyethylene resin particles.
  • the monomer was impregnated.
  • the temperature of the reaction system was raised to 135 ° C. and held for 3 hours, and the styrene monomer was polymerized (first polymerization) in the polyethylene resin particles.
  • the obtained expandable composite resin particles were immediately supplied to a pre-foaming machine (manufactured by Kasahara Kogyo Co., Ltd., product name “PSX40”), pre-foamed using water vapor at a pressure of 0.03 MPa, and a bulk density of 0.025 g / cm. Three pre-expanded particles were obtained.
  • the pre-expanded particles were allowed to stand at room temperature for 1 day and then filled into a mold of a molding machine. Then, water vapor at a pressure of 0.10 MPa was supplied into the mold for 30 seconds to foam-mold the pre-expanded particles, and a bumper having a rectangular parallelepiped shape of length 400 mm ⁇ width 300 mm ⁇ height 30 mm and a density of 0.025 g / cm 3 . A core material was manufactured. Both the fusion rate and appearance of the obtained bumper core material were good.
  • the temperature of the suspension containing the polyethylene resin particles is adjusted to 60 ° C., and the styrene monomer is added in a fixed amount over 30 minutes, and then stirred for 1 hour so that the first styrene is contained in the polyethylene resin particles.
  • the monomer was impregnated.
  • the temperature of the reaction system was raised to 135 ° C. and held for 3 hours, and the styrene monomer was polymerized (first polymerization) in the polyethylene resin particles.
  • the obtained expandable composite resin particles were immediately supplied to a pre-foaming machine (manufactured by Kasahara Kogyo Co., Ltd., product name “PSX40”), pre-foamed using water vapor at a pressure of 0.03 MPa, and a bulk density of 0.025 g / cm. Three pre-expanded particles were obtained.
  • the pre-expanded particles were allowed to stand at room temperature for 1 day and then filled into a mold of a molding machine. Then, water vapor with a pressure of 0.10 MPa is supplied into the mold for 30 seconds to foam-mold the pre-expanded particles, and the density of the rectangular parallelepiped shape having a length of 400 mm ⁇ width of 300 mm ⁇ height of 30 mm is 0.025 g / cm 3. Bumper core material was manufactured. Both the fusion rate and appearance of the obtained bumper core material were good.
  • PE represents a polyethylene resin
  • PS represents a polystyrene resin
  • PP represents a polypropylene resin.
  • Table 1 shows that the foamed molded product of the present invention is excellent in impact resistance and heat dimensional stability. Therefore, the foamed molded article of the present invention can be suitably used as a component packing material, an automobile member, a cushioning material, or a bumper core material, particularly as a bumper core material.

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Abstract

Particules de résine composites qui comprennent, à titre de composants de résine, 100 parties en poids d'une résine polyoléfinique et 100 à 400 parties en poids d'une résine polystyrène, la résine polyoléfinique ayant un point de ramollissement Vicat de 110 à 125°C et un taux de dispersité de 1,5 à 4,8.
PCT/JP2013/059303 2012-03-30 2013-03-28 Particules de résine composites, particules de résine composites expansibles, particules pré-expansées, mousse moulée, et matériau de cœur pour pare-chocs WO2013147040A1 (fr)

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DE112013001815.2T DE112013001815T5 (de) 2012-03-30 2013-03-28 Verbundharzpartikel, schäumbare Verbundharzpartikel, vorgeschäumte Partikel, Formschaumteile und Kernmaterial für Stoßstangen

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