WO2017056743A1 - Particules de résine à base de polyoléfine, modifiées au styrène, procédé pour leur production, particules expansibles, particules expansées et corps moulé en mousse - Google Patents

Particules de résine à base de polyoléfine, modifiées au styrène, procédé pour leur production, particules expansibles, particules expansées et corps moulé en mousse Download PDF

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Publication number
WO2017056743A1
WO2017056743A1 PCT/JP2016/073453 JP2016073453W WO2017056743A1 WO 2017056743 A1 WO2017056743 A1 WO 2017056743A1 JP 2016073453 W JP2016073453 W JP 2016073453W WO 2017056743 A1 WO2017056743 A1 WO 2017056743A1
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styrene
particles
mass
resin
polyolefin resin
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PCT/JP2016/073453
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English (en)
Japanese (ja)
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皓樹 大脇
宏佳 田中
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積水化成品工業株式会社
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Priority claimed from JP2016061859A external-priority patent/JP2017066359A/ja
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Publication of WO2017056743A1 publication Critical patent/WO2017056743A1/fr

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    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/18—Suspension polymerisation
    • 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
    • C08J9/16—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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions 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; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/16—Homopolymers or copolymers of alkyl-substituted styrenes

Definitions

  • the present invention relates to a styrene-modified polyolefin-based resin particle and a method for producing the same, and expandable particles, expanded particles, and a foamed molded product obtained thereby. More specifically, the present invention relates to a styrene-modified polyolefin resin particle capable of providing a foamed molded article having both good moldability and excellent heat resistance, and a method for producing the same, and expandable particles obtained thereby, foaming The present invention relates to particles and a foamed molded product.
  • Foamed molded bodies made of polystyrene resin are widely used as packaging materials and heat insulating materials because they have excellent buffering properties and heat insulating properties and are easy to mold.
  • the impact resistance and flexibility are insufficient, cracks and chips are likely to occur, and it is not suitable, for example, for packaging precision instrument products.
  • a foam-molded article made of polyolefin resin is excellent in impact resistance and flexibility, but requires a large facility for molding. Also, due to the nature of the resin, it must be transported from the raw material manufacturer to the molding processing manufacturer in the form of pre-expanded particles. Therefore, bulky pre-expanded particles are transported, and there is a problem that the manufacturing cost increases.
  • modified polyolefin resin particles also referred to as “modified polyolefin resin particles” and “modified resin particles” having the characteristics of the above two different resins and foam molded articles using them are disclosed. Proposed.
  • Patent Document 1 Japanese Patent No. 5732299 (Patent Document 1) includes 100 parts by mass of a polyethylene resin and 200 to 900 parts by mass of a polystyrene resin as resin components, and 0.900 to 0.916 g of polyethylene resin.
  • Modified resin particles having a density of / cm 3 , a melt flow rate of 1.0 to 5.0 g / 10 min measured at 190 ° C. under a load of 2.16 kg and a Vicat softening temperature of 88 to 95 ° C.
  • the modified resin particles are configured such that when the expandable particles obtained from the modified resin particles are allowed to stand for 300 seconds at 90 to 100 ° C., the modified resin particles are disclosed. Has been.
  • Patent Document 2 a styrene-based resin having a mass exceeding 300 parts by mass and not more than 1,000 parts by mass with respect to 100 parts by mass of a non-crosslinked linear low-density polyethylene resin component.
  • the base resin contains 3.2 to 40% by mass of a gel component composed of a graft polymer of a low-density polyethylene resin component and a polystyrene resin component, including a base resin containing components and a volatile foaming agent.
  • Procedure for passing through a 35-mesh wire mesh, procedure for measuring the dry powder mass of the polymer powder that has passed through the wire mesh, and the dry resin mass of resin particles that have not passed through the wire mesh, and the powder relative to the dry resin mass Styrene-modified linear low-density polyethylene-based expandable particles is a value obtained by following the procedure of calculating the weight percent of dry weight are disclosed.
  • Patent Document 3 discloses a thermoplastic resin foam molded article in which polyolefin resin foam particles (B) are dispersed in a foam (A) made of polystyrene resin, and further polystyrene.
  • the polystyrene resin constituting the foamed resin (A) is a copolymer having a monomer composition of 0 to 70% by mass of styrene, 10 to 80% by mass of ⁇ -methylstyrene, and 5 to 50% by mass of acrylonitrile.
  • a certain thermoplastic resin foam molded article is disclosed.
  • modified polyolefin resin particles and foamed molded products that can satisfy all the conditions have not been obtained.
  • improvement of heat resistance of modified polyolefin resin particles and foamed molded articles has been a conventional problem.
  • high heat resistance of polyolefin resin, adjustment of air bubbles, adjustment of molding conditions, change of polyolefin / polystyrene ratio, etc. Measures have been tried. Although these methods were certainly effective in improving the heat resistance, there were disadvantages such as a decrease in molding processability.
  • the present invention provides a styrene-modified polyolefin resin particle capable of providing a foamed molded article having both good moldability and excellent heat resistance, and a method for producing the same, and the foamable particles, foamed particles and It is an object to provide a foam molded article.
  • the inventors of the present invention pay attention to the modifying component among the modified polyolefin-based modified resin particles, and have a melting point of 124 ° C. to 145 ° C.
  • a polystyrene resin and using a polystyrene resin containing a resin component derived from 10 to 35% by mass of ⁇ -methylstyrene, and including 100 to 300 parts by mass of the polystyrene resin with respect to 100 parts by mass of the polyolefin resin The present inventors have found that a foamed molded article having excellent heat resistance can be obtained without greatly deteriorating moldability and capable of drastically improving moldability, thereby completing the present invention.
  • the polystyrene resin is 100 to 300 parts by mass with respect to 100 parts by mass of the polyolefin resin,
  • the polyolefin resin includes a resin having a melting point of 124 to 145 ° C .; Styrene-modified polyolefin resin particles are provided in which the polystyrene resin contains 10 to 35% by mass of a resin component derived from ⁇ -methylstyrene.
  • grains containing said styrene modified polyolefin resin particle and a foaming agent are provided. Furthermore, according to the present invention, there are provided expanded particles obtained by pre-expanding the expandable particles. Furthermore, according to this invention, the foaming molding obtained by carrying out the foaming molding of said foaming particle is provided. Moreover, according to this invention, the motor vehicle exterior material comprised by said foaming molding is provided.
  • a method for producing the above styrene-modified polyolefin resin particles (A) Dispersing seed particles composed of a polyolefin resin in an aqueous medium containing a dispersant, absorbing the styrene monomer in the seed particles, and then heating to polymerize the styrene monomer.
  • a styrene-modified polyolefin resin particle capable of providing a foamed molded article having both good moldability and excellent heat resistance, a method for producing the same, and the foamable particles, foamed particles and A foamed molded article can be provided.
  • Styrene modified polyolefin resin particles of the present invention (1)
  • the styrene-modified polyolefin resin particles have a polystyrene-equivalent weight average molecular weight Mw of 50,000 to 250,000, (2)
  • the styrene-modified polyolefin resin particles contain 1.5 to 5.0% by mass of carbon black.
  • Carbon black is contained in an amount of 3.0 to 10.0 parts by mass with respect to 100 parts by mass of polyolefin resin, and (4) Copolymerized with a styrene monomer with respect to 100 parts by mass of polystyrene resin.
  • the above excellent effect is further exhibited when at least one condition of containing 0.01 to 0.1 parts by mass of a resin component derived from a possible aromatic polyfunctional vinyl monomer is satisfied.
  • the step (B) after introducing a styrene monomer containing a monomer of a resin component derived from ⁇ -methylstyrene, impregnation / polymerization is performed.
  • the above excellent effect is further exhibited when a styrene monomer occupying 5 to 80% by mass of the total monomers to be provided is added.
  • the styrene-modified polyolefin resin particles of the present invention include a polyolefin resin and a polystyrene resin,
  • the polystyrene resin is 100 to 300 parts by mass with respect to 100 parts by mass of the polyolefin resin, the polyolefin resin has a melting point of 124 to 145 ° C., and the polystyrene resin is 10 to 35% by mass. It contains a resin component derived from ⁇ -methylstyrene.
  • Comparative Example 2 of Patent Document 1 includes a linear low density polyethylene resin (LLDPE, manufactured by Nihon Unicar Company, product name: FMRN-063, melting point 124 ° C., melt flow rate 1.3 g / 10 min, density Composite resin particles using 0.914 g / cm 3 (Vicat softening temperature 97 ° C.) are described.
  • LLDPE linear low density polyethylene resin
  • FMRN-063 melting point 124 ° C.
  • melt flow rate 1.3 g / 10 min
  • density Composite resin particles using 0.914 g / cm 3 Vicat softening temperature 97 ° C.
  • the styrene monomer occupies 90 parts by mass or more with respect to 100 parts by mass of all monomers, and ⁇ -methylstyrene may be included as another monomer. Is described.
  • the present invention is different from Patent Document 1 in that it contains 10 to 35% by mass of a resin component derived from ⁇ -methylstyrene among polystyrene resins.
  • a resin component derived from ⁇ -methylstyrene among polystyrene resins In Example 15 of the above-mentioned Patent Document 2, styrene monomer (358 parts by mass with respect to 100 parts by mass of polyethylene) and ⁇ -methylstyrene (100 parts by mass of polyethylene) were obtained using seed particles of polyethylene resin having a melting point of 126 ° C. It is described that a foamed molded article was obtained through a process of adding 2 parts by mass) to the part.
  • the amount of ⁇ -methylstyrene added is different as described above.
  • Patent Documents 1 and 2 describe that ⁇ -methylstyrene is used as a vinyl monomer (a monomer for polystyrene resin) in a styrene-modified polyolefin resin.
  • the inventor of the present invention increases the amount of low molecular weight components even when 10 to 35% by mass of ⁇ -methylstyrene of the polystyrene resin monomer is added by the methods described in Patent Documents 1 and 2. It has been confirmed by tests that sufficient heat resistance cannot be improved due to increase in residual monomers.
  • foam molding is possible and excellent heat resistance by a production method as described later (a combination of two kinds of initiators or multistage polymerization in which a monomer of a styrene resin is divided and added).
  • a foamed molded article of modified resin particles is obtained.
  • Patent Document 3 described above describes a foamed molded article in which foamed particles of a copolymer of styrene and ⁇ -methylstyrene and polyolefin resin foamed particles are mixed and molded integrally.
  • the present invention is different in that a polyolefin resin, a styrene resin and a resin component derived from ⁇ -methylstyrene are combined at the time of polymerization, and there are structural differences as follows.
  • a copolymer of styrene and ⁇ -methylstyrene is finely dispersed in a polyolefin resin component with a particle size of about 50 to 1000 nm, and the surface of the resin particle contains a large amount of polyolefin.
  • the foamed molded product described in Patent Document 3 has a structure in which styrene, ⁇ -methylstyrene foamed particles and polyolefin foamed particles are compounded at the time of molding. The top is very different.
  • the polyolefin resin used in the present invention includes a polyolefin resin having a melting point of 124 to 145 ° C.
  • the melting point is measured by analysis with a differential scanning calorimeter (DSC), and the details thereof will be described in Examples.
  • DSC differential scanning calorimeter
  • the melting point of the polyolefin resin is within the above range, styrene-modified polyolefin resin particles capable of providing a foamed molded article having both good moldability and excellent heat resistance can be obtained.
  • the melting point of the polyolefin resin is lower than 124 ° C., the heat resistance of the foamed molded product may be insufficient.
  • the melting point of the polyolefin-based resin exceeds 145 ° C.
  • the melting point of the polyolefin resin is, for example, 124 ° C, 125 ° C, 126 ° C, 127 ° C, 128 ° C, 129 ° C, 130 ° C, 131 ° C, 132 ° C, 133 ° C, 134 ° C, 135 ° C, 135 ° C, 136 ° C, 137 ° C.
  • a preferable melting point of the polyolefin resin is 130 to 145 ° C.
  • the polyolefin-based resin is not particularly limited as long as it has the above melting point, and includes a resin obtained by a known polymerization method, which may be cross-linked.
  • a resin obtained by a known polymerization method which may be cross-linked.
  • branched low density polyethylene linear low density polyethylene, medium density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer, these polymers
  • polypropylene resins such as polypropylene resins such as polypropylene, ethylene-propylene random copolymer, propylene-1-butene copolymer, and ethylene-propylene-butene random copolymer.
  • polystyrene resin preferably contains a component selected from polypropylene resin and polyethylene resin from the viewpoint of chemical resistance and molding processability.
  • the polystyrene-based resin is included as a modified resin component of the polyolefin-based resin, and includes 10 to 35% by mass of a resin component derived from ⁇ -methylstyrene. Therefore, 65 to 90% by mass of the polystyrene resin is a styrene resin component other than ⁇ -methylstyrene.
  • the polystyrene resin is not particularly limited as long as it is a resin mainly composed of a styrene monomer used in the technical field, and examples thereof include a styrene or a styrene derivative alone or a copolymer.
  • styrene derivative examples include vinyl toluene, chlorostyrene, ethyl styrene, isopropyl styrene, dimethyl styrene, bromostyrene, and the like. These may be used alone or in combination.
  • a polystyrene resin is preferable from the viewpoint of molding processability such as foamability and mechanical properties such as strength of a molded product.
  • the resin component derived from ⁇ -methylstyrene is less than 10% by mass, it may not be expected to improve the heat resistance of the obtained foamed molded article.
  • the resin component derived from ⁇ -methylstyrene exceeds 35% by mass, the polymerization efficiency may be extremely deteriorated in the production process, the amount of low molecular weight components may increase, and foamability may be greatly reduced. A large amount of styrene-derived monomers remain, which may cause odor and may reduce heat resistance due to the plasticizing effect of the remaining monomers.
  • the content (% by mass) of the resin component derived from ⁇ -methylstyrene is, for example, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25. 26, 27, 28, 29, 30, 31, 32, 33, 34, 35.
  • the content of the resin component derived from ⁇ -methylstyrene is preferably 10 to 25%.
  • the polystyrene resin is 100 to 300 parts by mass with respect to 100 parts by mass of the polyolefin resin. If the polystyrene resin is less than 100 parts by mass with respect to 100 parts by mass of the polyolefin resin, the modification effect by the polystyrene resin may not be obtained. On the other hand, when the polystyrene-based resin exceeds 300 parts by mass with respect to 100 parts by mass of the polyolefin-based resin, the amount of residual monomer in the modified resin particles increases, resulting in a decrease in heat resistance due to the plastic effect and generation of odor. It may cause.
  • Content (mass part) with respect to 100 mass parts of polyolefin resin of a polystyrene-type resin is 100,110,120,130,140,150,160,170,180,190,200,210,220,230,240, for example. 250, 260, 270, 280, 290, 300.
  • the content of polystyrene resin with respect to 100 parts by mass of polyolefin resin is preferably 120 to 220 parts by mass.
  • the resin component derived from the aromatic polyfunctional vinyl monomer copolymerizable with the styrene monomer is 0.01 to 0.000 per 100 parts by mass of the polystyrene resin. 1 part by mass is preferably contained, and divinylbenzene is particularly preferred from the viewpoint of reactivity with the styrene resin.
  • divinylbenzene include o-divinylbenzene, m-divinylbenzene, p-divinylbenzene, and the like. These may be used alone or in combination.
  • the resin component derived from the aromatic polyfunctional vinyl monomer has an effect of improving the mass average molecular weight of the modified resin particles, and its content is 0.01 parts by mass with respect to 100 parts by mass of the polystyrene resin. If it is less than 1, the effect may not be expected. On the other hand, when the content exceeds 0.1 parts by mass with respect to 100 parts by mass of the polystyrene-based resin, the molecular weight and the degree of crosslinking may become too high, and foamability may be reduced.
  • the content (parts by mass) of the resin component derived from the aromatic polyfunctional vinyl monomer to 100 parts by mass of the polystyrene resin is, for example, 0.01, 0.02, 0.03, 0.04, 0. .05, 0.06, 0.07, 0.08, 0.09, 0.1. More preferably, the content of the resin component derived from the aromatic polyfunctional vinyl monomer to the polystyrene resin is 0.02 to 0.05 parts by mass.
  • the modified resin particles of the present invention preferably have a polystyrene-reduced weight average molecular weight Mw of 50,000 to 250,000.
  • the weight average molecular weight Mw in terms of polystyrene of the modified resin particles is in the above range, in addition to improving the heat resistance of the obtained foamed molded article, excellent foamability can be expected.
  • the weight average molecular weight Mw in terms of polystyrene of the modified resin particles is less than 80,000, the foamable particles obtained do not have melt tension suitable for foaming, and in addition to the decrease in heat resistance of the foamed molded product obtained, foamability May also decrease.
  • the weight average molecular weight Mw in terms of polystyrene of the modified resin particles exceeds 200,000, the foamability of the foamable particles obtained may be lowered.
  • the polystyrene-reduced weight average molecular weight Mw ( ⁇ 10 3 ) of the modified resin particles is, for example, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190. , 200, 210, 220, 230, 240, 250. More preferable modified resin particles have a polystyrene-equivalent mass average molecular weight Mw of 100,000 to 200,000.
  • the method for producing the modified resin particles of the present invention includes: (A) Dispersing seed particles composed of a polyolefin resin in an aqueous medium containing a dispersant, absorbing the styrene monomer in the seed particles, and then heating to polymerize the styrene monomer. 1 polymerization step; (B) Then, a second polymerization step of polymerizing the styrene monomer while absorbing the styrene monomer is included, or the steps (A) and (B) are (C) then the step The method further includes the step of repeating (B).
  • the above method is a seed polymerization method.
  • the modified resin particles can be obtained by allowing the seed particles to absorb the monomer and polymerizing the monomer after or while absorbing the monomer.
  • the foamed particles can be obtained by impregnating the modified resin particles with a foaming agent after polymerization or while polymerizing.
  • the polymerization step of impregnating and polymerizing the styrene resin monomer into the seed particles made of polyolefin resin is repeated at least twice.
  • the shape of the modified resin particles can be made spherical, and the polymerization of the monomer of the styrene resin impregnated in the seed particles made of polyolefin resin proceeds. easy. The amount of monomer and resin is almost the same.
  • Step (A): First polymerization step Disperse seed particles comprising a polyolefin resin in an aqueous medium containing a dispersant, and absorb the styrene resin monomer in the seed particles, and then raise the temperature to polymerize the styrene resin monomer. .
  • the first polymerization step it is preferable to use a styrene resin monomer containing a monomer of a resin component derived from ⁇ -methylstyrene.
  • the seed particles can be obtained, for example, by melt-kneading the polyolefin-based resin with an extruder, extruding it into a strand shape, and cutting it with a desired particle diameter.
  • a die for obtaining seed particles of a predetermined size has a resin discharge hole diameter of preferably 0.2 to 1.0 mm, and the land length of the resin flow path is to maintain high dispersibility of the polystyrene resin.
  • the resin temperature at the die inlet of the resin extruded from the extruder is adjusted to 200 to 270 ° C. so that the pressure at the die resin flow path inlet can be maintained at 10 to 20 MPa. Is preferred.
  • Desired seed particles can be obtained by combining an extruder and a die having the screw structure, extrusion conditions, and underwater cutting conditions.
  • the seed particles may contain additives such as a polyolefin resin compatibilizing agent, a bubble adjusting agent, and an antistatic agent as long as the effects of the present invention are not impaired.
  • the particle diameter of the seed particles can be appropriately adjusted according to the average particle diameter of the modified resin particles, and the preferable particle diameter is in the range of 0.4 to 1.5 mm, more preferably 0.4 to 1.0 mm.
  • the average mass is 30 to 90 mg / 100 grains.
  • examples of the shape include a true spherical shape, an elliptical spherical shape (egg shape), a cylindrical shape, and a prismatic shape.
  • aqueous medium examples include water and a mixed medium of water and a water-soluble solvent (for example, a lower alcohol such as methyl alcohol or ethyl alcohol).
  • a water-soluble solvent for example, a lower alcohol such as methyl alcohol or ethyl alcohol.
  • a dispersant may be used to stabilize the dispersibility of the styrene monomer droplets and seed particles.
  • a dispersant include organic dispersants such as partially saponified polyvinyl alcohol, polyacrylate, polyvinyl pyrrolidone, carboxymethyl cellulose, and methyl cellulose; magnesium pyrophosphate, calcium pyrophosphate, calcium phosphate, calcium carbonate, magnesium phosphate, Examples thereof include inorganic dispersants such as magnesium carbonate and magnesium oxide. Among these, an inorganic dispersant is preferable because a more stable dispersion state may be maintained. When an inorganic dispersant is used, it is preferable to use a surfactant in combination. Examples of such surfactants include sodium dodecylbenzene sulfonate and sodium ⁇ -olefin sulfonate.
  • Styrene monomers are usually polymerized in the presence of a polymerization initiator.
  • the polymerization initiator is usually impregnated into the seed particles simultaneously with the styrene monomer.
  • the polymerization initiator is not particularly limited as long as it is conventionally used for the polymerization of styrene monomers.
  • These polymerization initiators may be used alone or in combination of two or more.
  • the polymerization initiator is suspended or emulsified and dispersed in advance in the aqueous medium when the polymerization initiator is added to the aqueous medium. It is preferable to add to the dispersion liquid above, or to add the polymerization initiator to the aqueous medium after previously dissolving it in the styrene monomer.
  • the amount of the polymerization initiator used is less than 0.1 parts by mass, the molecular weight becomes too high and foamability may be lowered.
  • the amount of the polymerization initiator used exceeds 0.9 parts by mass, the polymerization rate may become too high, and the dispersion state of the polystyrene resin particles in the polyolefin resin may not be controlled.
  • a preferred amount of the polymerization initiator is 0.2 to 0.5 parts by mass.
  • Polymerization of the styrene resin monomer can be carried out, for example, by heating at 60 to 150 ° C. for 2 to 40 hours. In the polymerization step, it is preferable to hold at a polymerization temperature or higher than the polymerization temperature for a long time, that is, to anneal. In the previous steps up to the annealing step, the styrene monomer and polymerization initiator absorbed in the seed particles have not completely completed the reaction, and there are not a few unreacted substances inside the modified resin particles. Existing.
  • the modified resin particles have a colorant, a flame retardant, a flame retardant aid, a plasticizer, a binding inhibitor, a cell regulator, a cross-linking agent, a filler, a lubricant, and a fusion promoter within the range that does not impair the physical properties.
  • An agent, an antistatic agent, a spreading agent and the like may be added.
  • Examples of the colorant include furnace black, ketjen black, channel black, thermal black, acetylene black, graphite, carbon fiber, and other carbon black, and may be a masterbatch blended in a resin.
  • the content of carbon black in the modified resin particles is preferably 1.5 to 5.0% by mass.
  • the carbon black content (mass%) is, for example, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2 4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.5, 4.0, 4.5, 5.0.
  • the carbon black is preferably contained in an amount of 3.0 to 10.0 parts by mass with respect to 100 parts by mass of the polyolefin resin.
  • Carbon black (mass part) with respect to 100 parts by mass of polyolefin resin is, for example, 3.0, 3.5, 4.0, 4.5, 5.0, 5.1, 5.2, 5.3, 5 .4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0 , 9.5, 10.0.
  • a coloring effect can be obtained without inhibiting the effects of the present invention.
  • a master batch previously mixed with a resin may be used, and the resin is a polyolefin resin that is compatible with the main resin of the seed particles without impairing the physical properties of the modified resin particles. Is preferred.
  • Flame retardants include tri (2,3-dibromopropyl) isocyanate, bis [3,5-dibromo-4- (2,3-dibromopropoxy) phenyl] sulfone, tetrabromocyclooctane, hexabromocyclododecane, trisdibromo Examples thereof include propyl phosphate, tetrabromobisphenol A, tetrabromobisphenol A-bis (2,3-dibromo-2-methylpropyl ether), tetrabromobisphenol A-bis (2,3-dibromopropyl ether), and the like.
  • flame retardant aids include organic peroxides such as 2,3-dimethyl-2,3-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane, dicumyl peroxide, cumene hydroperoxide, and the like. It is done.
  • the content of the flame retardant and the flame retardant auxiliary in the modified resin particles is preferably 1.0 to 5.0% by mass and 0.1 to 2.0% by mass, respectively.
  • plasticizer examples include glycerin fatty acid esters such as phthalic acid ester, glycerin diacetomonolaurate, glycerin tristearate and glycerin diacetomonostearate, adipic acid esters such as diisobutyl adipate, and plasticizers such as coconut oil. .
  • the plasticizer content of the modified resin particles is preferably 0.1 to 3.0% by mass.
  • binding inhibitor examples include calcium carbonate, silica, zinc stearate, aluminum hydroxide, ethylene bis stearamide, tricalcium phosphate, dimethyl silicon and the like.
  • air conditioner examples include ethylene bis stearamide, polyethylene wax and the like.
  • crosslinking agent examples include 2,2-di-t-butylperoxybutane, 2,2-bis (t-butylperoxy) butane, dicumyl peroxide, 2,5-dimethyl-2,5-di-t. -Organic peroxides such as butylperoxyhexane.
  • the filler examples include synthetically or naturally produced silicon dioxide.
  • Examples of the lubricant include paraffin wax and zinc stearate.
  • Examples of the fusion accelerator include stearic acid, stearic acid triglyceride, hydroxystearic acid triglyceride, stearic acid sorbitan ester, and polyethylene wax.
  • Examples of the antistatic agent include polyoxyethylene alkylphenol ether, stearic acid monoglyceride, polyethylene glycol and the like.
  • Examples of the spreading agent include polybutene, polyethylene glycol, and silicone oil.
  • Step (B): Second polymerization step Next, the styrene monomer is polymerized while absorbing the styrene resin monomer.
  • the second polymerization step it is preferable to use together polymerization initiators having different 10-hour half-lives.
  • the 10-hour half-life temperature (R1 ° C) of the first polymerization initiator is in the range of (T-40) to (T-20), and the second polymerization
  • the 10 hour half-life temperature of the initiator is preferably in the range of (R1 + 5) to (R1 + 20).
  • a mixture of a monomer of a styrene resin and a monomer of a resin component derived from ⁇ -methylstyrene is added and then 5 of all monomers to be added (subjected to impregnation and polymerization). It is preferable to add a styrene-based resin monomer occupying -80% by mass, and particularly preferably 40-80% by mass.
  • the modified resin particles preferably have an average particle diameter of 0.8 to 2.5 mm. If the average particle diameter of the modified resin particles is less than 0.8 mm, high foamability may not be obtained. On the other hand, when the average particle diameter of the modified resin particles exceeds 2.5 mm, the filling property of the pre-expanded particles during the molding process may be insufficient.
  • the average particle diameter of the modified resin particles is more preferably 1.0 to 1.8 mm.
  • Expandable particles are obtained by impregnating the modified resin particles of the present invention with a foaming agent by a known method.
  • a foaming agent When the temperature at which the modified resin particles are impregnated with the foaming agent is low, it takes time to impregnate, and the production efficiency of the expandable particles may decrease. Therefore, it is preferably 50 to 130 ° C, more preferably 60 to 100 ° C.
  • the foaming agent is preferably a volatile foaming agent and is not particularly limited as long as it is conventionally used for foaming polystyrene resins.
  • carbon such as isobutane, n-butane, isopentane, n-pentane, neopentane, etc.
  • volatile foaming agents such as aliphatic hydrocarbons having a number of 5 or less, and butane-based foaming agents and pentane-based foaming agents are particularly preferable.
  • pentane can be expected to act as a plasticizer.
  • the content of the foaming agent in the expandable particles is usually in the range of 2 to 10% by mass, preferably in the range of 3 to 10% by mass, particularly preferably in the range of 3 to 8% by mass.
  • the content of the foaming agent is small, for example, less than 2% by mass, it may not be possible to obtain a low-density foam molded product from the foamable particles, and the effect of increasing the secondary foaming power during in-mold foam molding is obtained. Therefore, the appearance of the foamed molded product may deteriorate.
  • the content of the foaming agent is large, for example, it exceeds 10% by mass, the time required for the cooling step in the production process of the foamed molded article using the foamable particles becomes long and the productivity may decrease.
  • the foamable particles can contain a foaming aid together with the foaming agent.
  • the foaming aid is not particularly limited as long as it is conventionally used for foaming polystyrene resins.
  • aromatic organic compounds such as styrene, toluene, ethylbenzene, xylene, cyclohexane, methylcyclohexane, etc.
  • solvents having a boiling point of 200 ° C. or less under 1 atm such as cycloaliphatic hydrocarbons, ethyl acetate, and butyl acetate.
  • the content of the foaming aid in the foamable particles is usually in the range of 0.3 to 2.5% by mass, and preferably in the range of 0.5 to 2% by mass.
  • the content of the foaming aid is small, for example, less than 0.3% by mass, the plasticizing effect of the polystyrene resin may not be exhibited.
  • the content of the foaming aid is large and exceeds 2.5% by mass, the foamed molded product obtained by foaming the foamable particles may be shrunk or melted to deteriorate the appearance, or foamable.
  • the time required for the cooling step in the production process of the foamed molded article using the particles may be long.
  • the foamable particles of the present invention preferably have a foaming ratio of 30 times or more, more preferably 35 times or more after 1-minute foaming with a gauge pressure of 0.07 MPa steam.
  • the evaluation method will be described in Examples.
  • the expanded particles of the present invention are obtained by pre-expanding the expandable particles of the present invention and heating them with steam (steam) with a gauge pressure of 0.004 to 0.09 MPa introduced, for example, in a sealed container. It is obtained by pre-foaming to a predetermined bulk density. Examples of the method include batch-type foaming in which steam is introduced, continuous foaming, and release foaming under pressure, and when necessary, air may be introduced simultaneously with water vapor.
  • the expanded particles of the present invention preferably have a bulk density of 20 to 500 kg / m 3 .
  • the bulk density of the expanded particles is less than 20 kg / m 3 , the expanded molded product tends to shrink and the appearance may be impaired, and the mechanical strength may not be sufficient.
  • the bulk density of the foamed particles exceeds 500 kg / m 3 , the merit of weight reduction as a foamed molded product may be impaired.
  • a preferred bulk density of the expanded particles is 25 to 100 kg / m 3 . The measuring method will be described in Examples.
  • the expanded particles of the present invention preferably have an average particle size of 1.5 to 7.5 mm.
  • the average particle diameter of the expanded particles is less than 1.5 mm, the foamability at the time of foam molding is low, and the elongation of the surface of the molded article may be deteriorated.
  • the average particle diameter of the expanded particles exceeds 7.5 mm, the filling properties of the expanded particles at the time of molding may be insufficient.
  • a more preferable average particle diameter of the expanded particles is 2.5 to 5.0 mm.
  • Foam molded body of the present invention is obtained by foam-molding the foam particles of the present invention, for example, filling the foam particles into a mold (cavity) of a foam molding machine, and heating again to expand the foam particles. It is obtained by thermally fusing the foamed particles while foaming.
  • the pressure regulation during molding of the foamed molded article of the present invention is preferably 0.05 to 0.27 MPa in terms of gauge pressure. If the pressure during molding is less than 0.05 MPa in gauge pressure, the steam control during molding may vary and the quality of the molded product may not be stable. On the other hand, if the pressure adjustment at the time of molding exceeds 0.27 MPa in gauge pressure, the amount of steam used at the time of molding increases and productivity may deteriorate, or equipment that can withstand high pressure use may be required. A preferable pressure during molding is 0.15 to 0.25 MPa in terms of gauge pressure. The measuring method will be described in Examples.
  • the foamed molded article of the present invention preferably has a density of 20 to 500 kg / m 3 . If the density of the foamed molded product is less than 20 kg / m 3 , the impact resistance may not be sufficient. On the other hand, when the density of the foamed molded product exceeds 500 kg / m 3 , the effect of reducing the weight of the foamed molded product is limited.
  • the bulk density of the foamed molded product is preferably 20 to 100 kg / m 3 . The measuring method will be described in Examples.
  • the foamed molded article of the present invention preferably has a dimensional change rate of less than 3.5%. A more preferable dimensional change rate is less than 2.0%.
  • the measuring method will be described in Examples.
  • the foamed molded article of the present invention has chemical resistance such that the appearance does not change even after 24 hours exposure to oils such as engine oil and brake oil, and chemicals such as grease, washer fluid, gasoline, and light oil.
  • oils such as engine oil and brake oil
  • chemicals such as grease, washer fluid, gasoline, and light oil.
  • the foamed molded product of the present invention can be used for various applications.
  • Examples of the use include bumper core materials, automobile interior materials, automobile exterior materials, electronic parts, various industrial materials including glass, food cushioning materials and transport containers.
  • the foamed molded article of the present invention has high heat resistance, it is a part that is attached to a position close to the engine or the radiator, and is easily affected by the outside air temperature or the heat of the internal combustion engine, among the above applications. It can be suitably used for an automobile exterior material (bumper core material).
  • “automobile” means a vehicle that includes a prime mover, a steering device, and the like, and can travel on the ground by using them. Also includes vehicles connected to overhead lines such as trolley buses.
  • the melting point (° C.) is measured by the method described in JIS K7121: 1987 “Method for measuring the transition heat of plastic”. That is, using a differential scanning calorimeter device (Seiko Denshi Kogyo Co., Ltd., model: DSC 6220), 7 mg of the sample was filled in the measurement container, and the nitrogen gas flow rate was 30 mL / min. The temperature is raised, lowered, and raised repeatedly at a temperature raising / lowering rate of ° C./min, and the melting peak temperature of the DSC curve at the second temperature rise is defined as the melting point (° C.).
  • Mass average molecular weight (Mw) of the modified resin particles For the measurement, a gel permeation chromatography (GPC) apparatus (manufactured by Tosoh Corporation, model: HLC-8121GPC / HT) and a column (manufactured by Tosoh Corporation, model: TSKgel GMHhr-H (20) HT) are used. . As measurement conditions, the column temperature is set to 140 ° C., and 1,2,4-trichlorobenzene is used as the 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 with a known molecular weight, and the mass average molecular weight (Mw) is determined as a polystyrene equivalent value.
  • GPC gel permeation chromatography
  • ⁇ Foaming properties of expandable particles The mass a (g) of about 2 g of expandable particles is weighed with two significant figures after the decimal point. The weighed expandable particles are put in a container, and it is confirmed that the temperature in the foaming tank is 90 ° C. or less. The container in which the expandable particles are put in the foaming tank is put, and water vapor with a gauge pressure of 0.07 MPa (vapor temperature: 117 ) Is introduced to increase the temperature in the foaming tank to 110 to 117 ° C. by pressurizing the inside of the foaming tank. At this time, the heating time is set to 1 minute, and the expansion ratio of the expanded particles immediately after taking out from the expansion tank is measured.
  • vapor temperature: 117 vapor temperature
  • the heating time is from the time when the temperature in the foaming tank becomes 110 ° C. or higher.
  • the expansion ratio (times) is obtained by placing expanded particles in a graduated cylinder, measuring volume b (cm 3 ), and dividing the volume b by mass a. From the obtained expansion ratio, the expandability of the expandable particles is evaluated based on the following criteria. ⁇ (Good): Foaming factor of 35 times or more ⁇ (Slightly bad): Foaming factor of 30 times or more and less than 35 times ⁇ (Poor): Foaming factor of less than 30 times
  • the foamed particles are filled in a 400 mm ⁇ 300 mm ⁇ 30 mm mold of a foam molding machine, and the foamed particles are heat-fused while being heated with water vapor, and the foamed particles are heat-sealed to have a top surface of 400 mm long ⁇ 300 mm wide.
  • a rectangular parallelepiped foam molded body having a thickness of 30 mm is obtained.
  • the obtained foamed molded product is evaluated according to the following criteria based on the lowest vapor pressure with a fusion rate of 90% or more.
  • the lowest vapor pressure at which a 90% fusion rate is obtained is referred to as molding pressure adjustment.
  • the fusion rate is measured by the following procedure.
  • a cutting line having a length of 300 mm and a depth of about 5 mm is put along the horizontal direction with a cutter on the upper surface of a 30 mm-thick rectangular foam-shaped body having an upper surface of length 400 mm ⁇ width 300 mm.
  • the foamed molded product is divided into two.
  • ⁇ Heat dimensional change rate of foamed molded product The change in the heating dimension of the foamed molded product is measured in accordance with Method B described in JIS K 6767: 1999 “Foamed Plastics-Polyethylene Test Method”, and the foamed molded product is evaluated from the obtained results. Specifically, a test piece having a length of 150 mm, a width of 150 mm, and a height of 20 mm is cut out from the foamed molded body. Then, on the surface of the test piece, three straight lines with a length of 50 mm directed in the vertical direction are written in parallel with each other at intervals of 50 mm, and three straight lines with a length of 50 mm directed in the horizontal direction are parallel with each other.
  • the test piece was left in a hot air circulating dryer having a temperature of 95 ° C. for 168 hours and then taken out, and the test piece was taken under standard conditions (temperature 20 ⁇ 2 ° C., humidity 65 ⁇ 5%) for 1 hour. Leave it over.
  • the lengths of the six straight lines entered on the surface of the test piece are measured, and the arithmetic average value L1 of the lengths of the six straight lines is calculated.
  • the degree of change S is calculated based on the following formula, and the absolute value of the degree of change S is defined as the heating dimensional change rate (%).
  • S 100 ⁇ (L1-50) / 50
  • the heating dimensional change (mm) of a structure having a length of 2,000 mm was assumed.
  • the foamed molded product is evaluated based on the following criteria. ⁇ (excellent): small dimensional change rate (0 ⁇ S ⁇ 2.0), excellent dimensional stability ⁇ (good): small dimensional change rate (2.0 ⁇ S ⁇ 3.5), dimensional stability ⁇ (possible): Dimensional change rate is seen (3.5 ⁇ S ⁇ 4.0), but practical use is possible ⁇ (impossible): dimensional change rate is noticeable (4.0 ⁇ S) , Practical use is impossible
  • a flat rectangular plate-shaped test piece having a length of 100 mm, a width of 100 mm, and a thickness of 20 mm is cut out from the foamed molded article, and left for 24 hours under conditions of a temperature of 23 ° C. and a humidity of 50%.
  • a test piece is cut out from a foaming molding so that the upper surface whole surface of a test piece may be formed from the skin of a foaming molding.
  • 1 g of gasoline is uniformly applied to the upper surface of the test piece and left for 60 minutes under the conditions of a temperature of 23 ° C. and a humidity of 50%.
  • medical agent is wiped off from the upper surface of a test piece, the upper surface of a test piece is visually observed, and it judges based on the following reference
  • the chemical resistance of a foaming molding is determined based on the following reference
  • Example 1 (Preparation of seed particles) Polypropylene resin PP (melting point 140 ° C .; manufactured by Prime Polymer Co., Ltd., brand: Prime Polypro F-744NP) is supplied to an extruder (Toshiba Machine Co., Ltd., model: SE-65) and melt kneaded at 230 to 250 ° C. Then, it was granulated by an underwater cutting method and cut into an oval shape (egg) to obtain seed particles. The average mass of the seed particles was 0.6 mg.
  • styrene and ⁇ -methyl prepared by dissolving 0.6 g of dicumyl peroxide (10-hour half-life temperature 116.4 ° C.) as a polymerization initiator in advance in the obtained suspension were prepared.
  • a mixture of 85 g of styrene was added dropwise over 30 minutes. After completion of dropping, the seed particles were impregnated (absorbed) by holding for 30 minutes. After impregnation, the temperature was raised to 140 ° C. and maintained at this temperature for 2 hours to polymerize styrene in the seed particles (first polymerization).
  • the temperature was raised to 70 ° C., and stirring was continued at this temperature for 4 hours to obtain 2200 g of expandable particles. Then, it cooled to 30 degrees C or less, taken out the foamable particle from the autoclave, and made it dehydrated and dried.
  • styrene prepared by dissolving 0.6 g of dicumyl peroxide as a polymerization initiator in advance was added dropwise to the obtained suspension over 30 minutes. After completion of dropping, the seed particles were impregnated (absorbed) by holding for 30 minutes. After impregnation, the temperature was raised to 140 ° C. and maintained at this temperature for 2 hours to polymerize styrene in the seed particles (first polymerization).
  • Example 2 The blending amount of styrene and ⁇ -methylstyrene in (first polymerization) is 287.5 g and 57.5 g, respectively, and the blending amount of styrene and ⁇ -methylstyrene used in (second polymerization)
  • the foamed molded products were obtained in the same manner as in Example 1 except that the weight was 612.5 g and 122.5 g, respectively, and their physical properties including intermediate products were evaluated.
  • Example 3 Except for changing (first polymerization) and (second polymerization) as follows, foamed molded articles were obtained in the same manner as in Example 1, and their physical properties including intermediate products were evaluated.
  • First polymerization In a 5 liter autoclave with a stirrer (manufactured by Nitto High Pressure Co., Ltd.), 40 g of magnesium pyrophosphate as a dispersant and 0.6 g of sodium dodecylbenzenesulfonate as a surfactant are dispersed in 2,000 g of pure water and dispersed. A medium was obtained. In the resulting dispersion medium, 900 g of seed particles were dispersed at 30 ° C.
  • the temperature of the first polymerization reaction liquid was lowered to 125 ° C. (cooled), and a dispersion prepared by dispersing 3.0 g of sodium dodecylbenzenesulfonate as a surfactant in 20 g of pure water in advance was taken for 10 minutes. And dripped. Thereafter, 2.3 g of dicumyl peroxide as a polymerization initiator and 3.4 g of di-tert-butyl peroxide were prepared and dissolved in 437 g of styrene, 168 g of ⁇ -methylstyrene and 0.22 g of divinylbenzene. The mixture was added dropwise over 7 hours.
  • Example 4 (Second polymerization) In the same manner as in Example 3 except that divinylbenzene was not used, foamed molded articles were obtained, and their physical properties including intermediate products were evaluated.
  • Example 5 Except for changing (first polymerization) and (second polymerization) as follows, foamed molded articles were obtained in the same manner as in Example 1, and their physical properties including intermediate products were evaluated.
  • First polymerization In a 5 liter autoclave with a stirrer (manufactured by Nitto High Pressure Co., Ltd.), 40 g of magnesium pyrophosphate as a dispersant and 0.6 g of sodium dodecylbenzenesulfonate as a surfactant are dispersed in 2,000 g of pure water and dispersed. A medium was obtained. In the resulting dispersion medium, 600 g of seed particles were dispersed at 30 ° C.
  • the temperature of the first polymerization reaction liquid was lowered to 125 ° C. (cooled), and a dispersion prepared by dispersing 3.0 g of sodium dodecylbenzenesulfonate as a surfactant in 20 g of pure water in advance was taken for 10 minutes. And dripped. Thereafter, 3.0 g of dicumyl peroxide as a polymerization initiator and 4.0 g of di-tert-butyl peroxide were prepared and dissolved in 724 g of styrene, 278 g of ⁇ -methylstyrene and 0.28 g of divinylbenzene. The mixture was added dropwise over 9 hours.
  • polyolefin resin PE1 (melting point: 126 ° C .; manufactured by Ube Maruzen Polyethylene Co., Ltd., brand: Umerit 140HK) is used, and dropwise addition of a mixture of styrene and ⁇ -methylstyrene in (second polymerization) Carrying out at 115 ° C.
  • Example 4 In the same manner as in Example 1 except that polyolefin resin PE2 (melting point: 121 ° C .; brand name: Harmolex NF444A) is used in (preparation of seed particles), a foam molded article is obtained, and an intermediate product is obtained. Their physical properties were evaluated. In Examples 1 to 3, the amount of residual monomer in the modified resin particles was measured.
  • Example 7 A foamed molded article was obtained in the same manner as in Example 1 except that (preparation of seed particles) was performed as follows, and their physical properties including intermediate products were evaluated.
  • Polypropylene-based resin PP (melting point 140 ° C .; manufactured by Prime Polymer Co., Ltd., brand: Prime Polypro F-744NP) 100 parts by mass and 45% by mass-containing carbon black masterbatch (manufactured by Dainichi Seika Kogyo Co., Ltd.) PP-RM10H381) 12.5 parts by mass is supplied to an extruder (Toshiba Machine Co., Ltd., model: SE-65), melted and kneaded at 230 to 250 ° C., granulated by an underwater cutting method, and oval (egg) To obtain seed particles.
  • the average mass of the seed particles was 0.6 mg.
  • the content of carbon black in the seed particles was 5.0% by mass, which was about 5.3 parts by mass when converted as the amount of carbo black with respect to
  • Example 8 A foamed molded article was obtained in the same manner as in Example 3 except that (preparation of seed particles) was made in the same manner as in Example 7, and their physical properties including intermediate products were evaluated.
  • the content of carbon black in the seed particles was 5.0% by mass, which was about 5.3 parts by mass when converted as the amount of carbo black with respect to 100 parts by mass of the resin component of the seed particles.
  • Example 9 Except for changing (preparation of seed particles), (first polymerization) and (second polymerization) as follows, in the same manner as in Example 1, foamed molded articles were obtained, including intermediate products. The physical properties of were evaluated.
  • styrene and ⁇ -methyl prepared by dissolving 0.6 g of dicumyl peroxide (10-hour half-life temperature 116.4 ° C.) as a polymerization initiator in advance in the obtained suspension were prepared.
  • a mixture of 85 g of styrene was added dropwise over 30 minutes. After completion of dropping, the seed particles were impregnated (absorbed) by holding for 30 minutes. After impregnation, the temperature was raised to 140 ° C. and maintained at this temperature for 2 hours to polymerize styrene in the seed particles (first polymerization).
  • Example 10 Except that the (first polymerization) and (second polymerization) were changed as follows, foamed molded articles were obtained in the same manner as in Example 9, and their physical properties including intermediate products were evaluated.
  • First polymerization In a 5 liter autoclave with a stirrer (manufactured by Nitto High Pressure Co., Ltd.), 40 g of magnesium pyrophosphate as a dispersant and 0.6 g of sodium dodecylbenzenesulfonate as a surfactant are dispersed in 2,000 kg of pure water and dispersed. A medium was obtained. In the resulting dispersion medium, 900 g of seed particles were dispersed at 30 ° C.
  • the temperature of the first polymerization reaction liquid was lowered to 125 ° C. (cooled), and a dispersion prepared by dispersing 3.0 g of sodium dodecylbenzenesulfonate as a surfactant in 20 g of pure water in advance was taken for 10 minutes. And dripped. Thereafter, 2 g of a mixture of 55 g of ⁇ -methylstyrene and 0.22 g of divinylbenzene prepared in advance by dissolving 0.7 g of dicumyl peroxide as a polymerization initiator and 1.2 g of di-tert-butyl peroxide were prepared. It was dripped over time.
  • styrene prepared by dissolving 3.0 g of dicumyl peroxide as a polymerization initiator in advance was added dropwise over 4 hours while maintaining the temperature at 125 ° C. Thereafter, the seed particles were impregnated and polymerized by holding for 1 hour. After the polymerization, the temperature was raised to 140 ° C. and held at this temperature for 3 hours to obtain 2,000 g of modified resin particles (mass ratio of seed particles to polystyrene: 45/55). In Examples 9 and 10, the residual monomer amount of the modified resin particles was measured.

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Abstract

L'invention concerne des particules de résine à base de polyoléfine, modifiées au styrène, contenant une résine à base de polyoléfine et une résine à base de polystyrène, la résine à base de polystyrène étant contenue en une quantité de 100-300 parties en masse par rapport à 100 parties en masse de la résine à base de polyoléfine, la résine à base de polyoléfine contenant une résine présentant un point de fusion de 124-145 °C et la résine à base de polystyrène contenant 10-35 % en masse d'un constituant de résine dérivé à partir d'α-méthylstyrène.
PCT/JP2016/073453 2015-09-29 2016-08-09 Particules de résine à base de polyoléfine, modifiées au styrène, procédé pour leur production, particules expansibles, particules expansées et corps moulé en mousse WO2017056743A1 (fr)

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WO2008117504A1 (fr) * 2007-03-27 2008-10-02 Sekisui Plastics Co., Ltd. Particules de résine de polystyrène modifiée à teneur en carbone, particules expansibles de résine de polystyrène modifiée à teneur en carbone, particules expansées de résine de polystyrène modifiée à teneur en carbone, mousse moulée de résine de polystyrène mod
JP2008239793A (ja) * 2007-03-27 2008-10-09 Sekisui Plastics Co Ltd 改質ポリスチレン系樹脂粒子、発泡性改質ポリスチレン系樹脂粒子、改質ポリスチレン系樹脂発泡粒子、改質ポリスチレン系樹脂発泡成形体およびこれらの製造方法
JP2009138146A (ja) * 2007-12-07 2009-06-25 Sekisui Plastics Co Ltd 発泡性樹脂粒子及びこの製造方法並びに発泡成形体
JP2010222546A (ja) * 2009-03-25 2010-10-07 Sekisui Plastics Co Ltd カーボン含有改質ポリスチレン系樹脂発泡粒子とその製造方法、カーボン含有改質ポリスチレン系樹脂発泡成形体とその製造方法
JP2011202110A (ja) * 2010-03-26 2011-10-13 Sekisui Plastics Co Ltd 発泡性熱可塑性樹脂粒子の予備発泡方法、予備発泡粒子および発泡成形体
JP2011202108A (ja) * 2010-03-26 2011-10-13 Sekisui Plastics Co Ltd 難燃剤含有複合樹脂粒子、予備発泡粒子、発泡成形体及びそれらの製造方法
JP2011219711A (ja) * 2010-03-26 2011-11-04 Sekisui Plastics Co Ltd 発泡性ポリスチレン系樹脂粒子、その製造方法、予備発泡粒子及び発泡成形体
JP2011208066A (ja) * 2010-03-30 2011-10-20 Sekisui Plastics Co Ltd 発泡成形体、車両用内装材、車両用タイヤスペーサおよび車両用ラゲージボックス
JP2011246644A (ja) * 2010-05-28 2011-12-08 Sekisui Plastics Co Ltd 自動車内装材及びその製造方法
JP2012077149A (ja) * 2010-09-30 2012-04-19 Sekisui Plastics Co Ltd 発泡性樹脂粒子、その製造方法、予備発泡粒子及び発泡成形体
WO2014157647A1 (fr) * 2013-03-29 2014-10-02 積水化成品工業株式会社 Particules de résine composites et particules de résine composites expansibles, particules de résine pré-expansées, et corps en mousse moulé les utilisant

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